JP6897936B6 - Photoreactive liquid crystal composition, display element, optical element, manufacturing method of display element, manufacturing method of optical element - Google Patents

Description

The present invention relates to a photoreactive liquid crystal composition, a display element and an optical element formed by having the photoreactive liquid crystal composition, and a method for manufacturing the display element and the optical element.

The current liquid crystal display element uses a liquid crystal alignment film that has been subjected to an alignment treatment in order to uniformly align the liquid crystal, except for some elements such as polymer dispersed liquid crystal (PDLC) (Polymer Dispersed Liquid Crystal, PDLC). Non-Patent Document 1). The alignment treatment of the liquid crystal alignment film is generally called a rubbing treatment after applying the liquid crystal alignment film, and the film surface is rubbed with a roller wrapped with a cloth. Since it is a method of rubbing the liquid crystal, there is a problem that scratches and scraps due to rubbing deteriorate the display performance of the liquid crystal display element. Further, this alignment treatment requires a number of steps such as a liquid crystal alignment film forming step, a liquid crystal alignment treatment step, and a liquid crystal alignment film cleaning step, which complicates the manufacturing process.
Therefore, if a liquid crystal cell in which the orientation of the liquid crystal can be controlled can be produced without using the liquid crystal alignment film, there is a great merit in terms of process and cost.

Patent Document 1 discloses a photoreactive liquid crystal composition that can actually provide an optical element and a display element without using a liquid crystal alignment film. The photoreactive liquid crystal composition disclosed in Patent Document 1 is a photoreactive side chain that causes at least one reaction selected from the group consisting of (A) (A-1) photocrosslinking and (A-2) photoisomerization. It has a photoreactive polymer liquid crystal having the same; and (B) a low molecular weight liquid crystal. By injecting the composition into a cell and irradiating it with polarized ultraviolet rays, (A) a photoreactive polymer liquid crystal and (B) a small molecule liquid crystal exhibit orientation, and an optical element and / or a display element is provided. Can be done.

However, in the photoreactive liquid crystal composition disclosed in Patent Document 1, there are cases where the uniform mixing property of (A) the photoreactive polymer liquid crystal and (B) the small molecule liquid crystal is not good. In particular, when the amount of (A) the photoreactive polymer liquid crystal is increased, (B) the uniform mixing property with the low molecular weight liquid crystal is lowered, and the photoreactive liquid crystal composition itself cannot be produced. Alternatively, there arises a problem that the display element cannot be provided.

WO2015 / 114864A1.

Therefore, an object of the present invention is to provide an element obtained by controlling the orientation of a liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, specifically, a display element and an optical element, and / or the present invention. An object of the present invention is to provide a photoreactive liquid crystal composition for producing an element.
In particular, an object of the present invention is to provide a photoreactive liquid crystal composition using a compound (B) having a high uniform mixing property with a low molecular weight liquid crystal used in the photoreactive liquid crystal composition, and in addition, the present invention. An object of the present invention is to provide an element obtained by controlling the orientation of a liquid crystal in a liquid crystal bulk, specifically, a display element and an optical element, without using a liquid crystal alignment film.
In particular, in addition to or other than the above object, an object of the present invention is a photoreactive liquid crystal composition using (B) a compound having a high uniform mixing property with a low molecular weight liquid crystal used in a photoreactive liquid crystal composition. It is an object of the present invention to provide a method for manufacturing an element obtained by controlling the orientation of a liquid crystal in a liquid crystal bulk, specifically, a display element and an optical element, without using a liquid crystal alignment film.

The present inventors have found the following inventions.
<1> (A) A photoreactive compound having a siloxane skeleton and a photoreactive group; and (B) a small molecule liquid crystal;
Photoreactive liquid crystal composition having.

INDUSTRIAL APPLICABILITY The present invention provides an element obtained by controlling the orientation of a liquid crystal in a liquid crystal bulk, specifically a display element and an optical element, without using a liquid crystal alignment film, and / or manufactures the element. A photoreactive liquid crystal composition for this purpose can be provided.
In particular, according to the present invention, it is possible to provide a photoreactive liquid crystal composition using a compound (B) having a high uniform mixing property with a small molecule liquid crystal used for the photoreactive liquid crystal composition. Further, the composition can provide an element obtained by controlling the orientation of a liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, specifically, a display element and an optical element.
In particular, according to the present invention, in addition to or in addition to the above effects, a photoreactive liquid crystal composition using (B) a compound having a high uniform mixing property with a low molecular weight liquid crystal used in the photoreactive liquid crystal composition. It is possible to provide a method for manufacturing an element obtained by controlling the orientation of a liquid crystal in a liquid crystal bulk, specifically, a display element and an optical element, without using a liquid crystal alignment film.

It is a figure which shows the polarization microscope image of the orientation state of the small molecule liquid crystal at room temperature about the liquid crystal cell A2 obtained in Example 1. FIG. It is a figure which shows the polarization microscope image of the orientation state of the small molecule liquid crystal at room temperature about the liquid crystal cell A4 obtained in the comparative example 3. FIG.

The present application is an element obtained by controlling the orientation of a liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film, specifically, a display element and an optical element, and / or photoreactivity for producing the element. A liquid crystal composition is provided. In particular, the present application provides a photoreactive liquid crystal composition using a compound (B) having a high uniform mixing property with a small molecule liquid crystal used for the photoreactive liquid crystal composition.
Further, the present application provides a method for manufacturing an element obtained by controlling the orientation of a liquid crystal in a liquid crystal bulk without using a liquid crystal alignment film. In particular, the present application provides a method for producing the above-mentioned element by using (B) a photoreactive liquid crystal composition using a compound having a high uniform mixing property with a small molecule liquid crystal used for the photoreactive liquid crystal composition.
Hereinafter, a photoreactive liquid crystal composition, an element obtained by the composition, and a method for manufacturing the element will be described.

<Photoreactive liquid crystal composition>
The photoreactive liquid crystal composition of the present invention has (A) a photoreactive compound having a siloxane skeleton and having a photoreactive group; and (B) a low molecular weight liquid crystal.
The photoreactive liquid crystal composition of the present invention contains only (A) a photoreactive compound; and (B) a small molecule liquid crystal; and other components such that the properties of (A) and (B) do not change. It may be essentially composed of only (A) and (B) having components. Moreover, the photoreactive liquid crystal composition of the present invention may have other components other than (A) or (B).

<< (B) Small molecule liquid crystal >>
As the small molecule liquid crystal (B) contained in the photoreactive liquid crystal composition of the present invention, a nematic liquid crystal or a ferroelectric liquid crystal conventionally used for a liquid crystal display element or the like can be used as it is.
Specifically, as (B) low molecular weight liquid crystal, cyanobiphenyls such as 4-cyano-4'-n-pentylbiphenyl and 4-cyano-4'-n-heptyloxybiphenyl; cholesteryl acetate, cholesteryl benzoate and the like. Cholesteryl esters; carbonate esters such as 4-carboxyphenyl ethyl carbonate, 4-carboxyphenyl-n-butyl carbonate; phenyl esters such as benzoic acid phenyl ester and phthalic acid biphenyl ester; benzylidene-2-naphthylamine, Schiff bases such as 4'-n-butoxybendylidene-4-acetylaniline; benzidines such as N, N'-bisbenzidene benzidine, p-dianis albendidin; 4,4'-azoxidianisol, 4, Azoxybenzenes such as 4'-di-n-butoxyazoxybenzene; liquid crystals of phenylcyclohexyl, turphenyl, phenylbicyclohexyl, etc. specifically shown below; and the like; Not done.

<< (A) Photoreactive compound >>
The (A) photoreactive compound used in the present invention (hereinafter, the (A) photoreactive compound may be simply abbreviated as “component (A)”) has a siloxane skeleton and has a photoreactive group.
As used herein, the term "photoreactive" refers to any one of (A-1) photocrosslinking, (A-2) photoisomerization, (A-3) photodegradation, and (A-4) phototransition. A property that produces a reaction; and any combination of these reactions;
The photoreactive group is at least one reaction selected from the group consisting of (A-1) photobridge, (A-2) photoisomerization, (A-3) photodegradation, and (A-4) phototransition. It is preferable to generate at least one reaction selected from the group consisting of (A-1) photocrosslinking and (A-2) photoisomerization, and more preferably (A-1). It is good to cause a photobridge reaction.
Examples of the photoreactive group include, but are not limited to, the following structures and derivatives thereof.

The component (A) is preferably a compound that i) exhibits liquid crystallinity in a predetermined temperature range and has a photoreactive group.
The component (A) preferably reacts with light in the wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in the temperature range of 50 to 300 ° C.
The component (A) preferably has a photoreactive group that reacts with light in the wavelength range of iii) 250 nm to 400 nm, particularly polarized ultraviolet rays.
The photoreactive group of the component (A) preferably has a mesogen group because it exhibits liquid crystallinity in the temperature range of iv) 50 to 300 ° C.

The component (A) is preferably at least one selected from the group consisting of the following formulas (A) -1 to (A) -4.
In the formulas (A) -1 to (A) -4, R ^{101 to} R ¹⁰⁸ each independently represent a monovalent organic group. ^{However, R 103 to} R ¹⁰⁵ of the following formula (A) -1 are defined depending on the value of m4. Details will be described later.
Here, the monovalent organic group is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms in a linear or branched chain, an alkoxy group having 1 to 6 carbon atoms in a linear or branched chain, substituted or unsubstituted. A group consisting of a phenyl group, a vinyl group, a mercapto group, a (meth) acrylic group, and a combination thereof (a hydrogen atom bonded to a carbon atom may be substituted with a halogen atom or a hydroxyl group, or not adjacent to each other. The carbon atom may be substituted with -O-, -CO-O-, -O-CO-, -NH-CO-O-, -O-CO-NH-, -NH-CO-NH-). It should be a group selected from.
Q ₁ to Q _4, and _{Q 8} each independently represent a photoreactive group.
Q is ₅ to Q ₇ are each independently, even photoreactive ^group, may be a monovalent organic group in the same manner as R 101 ^{to R 108.} When Q _{5 to} Q ₇ are independently monovalent organic groups, the groups have the same definition as ^{R 101 to} R ^108.
P ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms (the hydrogen atom bonded to the carbon atom may be substituted with a monovalent organic group, and the alkylene groups are not adjacent to each other. The carbon atom may be substituted with -O-, -CO-O-, -O-CO-, -NH-CO-O-, -O-CO-NH-, -NH-CO-NH-. Preferably, P ¹ is a linear alkylene group having 1 to 10 carbon atoms.
n11, n12, and n14 each independently represent an integer of 1 to 20, preferably 1 to 10, more preferably 1 to 4, and n13 is 3 to 20, preferably 3 to 10, more preferably 3 to 5. Represents an integer of.
m4 represents an integer of 1 to 4. ^{As described above, R 103 to} R ¹⁰⁵ of the following formula (A) -1 depend on the value of m4. When m4 = 1, R ^{103 to} R ¹⁰⁵ represent the above-mentioned monovalent organic group. When m4 = 2, it is preferable ^{that any two of R 103 to} R ¹⁰⁵ are the above-mentioned monovalent organic groups, and the remaining one is the group shown in parentheses of m4. Further, when m4 = 3, it is preferable ^{that any one of R 103 to} R ¹⁰⁵ is the above-mentioned monovalent organic group, and the remaining two are the groups shown in parentheses of m4. Further, when m4 = 4, it is preferable that ^{all of R 103 to} R ¹⁰⁵ are the groups shown in parentheses of m4.

In the photoreactive liquid crystal composition of the present invention, the weight ratio of (A) photoreactive compound to (B) low molecular weight liquid crystal ((A) photoreactive compound: (B) low molecular weight liquid crystal) is 0.2. : 99.8 to 20:80, preferably 1:99 to 15:85, more preferably 2:98 to 10:90.

As described above, the component (A) has a photoreactive group having photoreactivity. The structure of the group is not particularly limited, but it is preferable to cause one or more reactions of any one or more of the above (A-1) to (A-4), preferably the above (A-1) and / Or the reaction shown in (A-2) is preferable, and more preferably, the photocrosslinking reaction (A-1) is to occur. The structure that causes the (A-1) photocrosslinking reaction is preferable because the structure after the reaction can stably maintain the orientation of the component (A) for a long period of time even when exposed to external stress such as heat.
As for the structure of the photoreactive group of the component (A), it is preferable to have a rigid mesogen component because the orientation of the liquid crystal is stable. It is preferable that the component (A) has a rigid mesogen component and exhibits liquid crystallinity because the compatibility of the component (B) with the small molecule liquid crystal is improved.

Examples of the mesogen component include, but are not limited to, a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, and an azobenzene group.
The following structure is preferable as the mesogen group.

The photoreactive group of the component (A) is preferably a group consisting of at least one of the following formulas (1) to (6).

In the formula, A, B, and D are independently single-bonded, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-. Represents O- or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 carbon atoms). (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. The hydrogen atoms bonded to are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y _1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH-represents and the number of Xs is 2, the Xs may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-. It may be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. It is a group; however, when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring. When the number of Ps is 2 or more, the Ps may be the same or different, and when the number of Qs is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
When both l1 and l2 are 0, A also represents a single bond when T is a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are groups independently selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof.

The photoreactive group is preferably any one selected from the group consisting of the following formulas (7) to (10).
In the formula, A, B, D, Y ₁ , X, Y ₂ , and R have the same definition as above;
l represents an integer from 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer from 0 to 12 (where B is a single bond when n = 0).

The photoreactive group is preferably any one selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m, m1 and R have the same definitions as above.

The photoreactive group is preferably a group represented by the following formula (14) or (15).
In the formula, A, Y ₁ , l, m1 and m2 have the same definitions as above.

The photoreactive group is preferably a group represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definitions as above.

The photoreactive group is preferably a group represented by the following formula (20).
In the formula, A, Y ₁ , X, l and m have the same definitions as above.

<< Example of component (A) >>
Specific examples of the component (A) include, but are not limited to, the following compounds.

As described above, the photoreactive liquid crystal composition of the present invention may contain other components in addition to the component (A) or the component (B).
As other components, depending on the use of the components (A) and (B) to be used, for example, antioxidants such as hindered amines and hindered phenols, and photopolymerization or light at one or more terminals. Examples thereof include polymerizable compounds having a group to be crosslinked.
As a specific example of the polymerizable compound, the compound shown below (in the formula, V is _{represented by a single bond or -R 8} O-, preferably -R ₈ O-, and R ₈ has 1 to 10 carbon atoms, .W preferably of a straight chain or branched chain alkylene group having 2 to 6 carbon atoms, a single bond or a -OR ₉ -, preferably -OR ₉ - is represented by, _{R 9} is from 1 to 10 carbon atoms, preferably Indicates a linear or branched alkylene group having 2 to 6 carbon atoms. V and W may have the same structure or different, but if they are the same, synthesis is easy. R ₇ is H or carbon number. (Indicating 1 to 4 alkyl groups), but is not limited thereto.

<Elements obtained from photoreactive liquid crystal compositions and methods for manufacturing them>
The present application also provides an element obtained by the above-mentioned photoreactive liquid crystal composition, and a method for producing the element.
The device of the present invention is formed by having a liquid crystal cell having the above-mentioned photoreactive liquid crystal composition.
Examples of the element include a display element; and an optical element such as a diffraction grating, a lens, and a mirror;

The element of the present invention, specifically, a display element or an optical element can be formed by filling a cell with the above-mentioned photoreactive liquid crystal composition.
Specifically, the device of the present invention can be manufactured by the following steps.
[I] Two transparent substrates in which a photoreactive liquid crystal composition having (A) a photoreactive compound having a siloxane group and a photoreactive group; and (B) a low molecular weight liquid crystal; is arranged in parallel. The step of filling the space formed between them to form a liquid crystal cell; and [II] The liquid crystal cell obtained in [I] is irradiated with polarized ultraviolet rays from either of the two transparent substrates. Process;
By having
The element of the present invention can be formed, and specifically, an element in which the (B) small molecule liquid crystal has a predetermined orientation is formed in the liquid crystal cell.

The step [I] is a step of forming a liquid crystal cell by filling the space in which the above-mentioned photoreactive liquid crystal composition is formed in a space where at least the substrates on the side to be irradiated with ultraviolet rays, which are arranged in parallel, are formed between transparent substrates. be.
The liquid crystal cell is formed by forming a space by arranging two transparent substrates in parallel with each other separated to some extent, and filling the space with the above-mentioned photoreactive composition.
As the substrate, for example, glass; plastic such as acrylic or polycarbonate; or the like can be used. The substrate may be flexible, depending on the element being formed.

The substrate forms a film formed of various films such as polyvinyl alcohol, polyether, polyethylene, PET, polyamide, polyimide, acrylic, polycarbonate, polyurea, etc. on the space side depending on the element to be formed. May be good. The film used here may have the following effects, for example. That is, in the step [II] described later, in order to induce the photoreaction of the (A) photoreactive compound, the molecular length axis of the (A) photoreactive compound absorbs polarized light in the surface of the substrate. It should be located horizontally. On the other hand, since the (A) photoreactive compound is encapsulated in the liquid crystal cell as a composition with the (B) low molecular weight liquid crystal, the molecular major axis of the (A) photoreactive compound is horizontally located in the substrate surface. Therefore, (B) the low-molecular-weight liquid crystal should also be positioned horizontally in the substrate surface. Therefore, the above-mentioned film is preferably one in which the molecular major axis of the photoreactive composition can be positioned horizontally in the surface of the substrate, and such a film is not limited to the material.

The step [II] is a step of irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet rays. Since polarized ultraviolet rays are emitted from the outside of either of the two transparent substrates, the transparent substrate is a substrate that transmits polarized ultraviolet rays as described above.
The polarized ultraviolet light depends on the element to be formed, but ultraviolet light having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film used. Then, for example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.
In the process of irradiating polarized ultraviolet rays, the polarized ultraviolet rays are 15 ° C. higher than the isotropic phase transition temperature of the (B) low molecular weight liquid crystal in order to suppress the decrease in the degree of polarization of the irradiated polarized ultraviolet rays and the scattering of the polarized ultraviolet rays. It is better to irradiate at a lower temperature or higher, and more preferably at a temperature higher than the isotropic phase transition temperature. Within this temperature range, (A) the dichroism due to the polarized photoreaction of the photoreactive compound is maintained, and (B) the orientation of the small molecule liquid crystal becomes uniform, which is preferable.

By irradiating the first position of the optical element and the second position different from the first position with different polarized ultraviolet rays, the (B) small molecule liquid crystal is formed at the first position and the second position. Can form elements having different orientations, such as optical elements.
Specifically, the first position is irradiated with polarized ultraviolet rays having a first polarization axis, and the second position is irradiated with polarized ultraviolet rays having a second polarization axis different from the first polarization axis. By irradiating, it is possible to form an element in which the (B) small molecule liquid crystal has different orientations at the first and second positions of the optical element.
Further, for example, when the element to be formed is a diffraction grating, the orientation distribution in which the orientation is different at the position of the element by coherently exposing the liquid crystal cell with polarized ultraviolet rays, specifically, the orientation in which the orientation is different periodically. A diffraction grating that is an optical element having a sex distribution can be formed.

When irradiated with polarized ultraviolet rays, it is considered that the following mechanism occurs in the liquid crystal cell. That is, the photoreactive compound (A) in the liquid crystal cell has an orientation corresponding to the polarized ultraviolet rays.
Further, the (B) small molecule liquid crystal is oriented according to the orientation of the (A) photoreactive compound.
As a result, (A) the photoreactive compound and (B) the small molecule liquid crystal have orientation depending on the polarized ultraviolet rays.
For example, as described above, by coherently exposing the liquid crystal cell with polarized ultraviolet light, the (A) photoreactive compound has different orientations at the position of the element, and accordingly, (B) the small molecule liquid crystal. Also, it will have different orientation depending on the position of the element. Therefore, by coherently exposing the liquid crystal cell with polarized ultraviolet rays, a diffraction grating is formed, which is an optical element having an orientation distribution having different orientations at the positions of the elements, specifically, an orientation distribution having different orientations periodically. can do.

<Synthesis Example 1: Synthesis of photoreactive compound Si-1>

<< Synthesis of Compound C >>
Compound [B] (90.8 g, 412 mmol), triphenylphosphine (hereinafter referred to as PPh ₃ ) (130.0 g, 495 mmol), and tetrahydrofuran (hereinafter referred to as THF) (700 g) are placed in a 2 L four-necked flask. In addition, nitrogen substitution was performed to cool the solution to 0 ° C. Then, a solution of diisopropyl azodicarboxylate (hereinafter referred to as DIAD) (49.5 g, 996 mol) in THF (100 g) was gradually added, and then a solution of compound [A] (49.5 g, 996 mol) in THF (100 g). Was further added, and then the reaction was further carried out at 23 ° C. The reaction was followed up by HPLC, and after confirming the completion of the reaction, the reaction solution was washed with ethyl acetate / brine, and the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off by filtration and an evaporator to obtain an oily crude product. Hexane (1 L) was added to the obtained crude product, cooled and stirred at −20 ° C., the crystallized solid was removed by filtration, and the filtrate was purified by silica gel column chromatography to obtain the compound [C] as a yellow solid. Was obtained (110.3 g) (yield 98%).
^{1 1} H-NMR (400MHz, CDCl ₃ , δppm): 7.54 (1H, d), 7.44 (2H, d), 6.87 (2H, d), 5.86-5.78 (1H, m), 5.87-5.78 (1H, m) ), 5.10-4.97 (2H, m), 3.99 (2H, t), 2.22-2.09 (2H, m), 1.84-1.76 (2H, m), 1.61-1.52 (2H, m), 1.43 (9H, s) ).

<< Synthesis of Compound E >>
Compound [D] (29.43 g, 198 mmol), compound [C] (30.00 g, 99.2 mmol), Karstedt catalyst (1 mmol), and toluene (160 g) were added to a 300 mL four-necked flask, and after nitrogen substitution, Heat reflux was performed. The reaction was followed by HPLC, and after completion of the reaction, the reaction solution was concentrated by an evaporator and purified by silica gel column chromatography to obtain 29.4 g of an oily compound [E] (yield 66%).
^{1 1} H-NMR (400MHz, CDCl ₃ , δppm): 7.50 (1H, d), 7.41 (2H, d), 6.84 (2H, d), 6.19 (1H, d), 3.94 (2H, t), 1.83- 1.71 (2H, m), 1.42 (9H, s), 1.40-1.17 (4H, m), 0.54-0.42 (2H, m), 0.07-0.03 (15H, m).

<< Synthesis of photoreactive compound Si-1 >>
Compound [E] (29.48 g, 65.4 mmol) and formic acid (120 g) were added to a 300 mL four-necked flask, and the mixture was heated and stirred at 40 ° C. The reaction was followed by HPLC, and after completion of the reaction, the reaction solution was poured into distilled water (800 g) and separated by hexane / ethyl acetate. The organic layer was washed 3 times with distilled water, the organic layer was concentrated with an evaporator, and then purified by silica gel column chromatography to obtain 10.5 g of a white solid photoreactive compound Si-1 (yield 41%).
^{1 1} H-NMR (400MHz, CDCl ₃ , δppm): 7.74 (1H, d), 7.49 (2H, d), 6.90 (2H, d), 6.31 (1H, d), 4.12 (2H, t), 1.83- 1.74 (2H, m), 1.48-1.31 (6H, m), 0.54-0.50 (2H, m), 0.07-0.03 (15H, m).

<Synthesis Example 2: Synthesis of Photoreactive Compound Si-2>

17.2 g of photoreactive compound Si-2 was obtained using the same method as in Synthesis Example 1 except that compound [D] was changed to compound [F] (yield 56%).
^{1 1} H-NMR (400MHz, CDCl ₃ , δppm): 7.74 (1H, d), 7.49 (2H, d), 6.89 (2H, d), 6.31 (1H, d), 4.00-3.95 (2H, m), 1.81-1.74 (2H, m), 1.46-1.33 (6H, m), 0.54-0.50 (2H, m), 0.16-0.03 (21H, m).

<Synthesis Example 3: Synthesis of Photoreactive Compound Si-3>

13.5 g of photoreactive compound Si-3 was obtained using the same method as in Synthesis Example 1 except that compound [D] was changed to compound [H] (yield 89%).
^{1 1} H-NMR (400MHz, CDCl ₃ , δppm): 7.73 (1H, d), 7.48 (2H, d), 6.82 (2H, d), 6.31 (1H, d), 3.97-3.91 (2H, m), 1.79-1.74 (2H, m), 1.43-1.33 (6H, m), 0.54-0.50 (2H, m), 0.16-0.03 (21H, m).

<Synthesis Example 4: Synthesis of Photoreactive Compound Si-4>

<< Synthesis of Compound K >>
Compound [J] (84.0 g, 451 mmol), triphenylphosphine (hereinafter referred to as PPh ₃ ) (130.0 g, 495 mmol), and THF (700 g) were added to a 2 L four-necked flask, and the solution was replaced with nitrogen. Was cooled to 0 ° C. Then, a solution of DIAD (49.5 g, 496 mol) in THF (100 g) was gradually added, and then a solution of compound [A] (49.5 g, 996 mol) in THF (100 g) was further added, and then further added at 23 ° C. The reaction was carried out. The reaction was followed up by HPLC, and after confirming the completion of the reaction, the reaction solution was washed with ethyl acetate / brine, and the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off by filtration and an evaporator to obtain a crude product of compound [K]. The obtained crude product was purified by silica gel column chromatography to obtain 56.7 g of compound [K] (yield 47%).
^{1 1} H-NMR (400MHz, CDCl ₃ , δppm): 9.70 (1H, s), 7.64-7.62 (2H, m), 7.44-7.41 (2H, m), 7.01-6.98 (2H, m), 6.85-6.82 (2H, m), 5.88-5.79 (1H, m), 5.10-4.97 (2H, m), 3.99 (2H, t), 2.22-2.09 (2H, m), 1.84-1.76 (2H, m), 1.61 -1.52 (2H, m).

<< Synthesis of Compound M >>

Compound [K] (10.00 g, 37.3 mmol), compound [L] (6.65 g, 37.3 mmol), 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride in a 300 mL four-necked flask. Add salt (hereinafter referred to as EDC) (6.95 g, 44.8 mmol), N, N'-dimethylaminopyridine (hereinafter referred to as DMAP) (0.46, 3.73 mmol), and THF (150 g) 23. The reaction was carried out at ° C. The reaction was followed up by HPLC, and after confirming the completion of the reaction, the reaction solution was washed with ethyl acetate / distilled water, and the aqueous layer was removed by a liquid separation operation. The organic layer was further washed twice with distilled water, and then the organic layer was dried over magnesium sulfate. Then, the solvent was distilled off by filtration and an evaporator to obtain a crude product of compound [M]. The obtained crude product was purified by silica gel column chromatography to obtain 15.2 g of compound [M] (yield 95%).
^{1 1} H-NMR (400MHz, CDCl ₃ , δppm): 7.83 (1H, d), 7.68-7.67 (2H, m), 7.58-7.56 (2H, m), 7.55-7.48 (2H, m), 7.23-7.19 (2H, m), 7.06-7.05 (2H, m), 6.89-6.93 (2H, m), 6.30 (1H, d), 5.87-5.80 (1H, m), 5.11-4.99 (2H, m), 3.98 (2H, t), 3,85 (3H, s), 2.23-2.10 (2H, m), 1.83-1.77 (2H, m), 1.62-1.52 (2H, m).

<< Synthesis of photoreactive compound Si-4 >>

Compound [D] (0.8 g, 5.2 mmol), compound [M] (1.5 g, 3.5 mmol), nitrogen catalyst (0.1 mmol), and toluene (80 g) were added to a 300 mL four-necked flask. After the nitrogen substitution, the mixture was stirred at room temperature for 22 hours. The reaction was followed by HPLC, and after completion of the reaction, the reaction solution was concentrated by an evaporator and purified by silica gel column chromatography to obtain 0.6 g of a photoreactive compound [Si-4] (yield 38%). ..
¹ H-NMR (400MHz, CDCl ₃ , δppm): 7.85 (1H, d), 7.68-7.67 (2H, m), 7.47-7.55 (4H, m), 7.2 (2H, d), 6.92-6.96 (4H) , m), 6.48-6.52 (1H, d), 4.00 (2H, t), 3,85 (3H, s), 1.35-1.80 (8H, m), 0.51-0.53 (2H, t), 0.02-0.05 (15H, m).

<Synthesis Example 5: Synthesis of Photoreactive Compound Si-5>

The photoreactive compound Si was used in the same manner as in Synthesis Example 4 except that the compound [F] was changed to the compound [N] and the charging ratio of the compound [M] was doubled with respect to the compound [N]. 0.2 g of -5 was obtained (yield 11%).
^{1 1} H-NMR (400MHz, CDCl ₃ , δppm): 7.85 (2H, d), 7.68-7.67 (4H, m), 7.58-7.56 (4H, m), 7.55-7.48 (4H, m), 7.23-7.19 (4H, m), 7.06-7.05 (4H, m), 6.89-6.93 (4H, m), 6.50 (2H, d), 4.02-3.97 (4H, m), 3.85 (3H, s), 1.81-1.74 (4H, m), 1.46-1.33 (12H, m), 0.51-0.53 (4H, m), 0.02-0.05 (12H, m).

<Synthesis Example 6: Synthesis of Photoreactive Compound Si-6>

11.4 g of photoreactive compound Si-5 was obtained using the same method as in Synthesis Example 4 except that compound [F] was changed to compound [H] (yield 82%).
^{1 1} H-NMR (400MHz, CDCl ₃ , δppm): 7.82 (1H, d), 7.67-7.68 (2H, m), 7.60-7.58 (2H, m), 7.54-7.49 (2H, m), 7.24-7.18 (2H, m), 7.05-7.05 (2H, m), 6.89-6.93 (2H, m), 6.30 (1H, d), 4.02-3.97 (2H, m), 3,85 (3H, s), 1.82 -1.73 (2H, m), 1.44-1.31 (6H, m), 0.54-0.50 (2H, m), 0.17-0.04 (21H, m).

(Example 1)
After adding 5 parts by weight of the photoreactive compound represented by Si-4 synthesized in Synthesis Example 4 to 95 parts by weight of the small molecule liquid crystal ZLI-4792 (manufactured by Merck Co., Ltd.), the mixture is stirred at room temperature for 30 minutes and subjected to light. A reactive liquid crystal composition A1 was obtained. After stirring, it was confirmed that the photoreactive liquid crystal composition was uniformly mixed without any precipitation of Si-4 with respect to ZLI-4792 (Table 2). The photoreactive polymer liquid crystal represented by Si-4 exhibited liquid crystallinity at 118 ° C. or higher. The results are shown in Table 1. In Table 1, "C" is a crystalline phase (crystal state before becoming a liquid crystal), "N" is a nematic phase (a type of liquid crystal phase), and "I" is an isotropic phase. Indicates that there is. The numerical values between "C" and "N" indicate the temperature at which the crystal phase changes to the nematic phase, and the numerical values between "N" and "I" indicate the transition from the nematic phase to the isotropic phase. Indicates the temperature. More specifically, the thermal properties of "Si-4" in Table 1 indicate that the transition from the crystalline phase to the nematic phase at 118 ° C. and the transition from the nematic phase to the isotropic phase at 198 ° C.
Separately, two glass substrates having ITO on both sides of the substrate were laminated so that the ITO faced each other to obtain an empty cell of a parallel flat plate having a gap of 10 μm. After injecting the photoreactive liquid crystal composition into this empty cell by the capillary method, the photoreactive liquid crystal composition is heated to 110 ° C., which is equal to or higher than the isotropic phase temperature, and linearly polarized using a high-pressure mercury lamp. A liquid crystal cell A2 subjected to an orientation treatment was obtained by irradiating with ultraviolet rays. The wavelength of the linearly polarized ultraviolet rays used for the alignment treatment was 315 nm (50 mW / cm ² ), and the exposure amount was 500 mJ / cm ² .

<Orientation state of photoreactive liquid crystal composition>
After preparing A2, the orientation state of the small molecule liquid crystal at room temperature was confirmed by observing with a polarizing microscope. The results are shown in FIG. 1 and Table 3. The following can be seen from the results of FIG. That is, when the optical axis of the liquid crystal cell is tilted 45 degrees with respect to the polarizer and the analyzer, it becomes a bright state, and when it is arranged at 0 degrees or 90 degrees with respect to either the polarizer and the analyzer, it becomes dark. From the state, it can be seen that the low molecular weight liquid crystal in the liquid crystal cell is uniaxially oriented.

(Example 2)
The photoreactive liquid crystal composition B1 was obtained in the same manner as in Example 1 except that the amount of Si-4 added to the photoreactive liquid crystal composition was changed to 2 parts by weight and the amount of small molecule liquid crystal was changed to 98 parts by weight. rice field.
It was confirmed that the photoreactive liquid crystal composition B1 was uniformly mixed without any precipitation of Si-4 with respect to ZLI-4792. The results are shown in Table 2.
Next, after preparing the liquid crystal cell B2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1, the orientation state of the small molecule liquid crystal at room temperature was confirmed by observation with a polarizing microscope. The results are shown in Table 3. In Table 3, "good" means "uniform orientation", and "alignable" means "alignment of the liquid crystal can be induced, but some orientation defects such as defects are seen. And the orientation is not uniform. "

(Example 3)
A photoreactive liquid crystal composition C1 was obtained in the same manner as in Example 1 except that Si-4 added to the photoreactive liquid crystal composition was changed to Si-5.
It was confirmed that the photoreactive liquid crystal composition C1 was uniformly mixed without any precipitation of Si-5 with respect to ZLI-4792. The results are shown in Table 2.
Next, a liquid crystal cell C2 in which the photoreactive liquid crystal composition was encapsulated was prepared in the same manner as in Example 1 except that the exposure amount of the linearly polarized ultraviolet rays to be irradiated was 1000 mJ / cm ^{2, and then the liquid crystal cell C2 was observed by a polarizing microscope.} The orientation state of the low molecular weight liquid crystal at room temperature was confirmed. As a result, although not shown, it was confirmed that the small molecule liquid crystal in the liquid crystal cell was oriented uniaxially and the orientation uniformity was good (see Table 3), as in Example 1.

(Example 4)
A photoreactive liquid crystal composition D1 was obtained in the same manner as in Example 1 except that Si-4 added to the photoreactive liquid crystal composition was changed to Si-6. It was confirmed that the photoreactive liquid crystal composition D1 was uniformly mixed without any precipitation of Si-5 with respect to ZLI-4792. The results are shown in Table 2.
Next, after preparing the liquid crystal cell D2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 3, the orientation state of the small molecule liquid crystal at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the small molecule liquid crystal in the liquid crystal cell was oriented uniaxially and the orientation uniformity was good (see Table 3), as in Example 1.

(Example 5)
Small molecule liquid crystal used in Example 1: ZLI-4792 (manufactured by Merck & Co., Ltd.) was changed to E7 (manufactured by Merck & Co., Inc.), and a photoreactive liquid crystal composition E1 was obtained in the same manner as in Example 1.

It was confirmed that the photoreactive liquid crystal composition E1 was uniformly mixed without any precipitation of Si-4 with respect to E7. The results are shown in Table 2.
Next, after preparing the liquid crystal cell E2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1, the orientation state of the small molecule liquid crystal at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the small molecule liquid crystal in the liquid crystal cell was oriented uniaxially and the orientation uniformity was good (see Table 3), as in Example 1.

A photoreactive liquid crystal composition F1 was obtained in the same manner as in Example 1 except that Si-4 added to the photoreactive liquid crystal composition was changed to Si-1.
It was confirmed that the photoreactive liquid crystal composition F1 was uniformly mixed without any precipitation of Si-1 with respect to ZLI-4792. The results are shown in Table 2.
Next, after preparing the liquid crystal cell F2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1, the orientation state of the small molecule liquid crystal at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the small molecule liquid crystal in the liquid crystal cell was oriented uniaxially and the orientation uniformity was good (see Table 3), as in Example 1.

(Example 7)
The photoreactive liquid crystal composition G1 was obtained in the same manner as in Example 6 except that the amount of Si-1 added to the photoreactive liquid crystal composition was changed to 10 parts by weight.
It was confirmed that the photoreactive liquid crystal composition G1 was uniformly mixed without any precipitation of Si-4 with respect to ZLI-4792. The results are shown in Table 2.
Next, after preparing the liquid crystal cell G2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1, the orientation state of the small molecule liquid crystal at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the small molecule liquid crystal in the liquid crystal cell was oriented uniaxially and the orientation uniformity was good (see Table 3), as in Example 1.

(Example 8)
The photoreactive liquid crystal composition H1 was obtained in the same manner as in Example 1 except that Si-4 added to the photoreactive liquid crystal composition was Si-1 and the addition amount was changed to 1 part by weight.
It was confirmed that the photoreactive liquid crystal composition H1 was uniformly mixed without any precipitation of Si-1 with respect to ZLI-4792. The results are shown in Table 2.
Next, after preparing the liquid crystal cell H2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1, the orientation state of the small molecule liquid crystal at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the small molecule liquid crystal in the liquid crystal cell was oriented uniaxially and the orientation uniformity was good (see Table 3), as in Example 1.

(Example 9)
A photoreactive liquid crystal composition I1 was obtained in the same manner as in Example 7 except that Si-4 added to the photoreactive liquid crystal composition was changed to Si-2.
It was confirmed that the photoreactive liquid crystal composition I1 was uniformly mixed without any precipitation of Si-2 with respect to ZLI-4792. The results are shown in Table 2.
Next, after preparing the liquid crystal cell I2 in which the photoreactive liquid crystal composition was encapsulated in the same manner as in Example 1, the orientation state of the small molecule liquid crystal at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the small molecule liquid crystal in the liquid crystal cell was oriented uniaxially and the orientation uniformity was good (see Table 3), as in Example 1.

(Example 10)
A liquid crystal cell A3 in which the photoreactive liquid crystal composition A1 was encapsulated was prepared in the same manner as in Example 1 except that the exposure amount of the linearly polarized ultraviolet rays to be irradiated ^{was changed to 1000 mJ / cm 2, and then the liquid crystal cell A3 was observed by a polarizing microscope.} The orientation state of the low molecular weight liquid crystal at room temperature was confirmed. As a result, although not shown, it was confirmed that the small molecule liquid crystal in the liquid crystal cell was oriented uniaxially and the orientation uniformity was good (see Table 3), as in Example 1.

(Example 11)
In Example 4, the liquid crystal cell D3 in which the photoreactive liquid crystal composition D1 was encapsulated was prepared in the same manner as in Example 4, except that the exposure amount of the linearly polarized ultraviolet rays to be irradiated ^{was changed to 1500 mJ / cm 2.} By observing with a polarizing microscope, the orientation state of the low molecular weight liquid crystal at room temperature was confirmed. As a result, although not shown, it was confirmed that the small molecule liquid crystal in the liquid crystal cell was oriented uniaxially and the orientation uniformity was good (see Table 3), as in Example 1.

(Example 12)
In Example 4, the amount of Si-6 added to the photoreactive liquid crystal composition was changed to 10 parts by weight and the amount of small molecule liquid crystal was changed to 90 parts by weight. The composition J1 was obtained. It was confirmed that the photoreactive liquid crystal composition was uniformly mixed without any precipitation of Si-6 with respect to ZLI-4792. The results are shown in Table 2.
Next, after preparing the liquid crystal cell J2 in which the photoreactive liquid crystal composition was sealed in the same manner as in Example 4, the orientation state of the small molecule liquid crystal at room temperature was confirmed by observation with a polarizing microscope. As a result, although not shown, it was confirmed that the small molecule liquid crystal in the liquid crystal cell was oriented uniaxially and the orientation uniformity was good (see Table 3), as in Example 4.

(Comparative Example 1)
After adding 10 parts by weight of the photoreactive liquid crystal monomer represented by the following formula M6CB to 95 parts by weight of the small molecule liquid crystal ZLI-4792 (manufactured by Merck), the mixture is stirred at room temperature for 30 minutes, and the photoreactive liquid crystal composition K1 Got However, the photoreactive liquid crystal composition K1 had poor solubility in ZLI-4792 of the compound represented by the above formula M6CB, and could not be uniformly mixed. The results are shown in Table 2.
Since the composition could not be uniformly mixed, a liquid crystal cell could not be prepared.

(Comparative Example 2)
After adding 5 parts by weight of a photoreactive polymer liquid crystal represented by the following formula P6CB to 95 parts by weight of a small molecule liquid crystal ZLI-4792 (manufactured by Merck), the mixture is stirred at room temperature for 30 minutes to prepare a photoreactive liquid crystal composition. Obtained L1. However, the photoreactive liquid crystal composition L1 had poor solubility in ZLI-4792 of the polymer liquid crystal represented by the above formula P6CB, and could not be uniformly mixed. The results are shown in Table 2.
Since the composition could not be uniformly mixed, a liquid crystal cell could not be prepared.

(Comparative Example 3)
A liquid crystal cell A4 in which the photoreactive liquid crystal composition A1 was encapsulated was obtained by the same method as in Example 1 except that the temperature for irradiating the polarized ultraviolet rays was set to 45 degrees. Then, by observing with a polarizing microscope, the orientation state of the small molecule liquid crystal at room temperature was confirmed. The results are shown in FIG. 2 and Table 3.
The following can be seen from the results of FIG. That is, both when the optical axis of the liquid crystal cell is tilted 45 degrees with respect to the polarizer and the analyzer and when it is arranged at 0 or 90 degrees with respect to either the polarizer or the analyzer, the light and darkness Since was not confirmed, it can be seen that the small molecule liquid crystal in the liquid crystal cell is not oriented.

From Examples 1 to 12 and Comparative Examples 1 to 3, it can be seen that the photoreactive compounds disclosed in the present application have high solubility in small molecule liquid crystals, and it is easy to prepare a photoreactive liquid crystal composition.
Further, it was found that by irradiating the liquid crystal cell containing the photoreactive compound with linearly polarized ultraviolet rays, a liquid crystal cell in which the liquid crystal is uniformly oriented can be produced without using the liquid crystal alignment film.

Claims (14)

(A) Photoreactive compound having a siloxane skeleton and having a photoreactive group; and (B) Small molecule liquid crystal;
A photoreactive liquid crystal composition having,
The photoreactive groups are represented by the following formulas (1) to (6).
(In the formula, A, B, and D are independently single-bonded, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO. Represents -O- or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 carbon atoms). (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. The hydrogen atoms bonded to are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y _1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH-represents and the number of Xs is 2, the Xs may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-. It may be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. It is a group; however, when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring. When the number of Ps is 2 or more, the Ps may be the same or different, and when the number of Qs is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
When both l1 and l2 are 0, A also represents a single bond when T is a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are groups independently selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof. )
The above composition having any one selected from the group consisting of .

The photoreactive group is at least one selected from the group consisting of (A-1) photocrosslinking, (A-2) photoisomerization, (A-3) photodegradation, and (A-4) phototransition. The composition according to claim 1, which causes a reaction. The weight ratio of the (A) photoreactive compound to the (B) small molecule liquid crystal ((A) photoreactive compound: (B) small molecule liquid crystal) is 0.2: 99.8 to 20:80. The composition according to claim 1 or 2. The photoreactive compound (A) is represented by the following formulas (A) -1 to (A) -4.
(In the formula, R ^{101 to} R ¹⁰⁸ each independently represent a monovalent organic group;
Q ₁ to Q _4, and _{Q 8} each independently represents a photoreactive group;
Q ₅ to Q ₇ each independently represents or a monovalent organic group is a photoreactive group;
P ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms (the hydrogen atom bonded to the carbon atom may be substituted with a monovalent organic group, or adjacent to each other in the alkylene group. Absent carbon atoms may be substituted with -O-, -CO-O-, -O-CO-, -NH-CO-O-, -O-CO-NH-, -NH-CO-NH- ) Represents;
n11, n12, and n14 each independently represent an integer of 1 to 20;
n13 represents an integer from 3 to 20;
m4 represents an integer of 1 to 4. )
The composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of.

The photoreactive groups are represented by the following formulas (7) to (10).
(In the formula, A, B, and D are independently single-bonded, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO. Represents -O- or -O-CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 carbon atoms). (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH-represents and the number of Xs is 2, the Xs may be the same or different;
l represents an integer from 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer from 0 to 12 (where B is a single bond when n = 0);
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. The hydrogen atoms bonded to are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y ₁₎
The composition according to any one of claims 1 to 4 , which has any one selected from the group consisting of.

The photoreactive groups are represented by the following formulas (11) to (13).
(In the equation, A is a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, respectively. , Or -O-CO-CH = CH-;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH-represents and the number of Xs is 2, the Xs may be the same or different;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, and m1 represents an integer of 1 to 3;
R represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or phase selected from their substituents. It is a group in which different 2 to 6 rings are bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 5 carbon atoms. (Representing an alkyl group of), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or alkyl having 1 to 5 carbon atoms. It may be substituted with an oxy group, or represents a hydroxy group or an alkoxy group having 1 to 6 carbon atoms).
The composition according to any one of claims 1 to 4 , which has any one selected from the group consisting of.

The photoreactive group is the following formula (14) or (15).
(In the equation, A is a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO-O-, respectively. Or -O-CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 carbon atoms). (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
l represents an integer of 1 to 12, m1 and m2 represent an integer of 1 to 3)
The composition according to any one of claims 1 to 4 , which has a photoreactive side chain represented by.

The photoreactive group is the following formula (16) or (17) (in the formula, A is a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO. -, -CH = CH-CO-O-, or -O-CO-CH = CH-;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH-represents and the number of Xs is 2, the Xs may be the same or different;
l represents an integer of 1 to 12 and m represents an integer of 0 to 2)
The composition according to any one of claims 1 to 4 , which has a group represented by.

The photoreactive group is the following formula (20) (in the formula, A is a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-,- Represents CH = CH-CO-O- or -O-CO-CH = CH-;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 carbon atoms). (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH-represents and the number of Xs is 2, the Xs may be the same or different;
The composition according to any one of claims 1 to 4 , wherein l represents an integer of 1 to 12 and m represents an integer of 0 to 2).

An optical element formed by having a liquid crystal cell having the photoreactive liquid crystal composition according to any one of claims 1 to 9. A display device formed by having a liquid crystal cell having the photoreactive liquid crystal composition according to any one of claims 1 to 9. [I] A photoreactive liquid crystal composition having (A) a photoreactive compound having a siloxane skeleton and having a photoreactive group; and (B) a low molecular weight liquid crystal; the photoreactive group is as follows. Equations (1) to (6)
(In the formula, A, B, and D are independently single-bonded, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO. Represents -O- or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 carbon atoms). (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. The hydrogen atoms bonded to are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y _1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH-represents and the number of Xs is 2, the Xs may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-. It may be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. It is a group; however, when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring. When the number of Ps is 2 or more, the Ps may be the same or different, and when the number of Qs is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
When both l1 and l2 are 0, A also represents a single bond when T is a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are groups independently selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof. )
A step of filling a space formed between two transparent substrates arranged in parallel with a photoreactive liquid crystal composition having any one selected from the group consisting of two transparent substrates to form a liquid crystal cell; and [II. ] A step of irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet rays from either of the two transparent substrates;
(B) A method for manufacturing an optical element, wherein an optical element having a predetermined orientation of a small molecule liquid crystal is formed in the liquid crystal cell.

[I] A photoreactive liquid crystal composition having (A) a photoreactive compound having a siloxane skeleton and having a photoreactive group; and (B) a low molecular weight liquid crystal; the photoreactive group is as follows. Equations (1) to (6)
(In the formula, A, B, and D are independently single-bonded, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH-CO-, -CH = CH-CO. Represents -O- or -O-CO-CH = CH-;
S is an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
T is a single bond or an alkylene group having 1 to 12 carbon atoms, and the hydrogen atom bonded to them may be replaced with a halogen group;
Y ₁ represents a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or the same or selected from their substituents. It is a group consisting of 2 to 6 different rings bonded via a bonding group B, and the hydrogen atoms bonded to them are independently −COOR ₀ (in the formula, R ₀ is a hydrogen atom or 1 to 1 carbon atoms). (Representing an alkyl group of 5), -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. May be substituted with an alkyloxy group;
Y ₂ is a group selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. The hydrogen atoms bonded to are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, halogen group, alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R is hydroxy group, or an alkoxy group having 1 to 6 carbon atoms, or represents the same definition as Y _1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = When CH-represents and the number of Xs is 2, the Xs may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded to them are independently -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-. It may be substituted with CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
One of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q are independently selected from the group consisting of a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, an alicyclic hydrocarbon having 5 to 8 carbon atoms, and a combination thereof. It is a group; however, when X is -CH = CH-CO-O-, -O-CO-CH = CH-, P or Q on the side to which -CH = CH- is bonded is an aromatic ring. When the number of Ps is 2 or more, the Ps may be the same or different, and when the number of Qs is 2 or more, the Qs may be the same or different;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
When both l1 and l2 are 0, A also represents a single bond when T is a single bond;
When l1 is 1, B also represents a single bond when T is a single bond;
H and I are groups independently selected from a divalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and a combination thereof. )
A step of filling a space formed between two transparent substrates arranged in parallel with a photoreactive liquid crystal composition having any one selected from the group consisting of two transparent substrates to form a liquid crystal cell; and [II. ] A step of irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet rays from either of the two transparent substrates;
(B) A method for manufacturing a display element, wherein a display element having a predetermined orientation of a small molecule liquid crystal is formed in the liquid crystal cell.

The following formulas (A) 1-1 to (A) -1-3, (A) 2-1, (A) 3-1 and (A) -3-2 (in the formula, Me is a methyl group. A compound represented by any one of the formulas selected from the group consisting of (represented).

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