JP7092313B2 - Photoreactive liquid crystal composition, dimming element, manufacturing method of dimming element - Google Patents

Description

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

The current liquid crystal display element uses a liquid crystal alignment film that has been subjected to an alignment process in order to uniformly orient 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 rubbing treatment after applying the liquid crystal alignment film, but the method of rubbing the film surface with a roller wrapped with cloth is taken, but this method physically touches the film surface. Since it is a method of rubbing, 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 capable of controlling the orientation of the liquid crystal can be produced without using the liquid crystal alignment film, there is a great merit in terms of process and cost.

On the other hand, PDLC creates a liquid crystal cell using a low-molecular-weight liquid crystal mixed with a polymerizable compound that reacts with light in advance, and then irradiates ultraviolet rays from outside the cell to polymerize the polymerizable compound and immobilize the liquid crystal. It is a technology to do. However, since the liquid crystal alignment process is not performed in this technique, the alignment of the liquid crystal is not controlled, and the electro-optic characteristics are insufficient to apply the element to the dimming element or the display element. (See, for example, Non-Patent Document 1).

Japanese Unexamined Patent Publication No. 2006-201388. Japanese Patent Application Laid-Open No. 2003-307720.

LCD Handbook Maruzen Co., Ltd.

Therefore, an object of the present invention is to provide an element obtained by controlling the orientation of the liquid crystal in the liquid crystal bulk without using a liquid crystal alignment film, specifically, a dimming element, and / or to provide the element. It is an object of the present invention to provide a photoreactive liquid crystal composition for making.
Further, in addition to or other than the above object, an object of the present invention 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, dimming. The purpose is to provide a method for manufacturing an element.

The present inventors have found the following inventions.
<1> A photoreactive polymer liquid crystal having a photoreactive side chain that causes at least one reaction selected from the group consisting of (A) (A-1) photocrosslinking and (A-2) photoisomerization; A photoreactive liquid crystal composition comprising (B) a low molecular weight liquid crystal;
The weight ratio of (A) photoreactive polymer liquid crystal to (B) low molecular weight liquid crystal ((A) photoreactive polymer liquid crystal: (B) low molecular weight liquid crystal) is 3:97 to 20:80, preferably 3:97 to 20:80. The above-mentioned photoreactive liquid crystal composition, which is 4: 96 to 15:85, more preferably 5:95 to 13:87.

<2> A photoreactive polymer liquid crystal having a photoreactive side chain that causes at least one reaction selected from the group consisting of (A) (A-1) photocrosslinking and (A-2) photoisomerization; A photoreactive liquid crystal composition comprising (B) a low molecular weight liquid crystal;
The composition is exposed to polarized ultraviolet rays, and (A) the temperature is 50 ° C. lower than the lower limit of the temperature range in which the photoreactive polymer liquid crystal exhibits liquid crystallinity, preferably 65 to 150 ° C., more preferably 70 to. The above-mentioned photoreactive liquid crystal composition, wherein (B) the low molecular weight liquid crystal has a predetermined orientation by heating the composition to 120 ° C.
<3> In the above <1>, the composition is exposed to polarized ultraviolet rays, and (A) the temperature is 50 ° C. lower than the lower limit of the temperature range in which the photoreactive polymer liquid crystal exhibits liquid crystallinity, preferably 65. By heating the composition to ~ 150 ° C., more preferably 70 to 120 ° C., the low molecular weight liquid crystal (B) preferably has a predetermined orientation.
<4> In any of the above <1> to <3>, it is preferable that the (A) photoreactive polymer liquid crystal liquid crystal has (A-1) a photoreactive side chain that causes a photocrosslinking reaction.

<5> In any of the above <1> to <4>,
(A) The photoreactive polymer liquid crystal has the following formulas (1) to (6).
(In the formula, A, B, and D are independent, single bond, -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 to 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, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R represents a hydroxy group, an alkoxy group having ₁ to 6 carbon atoms, or represents the same definition as Y1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = Representing CH-, when 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. )
It is preferable to have any one of the photoreactive side chains selected from the group consisting of.

<6> In any of the above <1> to <5>,
(A) The photoreactive polymer liquid crystal has the following formulas (7) to (10).
(In the formula, A, B, and D are independent, single bond, -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 to 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 = Representing CH-, when 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, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R represents a hydroxy group, an alkoxy group having ₁ to 6 carbon atoms, or represents the same definition as Y1).
It is preferable to have any one of the photoreactive side chains selected from the group consisting of.

<7> In any of the above <1> to <5>,
(A) The photoreactive polymer liquid crystal has the following formulas (11) to (13).
(In the formula, 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 = Representing CH-, when 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 consisting of different 2 to 6 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 5 carbon atoms. (Representing an alkyl group of), -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. It may be substituted with an oxy group, or represents a hydroxy group or an alkoxy group having 1 to 6 carbon atoms).
It is preferable to have any one of the photoreactive side chains selected from the group consisting of.

<8> In any of the above <1> to <5>,
(A) The photoreactive polymer liquid crystal is the following formula (14) or (15).
(In the formula, 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 to 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)
It is preferable to have a photoreactive side chain represented by.

<9> In any of the above <1> to <5>,
(A) The photoreactive polymer liquid crystal has the following formula (16) or (17) (in the formula, A is a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, Represents -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 = Representing CH-, when 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)
It is preferable to have a photoreactive side chain represented by.

<10> In any of the above <1> to <5>,
(A) The photoreactive polymer liquid crystal has the following formula (20) (in the formula, A is a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH- Represents CO-, -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 to 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 = Representing CH-, when the number of Xs is 2, the Xs may be the same or different;
It is preferable to have a photoreactive side chain represented by (l represents an integer of 1 to 12 and m represents an integer of 0 to 2).

<11> A dimming element formed by having a liquid crystal cell having the photoreactive liquid crystal composition according to any one of <1> to <10>.
<12> A light control element formed by having a liquid crystal cell having the photoreactive liquid crystal composition according to any one of <1> to <10>, wherein the (B) low molecular weight liquid crystal is formed in the liquid crystal cell. The element having a predetermined orientation.

<13> [I] High photoreactivity with a photoreactive side chain that produces at least one reaction selected from the group consisting of (A) (A-1) photobridge and (A-2) photoisomerization. A step of filling a space formed between two transparent substrates arranged in parallel with a photoreactive liquid crystal composition having a molecular liquid crystal; and (B) low molecular weight liquid crystal; to form a liquid crystal cell;
[II] The step of irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet rays from either of the two transparent substrates; and [III] (A) the photoreactive polymer liquid crystal is liquid crystal. A step of heating the liquid crystal cell to a temperature 50 ° C. lower than the lower limit of the temperature range in which the liquid crystal is expressed, preferably 65 to 150 ° C., more preferably 70 to 120 ° C.;
(B) A method for manufacturing a dimming element, wherein a dimming element having a predetermined orientation of a small molecule liquid crystal is formed in the liquid crystal cell.

<14> In the above <13>, it is preferable to perform the step [III] during the step [II].
<15> In the above <13> or <14>, it is preferable to perform the [III] step after the [II] step.

<16> In any of the above <13> to <15>, the weight ratio of (A) photoreactive polymer liquid crystal to (B) low molecular weight liquid crystal ((A) photoreactive polymer liquid crystal: (B) The low molecular weight liquid crystal) is preferably 3:97 to 20:80, preferably 4:96 to 15:85, and more preferably 5:95 to 13:87.
<17> In any of the above <13> to <16>, it is preferable that the (A) photoreactive polymer liquid crystal liquid crystal has (A-1) a photoreactive side chain that causes a photocrosslinking reaction.

<18> In any of the above <13> to <17>, the photoreactive polymer liquid crystal (A) is the above formula (1) to (6) (in the formula, A, B, D, S, T, Any one light selected from the group consisting of Y ₁ , Y ₂ , R, X, Cou, q1, q2, q3, P, Q, l1, l2, H and I) having the same definition as above). It is preferable to have a reactive side chain.
<19> In any of the above <13> to <18>, the (A) photoreactive polymer liquid crystal has the above formulas (7) to (10) (in the formulas A, B, D, Y ₁ , X). , L, m, m1, _m2 , n, Y2 and R have the same definition as above) and preferably have any one photoreactive side chain selected from the group.

<20> In any of the above <13> to <18>, the photoreactive polymer liquid crystal (A) is the above formula (11) to (13) (in the formula, A, X, l, m, m1 and R preferably has any one photoreactive side chain selected from the group consisting of (having the same definition as above).
<21> In any of the above <13> to <18>, the (A) photoreactive polymer liquid crystal is the above formula (14) or (15) (in the formula, A, Y1, _l , m1 and m2). May have a photoreactive side chain represented by) (having the same definition as above).

<22> In any of the above <13> to <18>, the photoreactive polymer liquid crystal (A) is the above formula (16) or (17) (in the formula, A, X, l and m are the above. It is preferable to have a photoreactive side chain represented by).
<23> In any of the above <13> to <18>, the photoreactive polymer liquid crystal (A) is the above formula (20) (in the formula, A, Y ₁ , X, l and m are the same as the above. It is preferable to have a photoreactive side chain represented by) (having the same definition).

INDUSTRIAL APPLICABILITY According to the present invention, an element obtained by controlling the orientation of a liquid crystal in a liquid crystal bulk, specifically a dimming element, without using a liquid crystal alignment film, and / or for manufacturing the element. A photoreactive liquid crystal composition can be provided.
Further, in addition to or in addition to the above effects, according to the present invention, an element obtained by controlling the orientation of the liquid crystal in the liquid crystal bulk without using a liquid crystal alignment film, specifically, a dimming element. A method of manufacturing can be provided.

An example of an ultraviolet irradiation apparatus for manufacturing the dimming element of the present invention is shown. A schematic diagram of an experimental system for measuring the intensity of transmitted diffracted light of a liquid crystal cell obtained after polarization exposure of Examples , Comparative Examples 1 and Reference Examples 1 to 4 is shown. In the experimental system shown in FIG. 2, the results of measuring the transmitted light intensity (vertical axis) when the liquid crystal cells of Example 1, Reference Example 1 and Reference Example 2 are rotated (horizontal axis: angle) are shown. In the experimental system shown in FIG. 2, the results of measuring the transmitted light intensity (vertical axis) when the liquid crystal cells of Example 2, Reference Example 3 and Reference Example 4 are rotated (horizontal axis: angle) are shown.

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 dimming element, and / or a photoreactive liquid crystal composition for producing the element. Provide things.
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, specifically, a dimming element, without using a liquid crystal alignment film.
Hereinafter, a photoreactive liquid crystal composition, an element obtained by the composition, specifically a dimming element, and a method for manufacturing the element will be described.

<Photoreactive liquid crystal composition>
The photoreactive liquid crystal composition of the present invention comprises 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 high molecular weight liquid crystal; and (B) low molecular weight liquid crystal;
The photoreactive liquid crystal composition of the present invention comprises only (A) a photoreactive polymer liquid crystal; and (B) a low molecular weight liquid crystal; to the extent that the properties of (A) and (B) do not change. It may be essentially composed only of (A) and (B) having other 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 low-molecular-weight liquid crystal (B) contained in the photoreactive liquid crystal composition of the present invention, a nematic liquid crystal, a ferroelectric liquid crystal, or the like conventionally used for a liquid crystal display element or the like can be used as it is.
Specifically, (B) as the low molecular weight liquid crystal, cyanobiphenyls such as 4-cyano-4'-n-pentylbiphenyl and 4-cyano-4'-n-feptyroxybiphenyl; cholesteryl acetate, cholesteryl benzoate and the like. Cholesteryl esters; carbonate esters such as 4-carboxyphenylethyl 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-butoxybenziliden-4-acetylaniline; benzidines such as N, N'-bisbenzidene benzidine, p-dianisalvendidin; 4,4'-azoxidianisol, 4, Azoxybenzenes such as 4'-di-n-butoxyazoxybenzene; liquid crystals of phenylcyclohexyl, turphenyl, phenylbicyclohexyl, etc. specifically shown below; but are limited thereto. Not done.

<< (A) Photoreactive polymer liquid crystal >>
The (A) photoreactive polymer liquid crystal (hereinafter, may be simply abbreviated as "(A) component") contained in the photoreactive liquid crystal composition of the present invention includes (A-1) photocrosslinking and. (A-2) The present invention is not particularly limited as long as it has a photoreactive side chain that causes at least one reaction selected from the group consisting of photoisomerization.
As used herein, the term "photoreactive" refers to the property of causing either (A-1) photocrosslinking or (A-2) photoisomerization; and both reactions;
The component (A) preferably has a side chain that causes the (A-1) photocrosslinking reaction.

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

In the photoreactive liquid crystal composition of the present invention, the weight ratio of (A) photoreactive polymer liquid crystal to (B) low molecular weight liquid crystal ((A) photoreactive polymer liquid crystal: (B) low molecular weight liquid crystal) is , 3: 97 to 20:80, preferably 4: 96 to 15:85, and more preferably 5:95 to 13:87.
(A): When the ratio of (A) in (B) is within the above range, i) it is possible to obtain a uniform liquid crystal orientation, i) the amount of the orienting group required for orienting the liquid crystal can be secured. Iii) The density of the polymer matrix after the photoreactive polymer liquid crystal (A) reacts with polarized ultraviolet rays becomes a desired value, and iv) the low molecular weight liquid crystal (B) when a voltage is applied is desired. It is good in terms of responding.

As described above, the component (A) has a photoreactive side chain having photoreactivity. The structure of the side chain is not particularly limited, but has a structure that causes the reaction shown in (A-1) and / or (A-2) above, and has a structure that causes the (A-1) photocrosslinking reaction. Is preferable. 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 side chain of the component (A), it is preferable to have a rigid mesogen component because the orientation of the liquid crystal is stable.

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 structure of the main chain of the component (A) includes radically polymerizable groups such as hydrocarbons, (meth) acrylates, itaconates, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxanes. At least one selected from the group consisting of, but not limited to.
Further, the side chain of the component (A) is preferably a side chain 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 to 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, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R represents a hydroxy group, an alkoxy group having ₁ to 6 carbon atoms, or represents the same definition as Y1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = Representing CH-, when 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 side chain is preferably any one of the photoreactive side chains 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 side chain is preferably any one of the photoreactive side chains 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 side chain is preferably a photoreactive side chain represented by the following formula (14) or (15).
In the formula, A, Y1, _l , m1 and m2 have the same definitions as above.

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

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

Further, the component (A) may have any one liquid crystal side chain selected from the group consisting of the following formulas (21) to (31). For example, when the photoreactive side chain of the component (A) does not have liquid crystallinity, or when the main chain of the component (A) does not have liquid crystallinity, the component (A) has the following formulas (21) to ( It is preferable to have any one liquid crystal side chain selected from the group consisting of 31).
In the formula, A, B, q1 and q2 have the same definitions as above;
_Y3 is a group selected from the group consisting of monovalent benzene rings, naphthalene rings, biphenyl rings, furan rings, nitrogen-containing heterocycles, alicyclic hydrocarbons having 5 to 8 carbon atoms, and combinations thereof. Yes, the hydrogen atoms attached to them may be independently substituted with -NO ₂ , -CN, a halogen group, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R ₃ contains a hydrogen atom, -NO ₂ , -CN, -CH = C (CN) ₂ , -CH = CH-CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, and nitrogen. Represents a heterocycle, an alicyclic hydrocarbon having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, but in equations (23) to (24), the total of all m is 2 or more, and equations (25) to (26). ), The sum of all m is 1 or more, and m1, m2, and m3 independently represent integers of 1 to 3;
R ₂ is a hydrogen atom, -NO ₂ , -CN, a halogen group, a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a nitrogen-containing heterocycle, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. And represents an alkyl group or an alkyloxy group;
Z ₁ and Z ₂ represent a single bond, -CO-, -CH ₂ O-, -CH = N-, -CF _2- .

<< (A) Ingredient manufacturing method >>
The component (A) polymerizes the photoreactive side chain monomer having the photoreactive side chain, and in some cases, copolymerizes the photoreactive side chain monomer with the monomer having the liquid crystal side chain. By doing so, you can get it.

[Photoreactive side chain monomer]
The photoreactive side chain monomer, as used herein, refers to a monomer capable of forming a polymer having a photoreactive side chain at a side chain portion of the polymer when the polymer is formed.
As the photoreactive group of the side chain, the following structure and its derivative are preferable.

More specific examples of photoreactive side chain monomers include radically polymerizable groups such as hydrocarbons, (meth) acrylates, itaconates, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene. A polymerizable group composed of at least one selected from the group consisting of siloxane and a photoreactive side chain composed of at least one of the above formulas (1) to (6), preferably, for example, the above formula ( 7) A photoreactive side chain consisting of at least one of the above formulas (11) to (10), a photoreactive side chain consisting of at least one of the above formulas (11) to (13), represented by the above formula (14) or (15). It is preferable that the structure has a photoreactive side chain represented by the above formula (16) or (17), and a photoreactive side chain represented by the above formula (20).

As the photoreactive side chain monomer, for example, the following formulas PRM-1 to PRM-11 (in the formula, n represents an integer of 1 to 6, m represents an integer of 0 to 4, and X represents a hydrogen atom or a methyl group. , R represents a hydrogen atom, a linear or branched alkyl group or an alkoxy group having 1 to 3 carbon atoms, a halogen atom, a cyano group, or a nitro group, and R ₁ to R ₃ are independent hydrogen atoms. , A straight-chain or branched alkyl group or an alkoxy group having 1 to 3 carbon atoms, or a compound represented by a halogen atom, where p indicates an integer of 1 to 4), but is not limited thereto. ..

[Liquid crystal side chain monomer]
The liquid crystal side chain monomer, as used herein, refers to a monomer in which a polymer derived from the monomer exhibits liquidity and the polymer can form a mesogen group at a side chain site.
As the mesogen group possessed by the side chains, even if it is a group having a mesogen structure by itself such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid. good. The following structure is preferable as the mesogen group contained in the side chain.

More specific examples of the liquid crystal side chain monomer include hydrocarbons, (meth) acrylates, itaconates, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radically polymerizable groups. It is preferable that the structure has a polymerizable radical composed of at least one selected from the group consisting of siloxane and a side chain composed of at least one of the above formulas (21) to (31).
Specifically, as the liquid crystal side chain monomer, for example, the following formulas LCM-1 to LCM-9 (in the formula, n represents an integer of 1 to 6, X represents a hydrogen atom or a methyl group, and _R4 , R ₆ and R ₆₁ to R ₆₃ independently represent a hydrogen atom, a linear or branched alkyl or alkoxy group having 1 to 3 carbon atoms, a halogen atom, a cyano group, or a nitro group, and R ₅ is a hydrogen atom. , Indicates a linear or branched alkyl group having 1 to 6 carbon atoms), but is not limited thereto.

The component (A) can be obtained by the polymerization reaction of the photoreactive side chain monomer exhibiting the liquid crystal property described above. Further, it can be obtained by copolymerizing a photoreactive side chain monomer that does not exhibit liquidity and a liquid crystal side chain monomer, or by copolymerizing a photoreactive side chain monomer that exhibits liquidity and a liquid crystal side chain monomer. can. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.

Examples of other monomers include industrially available radical polymerization-reactive monomers.
Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate and tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Examples thereof include propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate and tert-butyl. Methacrylate, Cyclohexyl methacrylate, Isobornyl methacrylate, 2-Methylethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, Tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-Methyl-2-adamantyl methacrylate, 2- Examples thereof include propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate and the like. (Meta) acrylate compounds having a cyclic ether group such as glycidyl (meth) acrylate, (3-methyl-3-oxetanyl) methyl (meth) acrylate, and (3-ethyl-3-oxetanyl) methyl (meth) acrylate are also used. be able to.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether and the like.
Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

The method for producing the side-chain type polymer of the present embodiment is not particularly limited, and a general-purpose method that is industrially handled can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystal side chain monomer or a photoreactive side chain monomer. Of these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.

As the polymerization initiator for radical polymerization, known compounds such as a radical polymerization initiator and a reversible addition-fragmentation chain transfer (RAFT) polymerization reagent can be used.

The radical thermal polymerization initiator is a compound that generates radicals by heating to a temperature higher than the decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), and hydroperoxides (peroxidation). Hydrogen, tert-butylhydroxide, cumenehydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutylperoxycyclohexane, etc.) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy2-ethylcyclohexanoic acid-tert-amyl ester, etc.), persulfates (potassium persulfate, etc.) Examples thereof include sodium persulfate, ammonium persulfate, etc.) and azo radical compounds (azobisisobutyronitrile, and 2,2'-di (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such a radical thermal polymerization initiator may be used alone or in combination of two or more.

The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone and 2-hydroxy. -2-Methylpropiophenone, 2-Hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexylphenylketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthron, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-( 4-Molholinophenyl) -butanone-1, 4-ethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4,4'-tri ( t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3' , 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(2'-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [P-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s- Triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-Mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bi Su (2-chlorophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4, 4', 5,5'-Tetraphenyl-1,2'-biimidazole, 2,2'bis (2,4-dibromophenyl) -4,4', 5,5'-Tetraphenyl-1,2' -Bimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2) -Dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenylketone, bis (5-2,4-cyclopentadiene-1- Il) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4'-Tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di ( Methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2- (3- (3-) Methyl-3H-benzothiazole-2-ylidene) -1-naphthalen-2-yl-etanone, or 2- (3-methyl-1,3-benzothiazole-2 (3H) -iriden) -1- (2-) Benzoyl) Etanone and the like can be mentioned. These compounds may be used alone or in admixture of two or more.

The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, a bulk polymerization method, a solution polymerization method and the like can be used.

The organic solvent used for the reaction for producing the component (A), specifically, the polymerization reaction for the above-mentioned monomer is not particularly limited as long as the produced polymer can be dissolved. Specific examples are given below.

N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactum, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide , Gamma-butylollactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cell solve, ethyl cell solve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl Ether, Diethylene Glycol, Diethylene Glycol Monoacetate, Diethylene Glycol Dimethyl Ether, Dipropylene Glycol Monoacetate Monomethyl Ether, Dipropylene Glycol Monomethyl Ether, Dipropylene Glycol Monoethyl Ether, Dipropylene Glycol Monoacetate Monoethyl Ether, Dipropylene Glycol Monopropyl Ether, Dipropylene Glycol Monoacetate Monopropyl Ether, 3-Methyl-3-methoxybutyl Acetate, Tripropylene Glycol Methyl Ether, 3-Methyl-3-methoxybutanol, Diisopropyl Ether, Ethyl Isobutyl Ether, Diisobutylene, Amyl Acetate, Butyl Butyrate, Butyl Ether , Diisobutylketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, acetic acid Ethyl, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglime, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3- Examples thereof include ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.

These organic solvents may be used alone or in combination. Further, even if the solvent does not dissolve the produced polymer, it may be mixed with the above-mentioned organic solvent and used as long as the produced polymer does not precipitate.
Further, in radical polymerization, oxygen in the organic solvent causes an inhibition of the polymerization reaction, so it is preferable to use an organic solvent degassed to the extent possible.

The polymerization temperature in the case of radical polymerization can be selected from any temperature of 30 ° C to 150 ° C, but is preferably in the range of 50 ° C to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial reaction can be carried out at a high concentration and then an organic solvent can be added.

In the above-mentioned radical polymerization reaction, when the ratio of the radical polymerization initiator is large with respect to the monomer, the molecular weight of the obtained polymer is small, and when the ratio is small, the molecular weight of the obtained polymer is large. It is preferably 0.1 mol% to 10 mol% with respect to the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added at the time of polymerization.

[Recovery of polymer]
In order to recover the product obtained by the above reaction, that is, the component (A) from the reaction solution, it is preferable to put the reaction solution into a poor solvent.
Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, water and the like.
The polymer put into a poor solvent and precipitated can be collected by filtration and then dried at room temperature or by heating under normal pressure or reduced pressure. Further, by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the operation of re-precipitation recovery 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because the efficiency of purification is further improved.

As for the molecular weight of the component (A) of the present invention, the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method is preferably 2000 to 1000000, more preferably 5000 to 200,000.

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 components (A) and (B) used, the use of the photoreactive liquid crystal composition, and the like, for example, antioxidants such as hindered amines and hindered phenols, or one. Examples thereof include polymerizable compounds having a group that photopolymerizes or photocrosslinks at the above terminals.
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, It preferably represents a linear or branched alkylene group having 2 to 6 carbon atoms. W is represented by a single bond or -OR _9- , preferably -OR _9- , and R ₉ is preferably 1 to 10 carbon atoms. 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 a dimming device obtained by the above-mentioned photoreactive liquid crystal composition, and a method for manufacturing the device.
The device of the present invention is formed by having a liquid crystal cell having the above-mentioned photoreactive liquid crystal composition.

The device of the present invention can be formed by filling a liquid crystal cell with the above-mentioned photoreactive liquid crystal composition.
Specifically, the device of the present invention can be manufactured by the following steps.
[I] A photoreactive polymer liquid crystal having a photoreactive side chain that causes at least one reaction selected from the group consisting of (A) (A-1) photocrosslinking and (A-2) photoisomerization; And (B) a step of filling a space formed between two transparent substrates arranged in parallel with a photoreactive liquid crystal composition having a low molecular weight liquid crystal; to form a liquid crystal cell; and [II] [. A step of irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet light from either of the two transparent substrates;
By having the device of the present invention, specifically, a dimming device can be formed, specifically, an element in which (B) a low-molecular-weight liquid crystal has a predetermined orientation in a liquid crystal cell, specifically. A dimming element is formed in.

The step [I] is a step of filling a space in which the above-mentioned photoreactive liquid crystal composition is formed between transparent substrates by at least the substrates on the side to be irradiated with ultraviolet rays, which are arranged in parallel and spaced apart from each other, to form a liquid crystal cell. 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 have flexibility depending on the element to be 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 (A) the photoreactive polymer liquid crystal, (A) the molecular major axis of the photoreactive polymer liquid crystal absorbs the polarized light. It is preferable to arrange the (A) photoreactive polymer liquid crystal in the liquid crystal cell. Further, since (A) the photoreactive polymer liquid crystal is encapsulated in the liquid crystal cell as a composition with (B) the low molecular weight liquid crystal, the molecular major axis of (A) the photoreactive polymer liquid crystal is in the liquid crystal cell. In order to arrange the low molecular weight liquid crystal in a desired state, it is preferable to arrange the (B) low molecular weight liquid crystal in the liquid crystal cell in the desired state as well. That is, in order to sufficiently cause the photoreaction of (A) the photoreactive polymer liquid crystal, the direction of the incident light of the polarized ultraviolet light is perpendicular to the direction of the molecular major axis of (A) the photoreactive polymer liquid crystal. It is better to expose the polarized ultraviolet light so that it is close to.
For example, when polarized ultraviolet light is exposed from the normal direction of the liquid crystal cell, the molecular major axes of both (A) photoreactive polymer liquid crystal and (B) low molecular weight liquid crystal in the photoreactive composition are the substrate surface. It is preferable to arrange the substrate in the horizontal direction, and the film contained in the substrate is not limited to the material as long as it is such a film.
Further, when the molecular major axis of (A) the photoreactive polymer liquid crystal is not in the horizontal direction with the above-mentioned substrate surface, the incident angle of the polarized ultraviolet light is determined according to the arrangement state of the molecular major axis. Is good.

The step [II] is a step of irradiating the liquid crystal cell obtained in [I] with polarized ultraviolet rays. Since the polarized ultraviolet rays are emitted from the outside of either of the two transparent substrates, the transparent substrate is a substrate that transmits the polarized ultraviolet rays as described above.
The polarized ultraviolet rays depend on the element to be formed, but ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected via a filter or the like depending on the type of the coating film to be 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 light, for example, light emitted from a high-pressure mercury lamp can be used.

When irradiated with polarized ultraviolet rays, the following mechanism is considered to occur in the liquid crystal cell. That is, the (A) photoreactive polymer liquid crystal in the liquid crystal cell has an orientation corresponding to the polarized ultraviolet rays.
Further, the (B) low molecular weight liquid crystal is oriented according to the orientation of the (A) photoreactive polymer liquid crystal.
As a result, the (A) photoreactive polymer liquid crystal and (B) low molecular weight liquid crystal have orientation depending on the polarized ultraviolet rays.

It should be noted that the orientation can be obtained as described above only by exposure to polarized ultraviolet rays, but since it is insufficient, the step of further heating the [III] liquid crystal cell, specifically, (A) photoreactivity. It is further necessary to have a step of heating the liquid crystal cell to a temperature 50 ° C. lower than the lower limit of the temperature range in which the polymer liquid crystal exhibits liquid crystal properties. In this case, heating can be performed with exposure to polarized ultraviolet light and / or after exposure to polarized ultraviolet light.
Here, the heating is preferably at a temperature 50 ° C. lower ((Tx-50) ° C.) or higher than the lower limit (Tx) of the temperature range in which the photoreactive polymer liquid crystal exhibits liquid crystallinity. Is preferably carried out at 65 to 150 ° C., more preferably 70 to 120 ° C.
For example, i) exposing the liquid crystal cell to polarized ultraviolet light; ii) exposing the liquid crystal cell in a heated state in the above temperature range; iii) after performing the exposure as in the above i), heating in the above temperature range. That; or iv) heating in the above temperature range after ii); (A) the photoreactive polymer liquid crystal has orientation, and accordingly, (B) the low molecular weight liquid crystal also has orientation. Will have. By using such a step, (B) a dimming device in which the small molecule liquid crystal is oriented in one axis can be produced.

In the present application, the "dimming element" refers to an element that controls the transmission / non-transmission of light from the back surface by driving a liquid crystal whose orientation is controlled by applying a voltage, such as a display (display element). Also includes window dimming film (glass).

(Example 1)
After adding 5 parts by weight of the photoreactive polymer liquid crystal represented by the following formula P6CB to 95 parts by weight of the low molecular weight liquid crystal (E7) manufactured by Merck Co., Ltd. represented by the following formula E7, the mixture is stirred at 180 ° C. for 20 minutes. , A photoreactive liquid crystal composition was obtained.

Then, the liquid crystal cell A1 was produced by enclosing the photoreactive liquid crystal composition in a parallel flat plate cell having a gap of 2 μm made of a glass substrate having ITO on both sides of the substrate.
The obtained liquid crystal cell A1 was heated to 80 ° C. and exposed to polarized ultraviolet rays to form a liquid crystal cell B1 in which the orientation of the liquid crystal was controlled.
The photoreactive polymer liquid crystal represented by the formula P6CB exhibited liquid crystallinity at 115 ° C. or higher.

Specifically, using the uniform exposure apparatus (KIN-ITSU-KUN (manufactured by Yamashita Denso Co., Ltd.)) shown in FIG. 1, linear polarization having a wavelength of 313 nm (22 mW / cm ² ) is adjusted to an exposure amount of 2 J / cm ² . Was exposed from the normal direction of the liquid crystal cell A1. The temperature during exposure was controlled using a temperature controller manufactured by INSTEC. The uniform exposure apparatus 1 of FIG. 1 has an ultraviolet light emitting unit 2 that emits ultraviolet rays uniformly over the entire light emitting surface, a polarizing element 3 provided below the light emitting unit, and a sample table on which the sample 4 is placed. Has 5. Further, the temperature control unit 6 between the sample 4 and the sample table 5 can heat the sample during the exposure and / or the sample after the exposure via the temperature control unit 6. Be placed.

<Orientation state of small molecule liquid crystal>
After the liquid crystal cell B1 was manufactured, the transmitted light intensity when the liquid crystal cell was rotated was measured in the experimental system shown in FIG. 2 to confirm the orientation state of the low molecular weight liquid crystal. The orientation of the small molecule liquid crystal was also confirmed by a polarizing microscope.
The measurement results by the experiment shown in FIG. 2 are shown in FIG. 3, and the observation results by the polarizing microscope are shown in Table 1, respectively.

The experimental system 11 of FIG. 2 includes a He-Ne laser 12, a splitter 13, an analyzer 14, and a power meter 15, and a laser irradiated from the He-Ne laser 12 is a polarizing element 13 and an analyzer. 14 and the power meter 15 are arranged so as to receive them in this order. Further, the stator 13 and the analyzer 14 are arranged in a state of orthogonal Nicols. The sample 16 is arranged between the polarizing element 13 and the analyzer 14, and the transmitted light intensity when the sample 16 is rotated is detected by the power meter 15.

The following can be seen from FIG. That is, since the maximum transmitted light intensity was shown when the optical axis of the liquid crystal cell was tilted 45 degrees with respect to the polarizing element and the analyzer, it can be seen that the orientation of the liquid crystal in the liquid crystal cell is controlled in one axis. .. From this, it was shown that the liquid crystal in the liquid crystal cell is oriented in one axis.
In addition, from Table 1, it was found from the observation results of the polarizing microscope that the liquid crystal in the liquid crystal cell was oriented in one axis.
Further, it was confirmed that when a voltage was applied to the liquid crystal cell B1, the liquid crystal in the cell was driven according to the magnitude of the applied voltage, and it was confirmed that the liquid crystal cell B1 could operate as a dimming element.

(Example 2)
A liquid crystal cell A1 was created in the same manner as in Example 1. After exposing the liquid crystal cell A1 to ultraviolet rays polarized at room temperature, the liquid crystal cell was heated at 80 ° C. for 30 minutes to form a liquid crystal cell B2 in which the orientation of the liquid crystal was controlled.
In the obtained liquid crystal cell B2, the orientation state of the low molecular weight liquid crystal was observed by the experiment shown in FIG. 2 and a polarizing microscope in the same manner as in Example 1 (Table 1).
FIG. 4 shows the measurement results of the liquid crystal cell B2 by the experiment shown in FIG. From FIG. 4, it was found that the liquid crystal in the liquid crystal cell B2 was oriented in one axis. It was also found from the observation with a polarizing microscope that the liquid crystal in the liquid crystal cell B2 was oriented in one axis (Table 1, FIG. 4).
Furthermore, it was confirmed that the liquid crystal was driven by applying a voltage, and that the liquid crystal cell B2 could operate as a dimming element.

(Comparative Example 1)
A liquid crystal cell CE1 was produced in the same manner as in Example 1 except that the liquid crystal composition to be enclosed in the parallel flat plate cell was only E7, and the liquid crystal cell CE1 was subjected to polarization exposure in the same manner as in Example 1 to measure the transmitted light intensity. did. As a result, no angle dependence of the transmitted light intensity was observed even when the temperature of the heating performed together with the polarized light exposure was changed. Moreover, as a result of observation with a polarizing microscope, the orientation of the liquid crystal could not be confirmed.

( Reference example 1 )
A liquid crystal cell A1 was created in the same manner as in Example 1. The liquid crystal cell A1 was heated at 30 ° C. and exposed to polarized ultraviolet rays to form the liquid crystal cell CE2.
In the obtained liquid crystal cell CE2, the orientation state of the low molecular weight liquid crystal was observed by the experiment shown in FIG. 2 and a polarizing microscope in the same manner as in Example 1 (Tables 1 and 3). As a result, the angle dependence of the transmitted light intensity was small, and sufficient uniaxial orientation of the liquid crystal could not be confirmed. Moreover, as a result of observation with a polarizing microscope, the orientation of the liquid crystal was insufficient.

( Reference example 2 )
A liquid crystal cell A1 was created in the same manner as in Example 1. The liquid crystal cell A1 was heated at 50 ° C. and exposed to polarized ultraviolet rays to form the liquid crystal cell CE3.
In the obtained liquid crystal cell CE3, the orientation state of the low molecular weight liquid crystal was observed by the experiment shown in FIG. 2 and a polarizing microscope in the same manner as in Example 1 (Tables 1 and 3). As a result, the angle dependence of the transmitted light intensity was small, and sufficient uniaxial orientation of the liquid crystal could not be confirmed. Moreover, as a result of observation with a polarizing microscope, the orientation of the liquid crystal was insufficient.

( Reference example 3 )
A liquid crystal cell A1 was created in the same manner as in Example 1. After exposing the liquid crystal cell A1 to ultraviolet rays polarized at room temperature, the liquid crystal cell was heated at 30 ° C. for 30 minutes to form the liquid crystal cell CE4.
In the obtained liquid crystal cell CE4, the orientation state of the low molecular weight liquid crystal was observed by the experiment shown in FIG. 2 and a polarizing microscope in the same manner as in Example 1 (Tables 1 and 4). As a result, the angle dependence of the transmitted light intensity was small, and sufficient uniaxial orientation of the liquid crystal could not be confirmed. Moreover, as a result of observation with a polarizing microscope, the orientation of the liquid crystal was insufficient.

( Reference example 4 )
A liquid crystal cell A1 was created in the same manner as in Example 1. After exposing the liquid crystal cell A1 to ultraviolet rays polarized at room temperature, the liquid crystal cell was heated at 50 ° C. for 30 minutes to form the liquid crystal cell CE5.
In the obtained liquid crystal cell CE5, the orientation state of the low molecular weight liquid crystal was observed by the experiment shown in FIG. 2 and a polarizing microscope in the same manner as in Example 1 (Tables 1 and 4). As a result, the angle dependence of the transmitted light intensity was small, and sufficient uniaxial orientation of the liquid crystal could not be confirmed. Moreover, as a result of observation with a polarizing microscope, the orientation of the liquid crystal was insufficient.

From Examples 1 and 2 and Comparative Example 1, the liquid crystal compositions of Examples 1 and 2 having the liquid crystal composition of the present invention, that is, (A) a photoreactive polymer liquid crystal; and (B) a low molecular weight liquid crystal; It was found that the liquid crystal composition of Comparative Example 1 did not show photoreactivity while having photoreactivity. Further, it was found that by using the liquid crystal composition of Example 1, a liquid crystal cell in which the liquid crystal is oriented uniaxially can be produced. Furthermore, when Examples 1 and 2 were compared with Reference Examples 1 to 4 , it was found that a liquid crystal cell in which the liquid crystal was oriented in one axis could be produced by having a predetermined heating step.

Claims (11)

(A) A photoreactive polymer liquid crystal having a photoreactive side chain that causes at least one reaction selected from the group consisting of (A-1) photocrosslinking and (A-2) photoisomerization; and (B). ) Low molecular weight liquid crystal (excluding those having a polymerizable group and discotic liquid crystal compounds) ; a photoreactive liquid crystal composition having;
The weight ratio of (A) photoreactive high molecular weight liquid crystal to (B) low molecular weight liquid crystal ((A) photoreactive high molecular weight liquid crystal: (B) low molecular weight liquid crystal) is 3: 97 to 20:80. The photoreactive liquid crystal composition. The photoreactive liquid crystal composition according to claim 1 , wherein the (A) photoreactive polymer liquid crystal has ( A-2) a photoreactive side chain that causes a photoisomerization reaction . The composition according to claim 1 , wherein the (A) photoreactive polymer liquid crystal has a photoreactive side chain that causes (A-1) a photocrosslinking reaction.
The photoreactive polymer liquid crystal (A) has the following formulas (1) to (6).
(In the formula, A, B, and D are independent, single bond, -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 to 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, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R represents a hydroxy group, an alkoxy group having ₁ to 6 carbon atoms, or represents the same definition as Y1;
X is a single bond, -COO-, -OCO-, -N = N-, -CH = CH-, -C≡C-, -CH = CH-CO-O-, or -O-CO-CH = Representing CH-, when 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 composition according to any one of claims 1 to 3 , which has any one photoreactive side chain selected from the group consisting of.

The photoreactive polymer liquid crystal (A) has the following formulas (7) to (10).
(In the formula, A, B, and D are independent, single bond, -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 to 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 = Representing CH-, when 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, a halogen group, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. May be substituted with an alkyloxy group of;
R represents a hydroxy group, an alkoxy group having ₁ to 6 carbon atoms, or represents the same definition as Y1).
The composition according to any one of claims 1 to 4 , which has any one photoreactive side chain selected from the group consisting of.

The photoreactive polymer liquid crystal (A) has the following formulas (11) to (13).
(In the formula, 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 = Representing CH-, when 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 consisting of different 2 to 6 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 5 carbon atoms. (Representing an alkyl group of), -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. 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 photoreactive side chain selected from the group consisting of.

The photoreactive polymer liquid crystal (A) is the following formula (14) or (15).
(In the formula, 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 to 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 (A) photoreactive polymer liquid crystal has 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 = Representing CH-, when 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 photoreactive side chain represented by.

The (A) photoreactive polymer liquid crystal has the following formula (20) (in the formula, A is a single bond, -O-, -CH _2- , -COO-, -OCO-, -CONH-, -NH. Represents -CO-, -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 to 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 = Representing CH-, when 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) having a photoreactive side chain.

A dimming device formed by having a liquid crystal cell having the photoreactive liquid crystal composition according to any one of claims 1 to 9 . A light control element formed by having a liquid crystal cell having the photoreactive liquid crystal composition according to any one of claims 1 to 9 , wherein (B) a low molecular weight liquid crystal is predetermined in the liquid crystal cell. The above-mentioned dimming element having the orientation of.

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