JP2020076987A - Liquid crystal composition and liquid crystal dimming element - Google Patents

Abstract

To provide a reverse mode dimming element which exhibits good wettability and vertical orientation with respect to a plastic substrate, the haze rate of which at no voltage applied time is low, and which exhibits high transparency, a composition that is manufacturable with good yield, and an element using this composition.SOLUTION: Provided are a composition including a liquid crystal composition and a vertical orienting agent, the contact angle of which is 27 degrees to 37 degrees, with respect to a substrate the surface free energy of which is 28.31±1.06 mJ/m; a composition including a liquid crystal composition and a vertical orienting agent, the contact angle of which is 27 degrees to 37 degrees, with respect to a substrate the surface free energy of which is 39.0 to 50.0 mJ/m; a composition including a liquid crystal composition and a vertical orienting agent, the contact angle of which is 27 degrees to 37 degrees, with respect to a substrate the surface free energy of which is 27.25 to 50.0 mJ/m.SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal composition. Specifically, it relates to a composition for use in a liquid crystal light control device, which is a combination of a polymerizable compound and a non-polymerizable nematic liquid crystal compound.
The liquid crystal light control device is a light control device that utilizes light scattering. This liquid crystal light control device is used in building materials such as window glass and room partitions, and in-vehicle parts. For these elements, in addition to a hard substrate such as a glass substrate, a soft substrate such as a plastic film is used. In the liquid crystal composition sandwiched between these substrates, the alignment of liquid crystal molecules is changed by adjusting the applied voltage. Since the light transmitted through the liquid crystal composition can be controlled by this method, the liquid crystal light control device is widely used for displays, optical shutters, light control windows, smart windows, and the like.

  An example of the liquid crystal light control device is a polymer dispersion type of light scattering mode. The liquid crystal composition is dispersed in the polymer. This element has the following features. The device is easy to manufacture. Since it is easy to control the film thickness over a wide area, it is possible to manufacture a device having a large screen. Since no polarizing plate is required, bright display is possible. Wide viewing angle due to light scattering. Since this element has such excellent properties, it is expected to be used as a light control glass, a projection type display, a large area display and the like.

  Another example is a polymer network type liquid crystal light control device. In this type of device, the liquid crystal composition is present in a three-dimensional network of polymers. This composition differs from the polymer dispersion type in that it is continuous. This type of device also has the same characteristics as the polymer-dispersed device. There is also a liquid crystal light control device in which a polymer network type and a polymer dispersion type are mixed.

  The liquid crystal light control device has a normal mode and a reverse mode. In normal mode, it is opaque when no voltage is applied and becomes transparent when voltage is applied. In the reverse mode, it is transparent when no voltage is applied and becomes opaque when a voltage is applied. A composition having a positive dielectric anisotropy is used for a device having a normal mode. A composition having a negative dielectric anisotropy is used for an element having a reverse mode.

  Currently, the normal mode element is widely used, but when the element is frequently used in the transparent state, the reverse mode element can reduce the power consumption. Also, from the viewpoint of safety, a reverse mode element that becomes transparent when electricity cannot be applied to the element is effective for application to windows of automobiles and is being studied.

  In order to obtain a transparent state in a reverse mode device, it is general that the liquid crystal is vertically aligned when forming the polymer network. In order to obtain vertical alignment of liquid crystal, a vertical alignment film made of polyimide or the like is used (Patent Document 1). On the other hand, a method of vertically aligning the liquid crystal by adding a vertical aligning agent to the liquid crystal instead of the vertical alignment film has recently been studied (Patent Documents 2 and 3).

International Publication No. 2015/199148 JP, 2000-321562, A International Publication No. 2018/015323

  Plastic substrates are widely used from the viewpoints of weight reduction, area increase, thinning, and the like of liquid crystal light control devices. In many plastic substrates, when a reverse mode liquid crystal light control device is formed, the wettability of the composition with respect to the substrate is poor and cissing is likely to occur. Therefore, an object of the present invention is to provide a composition showing good wettability and vertical alignment on a plastic substrate, and further, a haze ratio when no voltage is applied is low and a reverse showing high transparency. It is an object of the present invention to provide a mode dimming device and a composition which can be manufactured with high yield.

The inventors have found the following [1] to [17].
[1] A composition containing a liquid crystal composition and a vertical aligning agent, wherein a contact angle is 37 degrees or less and 27 degrees or more with respect to a substrate having a surface free energy of 28.31 ± 1.06 mJ / m ^2. Composition.
[2] A composition containing a liquid crystal composition and a vertical aligning agent, wherein a contact angle is 37 degrees or less and 27 degrees or more with respect to a substrate having a surface free energy of 39.0 to 50.0 mJ / m ^2. Composition.
[3] A composition containing a liquid crystal composition and a vertical alignment agent, wherein the contact angle is 37 degrees or less and 27 degrees or more with respect to a substrate having a surface free energy of 27.25 to 50.0 mJ / m ^2. Composition.
[4] The composition according to any one of [1] to [3], wherein the component that increases the surface tension is a vertical alignment agent.
[5] The composition of [4], wherein the vertical alignment agent has a polymerizing group.
[6] The composition according to [5], wherein the vertical aligning agent has OH and the polymerizing group is a radical polymerizing group.
[7] The composition of [6], wherein the vertical aligning agent is a compound represented by formula (1) or a compound represented by formula (2).

(In formula (1),
R ¹ is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, alkyl having 1 to 20 carbons in which at least one hydrogen is replaced by fluorine, or carbon in which at least one hydrogen is replaced by fluorine. Is an alkoxy of the numbers 1 to 20,
Each ring M is 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,7-diyl,
Each Z ¹ is a single bond, alkylene having 2 to 10 carbons, or carbonyloxy, and CH _{2 which} is not adjacent to alkylene having 2 to 10 carbons may be replaced by O.
p is 0, 1, 2, or 3;
Ring L ¹ is a single bond, 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,7-diyl,
Z ² is a single bond or alkylene having 2 to 10 carbons, and CH _{2 which} is not adjacent to alkylene having 2 to 10 carbons may be replaced with O, and 1 H is hydroxy, (meth) acryloyl. Alternatively, it may be replaced with a group containing 2-hydroxymethylacryloyl. )

(In formula (2),
R ¹ is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, alkyl having 1 to 20 carbons in which at least one hydrogen is replaced by fluorine, or carbon in which at least one hydrogen is replaced by fluorine. Is an alkoxy of the numbers 1 to 20,
Each ring M is 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,7-diyl,
Each Z ¹ is a single bond, alkylene having 2 to 10 carbons, or carbonyloxy, and CH _{2 which} is not adjacent to alkylene having 2 to 10 carbons may be replaced by O.
p is 0, 1, 2, or 3;
Ring L ² is a single bond, 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,7-diyl,
Z ³ is alkylene having 2 to 10 carbon atoms, at least one H of CH ₂ not adjacent to O is replaced with OH, and non-adjacent CH ₂ of alkylene having 2 to 10 carbon is replaced with O. Often,
Alternatively, when Z ³ is a direct bond and ring L ² has a structure other than a single bond, at least one H bonded to ring L ² is replaced with OH,
R ² is hydrogen or methyl. )
[8] The composition according to any one of [4] to [7], which contains 6 parts by weight or more of a vertical alignment agent with respect to 100 parts by weight of the liquid crystal composition.
[9] Any one of [7] or [8], containing at least one polymerizable compound selected from the group of compounds represented by formula (3), formula (4), and formula (5). Composition.

(In Formula (3), Formula (4), and Formula (5), each ring G is independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine- 2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, wherein at least one hydrogen is fluorine, chlorine, cyano. , Hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkoxycarbonyl having 1 to 12 carbons, or alkanoyl having 1 to 12 carbons. may be substituted; Z ¹⁰ are each independently a single bond, -O -, - COO -, - OCO-, or a -OCOO-; Z ¹¹ is independently Te single _{bond, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - COS -, - SCO -, - OCOO -, - CONH -, - NHCO -, - CF 2 O-, _{-OCF 2 -, - CH 2 CH} 2 -, - CF 2 CF 2 -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH = CH -, - N = CH -, - CH = N -, - N = C (CH 3) -, - C (CH 3) = N -, - N = N-, or a -C≡C-; Z ¹² is a single bond, -O- or -COO-; X is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, carbon Alkoxy having 1 to 20 carbons or alkoxycarbonyl having 1 to 20 carbons ;
e is an integer of 1 to 4; f and g are independently an integer of 0 to 3; the sum of f and g is 1 to 4; h is an integer of 0 to 20 independently. R ² is independently hydrogen or CH ₃ . )
[10] The composition according to any one of [7] to [9], containing at least one polymerizable compound represented by the formula (6).

In formula (6), Z ¹³ is a single bond or alkylene having 1 to 80 carbons, and in this alkylene, at least one hydrogen is alkyl having 1 to 20 carbons, fluorine, or the following formula (7). may be substituted with a group represented by at least one of -CH ₂ -, -O -, - CO -, - COO-, or --OCO -, - NH-, or -N (R ⁵⁾ - in ^{May be} replaced; when they are replaced by a plurality of —O—, these —O— are not adjacent to each other; R ⁵ is alkyl having 1 to 12 carbons; at least one —CH ₂ —CH ₂ -May be replaced by -CH = CH-, or -C≡C-;
R ¹⁰ is alkyl having 1 to 20 carbons, in which at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ — is —O—, —CO—, —COO. -, or may be replaced by -OCO-; when it is replaced by a plurality of -O-, these -O- is not adjacent; at least one of -CH ₂ -, a saturated aliphatic compound of carbocyclic , A heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, or a heterocyclic unsaturated aliphatic compound, which may be replaced by a divalent group formed by removing two hydrogens. , These divalent groups have 5 to 35 carbon atoms, and at least one hydrogen may be replaced by alkyl having 1 to 12 carbon atoms, and in this alkyl, one —CH ₂ — is — O -, - CO -, - COO-, or it may be replaced by -OCO-; R ² is hydrogen or CH _3.

In the formula (7), Z ¹⁴ is alkylene having 1 to 12 carbons, R ² is hydrogen or CH ₃ , and * represents a connecting position.
[11] The composition according to any one of [1] to [10], wherein the liquid crystal composition contains at least one compound selected from the compounds represented by formula (10).

In the formula (10), R ²⁰ and R ²¹ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen being replaced by fluorine. Alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine; each ring A is independently 1,4-cyclohexylene, 2,5-tetrahydro- 2H-pyranylene, 1,4-phenylene, monofluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, chloro-fluoro-1,4-phenylene, or 7,8-difluorochroman-2. , 6-diyl, 1,1,7-trifluoroindan-2,5-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 4,7-difluorochromene-3,8-diyl,
At least one is 2,3-difluoro-1,4-phenylene, chloro-fluoro-1,4-phenylene, 7,8-difluorochroman-2,6-diyl, 1,1,7-trifluoroindane-2. , 5-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 4,7-difluorochromene-3,8-diyl; Z ²⁰ is a single bond, -CH = CH-, -C [identical to] C-, methyleneoxy, or carbonyloxy; c is an integer of 1 to 4.
[12] The composition of [11], wherein the compound of formula (10) is at least one selected from the structures below.

In formulas (10-1) to (10-33), R ²⁰ and R ²¹ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and carbon. Alkenyloxy having 2 to 12 carbons, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine, or alkenyl having 1 to 12 carbons having at least one hydrogen in fluorine.
[13] The composition according to any one of [1] to [11], wherein the liquid crystal composition contains at least one compound selected from the compounds represented by formula (11).

In the formula (11), R ²² and R ²³ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen being replaced by fluorine. Alkyl having 1 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine; each ring B is independently 1,4-cyclohexylene, 1,4-phenylene, Monofluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ²¹ is a single bond, —CH═CH—, —C≡C—, methyleneoxy, or carbonyloxy. Yes; c is an integer from 1 to 4.
[14] The composition of [13], wherein the compound represented by formula (11) is at least one selected from the group of compounds represented by formula (11-1) to formula (11-22). ..

In formulas (11-1) to (11-22), R ²² and R ²³ are independently at least alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least Alkyl having 1 to 12 carbons in which one hydrogen is replaced by fluorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine.
[15] The composition according to any one of [1] to [14], which contains a photopolymerization initiator as an additive.
[16] An element for switching between a transparent state and a scattering state, which uses the composition according to any one of [1] to [15].
[17] The device of [16] using a plastic substrate.

  The composition of the present invention provides a composition that exhibits good wettability and vertical alignment on a plastic substrate. Therefore, when the composition of the present invention is used, repelling between the substrate and the composition is suppressed, the haze ratio when no voltage is applied is low, and a reverse mode light control element exhibiting high transparency can be obtained with good yield. Can be manufactured.

  In the present invention, the “composition” is a material containing a liquid crystal compound and a vertical alignment agent. If necessary, the "composition" may contain a polymerizable compound. The composition may not have a nematic phase.

The “vertical aligning agent” is a compound having the ability to align the long axis of the molecule of the composition or the liquid crystal composition perpendicularly to the substrate. The "vertical aligning agent" may be a single compound or a mixture.
In the present invention, the “liquid crystal compound” is a compound having a liquid crystal phase and a compound serving as a component of a composition having a liquid crystal phase. The liquid crystal phase includes a nematic phase, a smectic phase and the like.

  In the present invention, the “liquid crystal composition” may include the above additives. These additives adjust or improve the properties of the optically active compound, the antioxidant, the ultraviolet absorber, the dye, the defoaming agent, the polar compound and other liquid crystal compositions. Unless otherwise specified, the amounts of the components in the “liquid crystal composition” are expressed as percentages based on the total weight of the liquid crystal compound in the “liquid crystal composition”.

The “polymerizable compound” is a polymerizable compound added for the purpose of forming a polymer network in the liquid crystal composite.
In the present invention, the “liquid crystal composite” is a product obtained by polymerizing the composition.

  In the present invention, the “liquid crystal light control device” is a device containing a composition or a liquid crystal composite, and adjusting the transmission or scattering state of light by the action of the composition or the liquid crystal composite. The liquid crystal light control device is a display, an optical shutter, a light control window, a smart window, or the like.

In the present invention, the “polymerizable group” is a functional group which, when included in a compound, is converted into a polymer having a large molecular weight by polymerization by means such as light, heat and a catalyst.
In the present invention, “polymerizable” is a form expression that means to include a polymerizable group.

In the present invention, "non-polymerizable" is an adjective meaning that it does not contain a polymerizing group.
In the present invention, the compound represented by the formula (O) and the compound (O) are the same.
In the present invention, “repellency” means a phenomenon in which, when a composition is present between substrates, a region where the composition does not exist is generated. For example, it is a phenomenon in which the composition layer does not exist on a part of the surface of the base material, or a dent appears such that the composition layer is pushed away from the surface of the base material.

In the present invention, the “maximum temperature” is simply the maximum temperature of the nematic phase.
In the present invention, the “minimum temperature” is simply the minimum temperature of the nematic phase.
“High specific resistance” means that the liquid crystal composition has a large specific resistance in the initial stage and has a large specific resistance after being used for a long time. “High voltage retention” means that the device has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature at the initial stage, and after a long time use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. Means to have a retention rate.

  In the present invention, "increasing the dielectric anisotropy" means increasing the absolute value of the dielectric anisotropy without changing the sign of the dielectric anisotropy. For example, when the dielectric anisotropy is positive, “increasing the dielectric anisotropy” means that when the composition has a value that increases positively and the dielectric anisotropy is negative, “Increasing the rate anisotropy” means that the value increases negatively.

  Regarding the liquid crystal compound, for example, 2-fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to left-right asymmetric divalent groups created by removing two hydrogens from a ring, such as tetrahydropyran-2,5-diyl. This rule also applies to divalent linking groups such as carbonyloxy (-COO- or -OCO-).

  For example, unless stated otherwise, tetrahydropyran-2,5-diyl does not position oxygen. Specifically, tetrahydropyran-2,5-diyl is

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Both are applicable.

In the present invention, the “mesogen” is a rigid site that exhibits liquid crystallinity.
The alkyl in the liquid crystal compound and the terminal group of the liquid crystal compound are linear or branched and do not contain cyclic alkyl. In order to expand the liquid crystal temperature range, a straight chain alkyl is preferable to a branched alkyl in a liquid crystal compound. Here, the terminal group is alkoxy, alkenyl or the like.
In order to increase the maximum temperature, 1,4-cyclohexylene in the liquid crystal compound preferably has a trans configuration.

<Composition>
The composition of the present invention is a composition containing a liquid crystal composition and a vertical alignment agent, and has a contact angle of not more than 37 degrees with respect to a substrate having a surface free energy of 28.31 ± 1.06 mJ / m ^2. More than a degree.
The composition of the present invention is a composition containing a liquid crystal composition and a vertical alignment agent, and has a contact angle of 37 degrees with respect to a substrate having a surface free energy of 39.0 to 50.0 mJ / m ^2. It is 27 degrees or more.
Furthermore, the composition of the present invention is a composition containing a liquid crystal composition and a vertical alignment agent, and has a contact angle of 37 degrees with respect to a substrate having a surface free energy of 27.25 to 50.0 mJ / m ^2. It is 27 degrees or more.

  The light control element has a pair of substrates and a composition interposed between the substrates. Plastic substrates such as polyethylene terephthalate, acrylic, and polycarbonate have the property of being difficult to wet with a composition containing a liquid crystal compound or a polymerizable compound. Therefore, in the present invention, the wettability is defined by the contact angle of the composition with respect to the substrate having the surface free energy in the predetermined range, and the composition having the contact angle in the predetermined range is applied to a plastic substrate or the like. It is to improve the wetness of.

  The substrate used for the device is not particularly limited as long as the composition has a contact angle in this range. One substrate may be a plastic substrate, and the other substrate may be a plastic substrate or a different substrate (glass substrate). Generally, an inorganic material such as glass has a property of easily wetting the composition.

Since the composition of the present invention contains a vertical aligning agent, it has a high self-orientation property and can be suitably used for a substrate having no alignment film.
When the contact angle of the composition is within the above numerical range, the liquid crystal retains vertical alignment of the liquid crystal and at the same time has good wettability to the plastic substrate. Therefore, it is possible to suppress the cissing of the composition at the time of manufacturing the device, and it is possible to manufacture a reverse mode device having no defective region. At this time, the wettability with respect to the substrate is further improved, so that the contact angle of the composition is more preferably 36.0 degrees or less, and most preferably 34.0 degrees or less. Further, in order to further improve the orientation of the liquid crystal, it is more preferable that the contact angle of the composition is 28.0 degrees or more, and most preferably 28.5 degrees or more. The contact angle can be adjusted by the weight ratio of each material in the composition, the type of vertical alignment agent, the type of polymerizable compound, and the like, which will be described in detail later.

Vertical Alignment Agent Adjust the surface tension of the composition to reduce the contact angle of the composition with the plastic substrate. Therefore, it is preferable that the composition contains a compound containing a functional group containing a hetero element. Examples of the functional group containing a hetero element include —OH, —O—, —NH ₂ , and —NH—.

  In the present invention, the vertical aligning agent having the functional group is used as a compound that adjusts the surface tension of the composition to reduce the contact angle. The vertical aligning agent used in the present invention is a compound or a mixture thereof having a property of vertically aligning the liquid crystal compound in the composition in contact with the substrate with respect to the substrate. The vertical aligning agent used in the present invention exhibits good vertical aligning property with respect to the liquid crystal compound, improves wettability between the plastic substrate and the composition, and has a uniform haze ratio in a wide area in the light control device. Can be given.

  In order to adjust the surface tension, a vertical aligning agent having an OH group at the end is preferable. For example, an alcohol compound having 8 to 20 carbon atoms can be used, and 1-dodecanol and the like are exemplified.

  Further, in order to stably drive the light control element without deterioration of the light control element over time, the vertical alignment agent is preferably a compound having a polymerizing group. The polymerizing group contained in the vertical alignment agent is preferably a radical polymerizing group capable of polymerizing by radical polymerization. Further, the polymerizing group contained in the vertical alignment agent is more preferably a polymerizing group such as an acryloyl group because it is easily miscible with the liquid crystal composition and particularly has high solubility in the liquid crystal composition.

  The vertical aligning agent suitable in the present invention is preferably a compound selected from the group represented by the following formulas (1) and (2).

In equation (1),
R ¹ is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, alkyl having 1 to 20 carbons in which at least one hydrogen is replaced by fluorine, or carbon in which at least one hydrogen is replaced by fluorine. Is an alkoxy of the numbers 1 to 20,
Each ring M is 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,7-diyl,
Each Z ¹ is a single bond, alkylene having 2 to 10 carbons, or carbonyloxy, and CH _{2 which} is not adjacent to alkylene having 2 to 10 carbons may be replaced by O.
p is 0, 1, 2, or 3;
Ring L ¹ is a single bond, 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,7-diyl,
Z ² is a single bond or alkylene having 2 to 10 carbons, and CH _{2 which} is not adjacent to alkylene having 2 to 10 carbons may be replaced with O, and 1 H is hydroxy, (meth) acryloyl. Alternatively, it may be replaced with a group containing 2-hydroxymethylacryloyl.

In equation (2),
R ¹ , the rings M, Z ¹ and p are the same as in the compound of formula (1).
Ring L ² is a single bond, 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,7-diyl,
Z ³ is alkylene having 2 to 10 carbon atoms, at least one H of CH ₂ not adjacent to O is replaced with OH, and non-adjacent CH ₂ of alkylene having 2 to 10 carbon is replaced with O. Often,
Alternatively, when Z ³ is a direct bond and ring L ² has a structure other than a single bond, at least one H bonded to ring L ² is replaced with OH,
R ² is hydrogen or methyl.

  Suitable examples of the compound represented by the formula (1) or (2) are shown.

In formula (1-1) to formula (1-12),
R ⁵⁰ and R ⁵¹ are alkyl having 7 to 20 carbons, alkoxy having 7 to 20 carbons, alkyl having 5 to 20 carbons in which at least one hydrogen is replaced by fluorine, or at least one hydrogen being replaced by fluorine Is an alkoxy having 5 to 20 carbon atoms,
R ⁵² and R ⁵³ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine, or at least one hydrogen being replaced by fluorine Is an alkoxy having 1 to 12 carbon atoms,
Z ²¹¹ is a single bond, a straight-chain alkylene of 1 to 6 carbon atoms or -O (CH _{2), n} - a, where, n is 2 to 6.

In formula (1-13) to formula (1-19),
R ⁵⁰ , R ⁵¹ and R ⁵² are the same as those in the formulas (1-1) to (1-12).
Z ²¹² is a hydroxy group, a (meth) acryloyloxy group, or a 2-hydroxymethylacryloyloxy group.

In formula (2-1) to formula (2-4),
R ⁵⁰ and R ⁵¹ are the same as those in the formulas (1-1) to (1-3).
R ² is hydrogen or methyl similarly to the above formula (2).

  In order to adjust the contact angle of the composition, the formulas (1-1) to (1-3), (1-13) to (1-15), and (2-1) to (2-4) are used. It is preferable to use the compound described above. In order to reduce the deterioration of the performance of the liquid crystal light control device over time, it is preferable to use the compounds represented by (1-2) to (1-12) and (1-14) to (1-19). .. Furthermore, in order to exhibit both effects, it is preferable to use two or more kinds of the above-described vertical aligning agents having different effects in combination.

  The content of these vertical alignment agents may be in the range that gives the contact angle that is a feature of the present invention. This range is 5 parts by weight or more based on 100 parts by weight of the liquid crystal composition, and in order to improve wettability and give a lower contact angle, 6 parts by weight or more is preferable, and 7 parts by weight or more is more preferable. .. Most preferred is 8 parts by weight or more.

Further, in order to maintain the vertical alignment of the liquid crystal, it is preferably 20 parts by weight or less, more preferably 15 parts by weight or less. Most preferably, it is 12 parts by weight or less.
The content of the vertical aligning agent with respect to the weight of the liquid crystal composition is not particularly limited as long as the function of vertically aligning the liquid crystal can be exhibited. Usually, if the amount is 0.5 part by weight or more, most of them exhibit the effect.

-Polymerizable compound The vertical aligning agent is a polymerizable compound, and it is preferable to include a polymerizable compound other than the vertical aligning agent. By including the polymerizable compound in the composition, the haze ratio in the scattering state of the light control device can be improved and the driving voltage can be lowered. Further, in order to facilitate miscibility with the liquid crystal compound, this polymerizable compound is preferably a compound having a skeleton similar to that of the liquid crystal. In order to reduce the deterioration of the performance of the liquid crystal light control device over time, it is preferable that the polymerizable compound contains three or more polymerizable groups.

The polymerizable compound used in the present invention is a compound having poor performance for vertically aligning a liquid crystal composition and poor performance for increasing surface tension.
Specifically, the compound (3), the compound (4), the compound (5) and the compound (6) can be preferably used. A plurality of these polymerizable compounds may be selected and used in combination.

  The compounds represented by formula (3), formula (4), and formula (5) are represented by the following general formula.

Compound (3), the compound (4) and the compound (5) at least one acryloyloxy (-OCO-CH = CH _2, the formula (3) R ² is hydrogen to (5)) or methacryloyloxy (- having OCO- a _{(CH 3) C = CH 2} , R 2 is CH ₃ in the formula (3) to (5)). The liquid crystal compound has a mesogen (a rigid portion that exhibits liquid crystallinity), and these compounds also have a mesogen. Therefore, these compounds are aligned in the same direction by the action of the alignment film together with the liquid crystal compound. This orientation is maintained after polymerization. Such a liquid crystal composite has high transparency.

  In formula (3), formula (4), and formula (5), each ring G is independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine-2. , 5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, wherein at least one hydrogen is fluorine, cyano, hydroxy, Formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, substituted with alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkoxycarbonyl having 1 to 12 carbons, or alkanoyl having 1 to 12 carbons Good. In formula (3), formula (4), and formula (5), preferred rings are 1,4-cyclohexylene, 1,4-phenylene, monofluoro-1,4-phenylene, 2-methyl-1, It is 4-phenylene, 2-methoxy-1,4-phenylene, or 2-trifluoromethyl-1,4-phenylene. A more preferred ring is 1,4-cyclohexylene or 1,4-phenylene.

Z ^{10 s} are each independently a single bond, —O—, —COO—, —OCO—, or —OCOO—;
Z ^11's are each independently a single bond, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, _{-CF 2 O -, - OCF 2} -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH = CH -, - N = CH -, - CH = N -, - N = C (CH 3) -, - C (CH 3) = N -, - N = N-, or -C≡ C-;
Z ¹² represents a single bond, -O- or -COO -, - OCO-, or -OCOO-.

At this time, in formula (5), preferred Z ¹¹ is a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH ₂ CH ₂ COO—, or -OCOCH ₂ CH ₂ - it is.

X is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, or alkoxy having 1 to 20 carbons. Carbonyl;
e is an integer of 1 to 4; f and g are independently an integer of 0 to 3; the sum of f and g is 1 to 4; h is an integer of 0 to 20 independently. R ² is independently hydrogen or CH ₃ as in (2).

  Specific examples of the compound (3) are shown below.

In formulas (3-1) to (3-24), R ² is hydrogen or methyl, as in formula (2), and d is an integer of 1 to 20. Since the compatibility with the composition is good, d is preferably an integer of 3 to 12.

  Specific examples of the compound (4) are shown below.

In formulas (4-1) to (4-31), R ² is independently hydrogen or CH ₃ , and f and h are independently integers from 1 to 20. From the viewpoint of good compatibility with the composition, f and h are preferably integers of 3 to 12. From the viewpoint of ease of production, it is more preferable that f = h.

  Specific examples of the compound (5) are shown below.

In formulas (5-1) to (5-10), R ² is independently hydrogen or CH ₃ , and i, k, and m are independently integers from 1 to 20. It is preferable that i, k, and m are integers of 3 to 12 because of good compatibility with the composition. It is more preferable that i = k = m for ease of manufacturing.

  The compound represented by Formula (6) is a polymerizable compound other than Formula (3), Formula (4), and Formula (5), and is not a liquid crystal compound. For this reason, the effect of reducing the haze ratio when transparent is small. However, it is an inexpensive material, has a high effect of reducing the driving voltage, and is suitable for use in the composition for improving the device characteristics.

In formula (6), Z ¹³ is a single bond or alkylene having 1 to 80 carbons, and in this alkylene, at least one hydrogen is alkyl having 1 to 20 carbons, fluorine, or the following formula (7). may be substituted with a group represented by at least one of -CH ₂ -, -O -, - CO -, - COO-, or --OCO -, - NH-, or -N (R ⁵⁾ - in When substituted with a plurality of —O—, these —O— are not adjacent to each other; R ⁵ is alkyl having 1 to 12 carbons; and at least one —CH ₂ —CH ₂ — is , -CH = CH-, or -C = C-;
R ¹⁰ is alkyl having 1 to 20 carbons, in which at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ — is —O—, —CO—, —COO. -, or -OCO- may be replaced by; if Okikaeraru a plurality of -O-, these -O- is not adjacent; at least one of -CH ₂ -, a saturated aliphatic carbocyclic A compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, or a heterocyclic unsaturated aliphatic compound, which may be replaced by a divalent group formed by removing two hydrogens Well, in these divalent groups, the number of carbon atoms is 5 to 35, and at least one hydrogen may be replaced by alkyl having 1 to 12 carbon atoms, and in this alkyl, one —CH ₂ — is -O -, - CO -, - COO-, or may be replaced by -OCO-; R ² is hydrogen or CH _3.

In the formula (7), Z ¹⁴ is alkylene having 1 to 12 carbons, R ² is hydrogen or CH ₃ , and * represents a connecting position.
At this time, when the compound (6) is volatile, its oligomer may be used.

In order to reduce the driving voltage of the device, it is preferable to select a monofunctional compound as the compound represented by the formula (6).
Among the compounds represented by the formula (6), monofunctional compounds are shown in the following (6-1-1) to (6-1-6).

In formulas (6-1-1) to (6-1-5), R ³⁰ is alkyl having 5 to 20 carbon atoms, and in this alkyl, at least one —CH ₂ — is —O—, -CO -, - COO-, or may be replaced by -OCO-, R ³¹ are each independently alkyl having 3 to 10 carbon atoms, in the alkyl, at least one of -CH ₂ -, It may be replaced with -O-, -CO-, -COO-, or -OCO-.

In order to improve the adhesion of the device, the compound represented by the formula (6) is further substituted with the compound represented by the formula (7), di (meth) acrylate, tri (meth) acrylate, or tetra. It is preferred to use polyfunctional (meth) acrylates such as (meth) acrylate. When the molecular chain of Z ¹³ is short, the cross-linking sites of the polymer are close to each other, resulting in a small mesh. When the molecular chain of Z ¹³ is long, the cross-linking site of the polymer is separated and the degree of freedom of molecular motion is improved, so that the driving voltage is lowered. When Z ¹³ has a branched structure, the degree of freedom is further improved, so that the driving voltage is further reduced. In the compound (6), when the number of the polymer groups is large, the polymer surrounding the droplet becomes hard or the network becomes dense due to the crosslinking.

  Suitable examples of the polyfunctional compound (6) are shown in (6-2-1) to (6-2-5) below.

In the formula (6-2-1), n is an integer of 1 to 10,
In the formula (6-2-2), m is an integer of 2 to 20,
In formula (6-2-3), R ³⁵ is independently alkyl having 1 to 5 carbons, and R ³⁶ is independently alkyl having 1 to 20 carbons. At least one —CH ₂ — may be replaced by —O—, —CO—, —COO—, or —OCO—, and R ³⁵ and R ³⁶ in the same formula may be the same or different. Z ⁷ is alkylene having 10 to 30 carbon atoms, and in this alkylene, at least one —CH ₂ — is replaced with —O—, —CO—, —COO—, or —OCO—. And the alkylene includes those having a branched alkyl,
In formula (6-2-4), p is an integer of 3 to 10, Q ¹ and Q ² are different from each other, and are hydrogen or methyl,
In the formula (6-2-5), R ³⁷ is OH, (meth) acryloyl, or a structure in which a residue other than R ^{37 in the} formula (6-2-5) is bonded via —O—, and R ² Are each independently hydrogen or CH ₃ .

  Specific examples of the compound (6-2-3) are shown below.

In formula (6-2-3-1) and formula (6-2-3-2), for example, R ³⁸ is ethyl, R ³⁹ is independently —CH ₂ OCOC ₉ H ₁₉ , —CH _{2 OCOC 10 H 21, -CH 2 OC} 8 H 17, or -CH ₂ OC ₁₁ H _23.

In order to improve other properties, a polymerizable compound other than the polymerizable compounds of formulas (3) to (6) may be used in combination.
The content of the polymerizable compound (the total amount of the polymerizable compounds represented by the formulas (3) to (6)) is 1 part by weight or more, preferably 3 parts by weight or more, based on 100 parts by weight of the liquid crystal composition. It is preferably at least parts by weight.

The upper limit is 50 parts by weight or less, preferably 45 parts by weight or less, and preferably 40 parts by weight or less, based on the total weight of the liquid crystal composition.
When a plurality of polymerizable compounds are used, the type and ratio thereof are appropriately selected in view of the haze ratio in the scattering state in the light control device, the driving voltage, the ease of mixing with the liquid crystal compound, and the like.

  The ratio of the polymerizable compounds of formulas (3) to (5) having a mesogenic structure in the polymerizable compound is 1% by weight or more, preferably 3 parts by weight or more, based on the total amount of the polymerizable compounds, and 5 It is preferably at least parts by weight. The upper limit is 30 parts by weight or less, preferably 20 parts by weight or less, and preferably 15 parts by weight or less, based on the total amount of the polymerizable compound.

  In order to improve the stability of the liquid crystal composite and the adhesion between the substrate and the liquid crystal composite, in the polymerizable compounds of the formulas (3) to (6), the polyfunctional compound of the formula (4) or the formula (5) is used. Is particularly preferably used.

Liquid crystal composition As the liquid crystal composition, known liquid crystal compounds can be used, but from the viewpoint of improving the rate of change in the Haze ratio of the device, lowering the driving voltage, and improving weather resistance, the formula (10) and It preferably contains at least one liquid crystal compound selected from formula (11). The liquid crystal compounds of formulas (10) and (11) are non-polymerizable nematic liquid crystal compounds, and a liquid crystal composition containing this compound is used as a nematic liquid crystal component. By using such a liquid crystal composition in combination with the above-mentioned polymerizable compound, it has a low driving voltage, high transparency when no voltage is applied, and high haze when a voltage is applied. Provided is a polymerizable composition for use in a liquid crystal light control device.

  The compound represented by the formula (10) is a so-called negative type liquid crystal compound in which dielectric anisotropy is expressed in the direction perpendicular to the molecular long axis of the compound.

In equation (10),
R ²⁰ and R ²¹ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, and at least one hydrogen being fluorine. A substituted alkyl having 1 to 12 carbons or an alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine, and c is an integer of 1 to 4,
Each ring A is independently 1,4-cyclohexylene, 2,5-tetrahydro-2H-pyranylene, 1,4-phenylene, monofluoro-1,4-phenylene, 2,3-difluoro-1,4. -Phenylene, chloro-fluoro-1,4-phenylene, 7,8-difluorochroman-2,6-diyl, 1,1,7-trifluoroindane-2,5-diyl, 4,6-difluorodibenzofuran-3 , 7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 4,7-difluorochromene-3,8-diyl,
At least one ring A is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 7,8-difluorochroman-2,6-diyl, 1,1,7 -Trifluoroindane-2,5-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 4,7-difluorochromene-3,8 -Jeil,
Z ²⁰ is a single bond, —CH═CH—, —C≡C—, methyleneoxy, or carbonyloxy.

  The compound represented by the formula (11) is a liquid crystal compound that exhibits little dielectric anisotropy or has a small dielectric anisotropy.

In equation (11),
R ²² and R ²³ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and 1 to 12 carbons in which at least one hydrogen has been replaced by fluorine. Or an alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine, c is an integer from 1 to 4,
Each ring B is independently 1,4-cyclohexylene, 1,4-phenylene, monofluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or naphthalene-2,6-. Jeil,
Z ²¹ is a single bond, —CH═CH—, —C≡C—, methyleneoxy, or carbonyloxy.

In order to increase stability to light and heat, in the formula (10) and the formula (11), R ²⁰ , R ²¹ , R ²² and R ²³ are preferably alkyl having 1 to 12 carbons, and 1 to 8 carbons. Is more preferable, and alkyl having 1 to 5 carbon atoms is further preferable.

In order to enhance the dielectric anisotropy and / or to extend the driving temperature range of the liquid crystal light control device, R ²⁰ , R ²¹ , R ²² and R ²³ in Formula (10) and Formula (11) are , An alkoxy having 1 to 12 carbons is preferable, an alkoxy having 1 to 8 carbons is more preferable, and an alkoxy having 1 to 5 carbons is further preferable.

In order to enhance the dielectric anisotropy and / or to widen the driving temperature range of the liquid crystal light control device, R ²⁰ , R ²¹ , R ²² and R ²³ in formula (10) and formula (11) are , Vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl. , 4-hexenyl, or 5-hexenyl is preferable, and vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl is more preferable.

  In this case, the conformation of the double bond of alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl is preferably trans, 2-butenyl and 2-pentenyl. The conformation of the double bond of 2-hexenyl is preferably cis.

In order to enhance the dielectric anisotropy and / or to extend the driving temperature range of the liquid crystal light control device, R ²⁰ , R ²¹ , R ²² and R ²³ in Formula (10) and Formula (11) are , Vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy is preferable, and allyloxy or 3-butenyloxy is more preferable.

In order to enhance the dielectric anisotropy and / or to extend the driving temperature range of the liquid crystal light control device, R ²⁰ , R ²¹ , R ²² and R ²³ in Formula (10) and Formula (11) are , Fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl, or 8-fluorooctyl is preferable, 2-fluoroethyl, 3-fluoro. More preferred is propyl, 4-fluorobutyl, or 5-fluoropentyl.

  In order to enhance the dielectric anisotropy and / or to extend the driving temperature range of the liquid crystal light control device, in the formula (10), ring A is 1,4-cyclohexylene or 1,4-phenylene, respectively. , 2,3-Difluoro-1,4-phenylene or 7,8-difluorochroman-2,6-diyl are preferred.

In formula (10), ring A is preferably chloro-fluoro-1,4-phenylene in order to reduce the optical anisotropy.
In order to enhance the dielectric anisotropy and / or to widen the driving temperature range of the liquid crystal light control device, in the formula (11), the ring B is 1,4-cyclohexylene, 1,4-phenylene or mono. Fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, or naphthalene-2,6-diyl is preferred.

In formula (11), the ring B is preferably naphthalene-2,6-diyl in order to increase the refractive index anisotropy.
In formula (10), Z ²⁰ and Z ²¹ are preferably a single bond, —CH═CH—, —C≡C—, carbonyloxy, or methyleneoxy for expanding the liquid crystal temperature range.

In formula (10), Z ²⁰ or Z ²¹ is preferably a single bond or ethylene in order to widen the driving temperature range of the liquid crystal light control device.
In formula (10), Z ²⁰ or Z ²¹ is preferably a single bond in order to improve stability against light and heat.

In order to enhance the dielectric anisotropy, in formula (10), Z ²⁰ or Z ²¹ is preferably methyleneoxy.
In order to increase the refractive index anisotropy, in formula (10), Z ²⁰ or Z ²¹ is preferably a single bond, —CH═CH—, and —C≡C—.

  In order to keep the temperature of the liquid crystal composition within the practical range, in the formula (11), c is preferably an integer of 1 to 4. In order to lower the minimum temperature, in the formula (11), c is preferably 1. In order to raise the maximum temperature, in the formula (11), c is preferably 2 or 3.

  Compound (10) and compound (11) have the properties shown in Table 1. In Table 1, L indicates that the absolute value of the characteristic is large, M indicates that the absolute value of the characteristic is medium, S indicates that the absolute value of the characteristic is small, and 0 indicates that the absolute value of the characteristic is extremely small. means. Those skilled in the art can adjust the characteristics of the liquid crystal composition based on Table 1.

In the present invention, either the compound (10) or the compound (11) may be used as the liquid crystal compound, or both the compound (10) and the compound (11) may be used.
The content of the compound (10) in the liquid crystal composition is 10 to 100% by weight in order to reduce the driving voltage in the liquid crystal light control element and / or to widen the usable temperature range in the liquid crystal light control element. %, More preferably 20 to 90% by weight, even more preferably 30 to 85% by weight, even more preferably 40 to 80% by weight.
In order to broaden the usable temperature range in the liquid crystal light control device, the content of the compound (11) in the liquid crystal composition is preferably 0 to 90% by weight, more preferably 10 to 80% by weight, and 15 to 70% by weight. % By weight is more preferred and 20 to 60% by weight is even more preferred.

  The liquid crystal composition may not contain the other liquid crystal compounds of the compounds (10) and (11), but may further contain other liquid crystal compounds, if necessary, together with additives and the like. The "other liquid crystal compound" is a non-polymerizable liquid crystal compound different from the formulas (10) and (11). Such compounds are mixed with the liquid crystal composition for the purpose of further adjusting the characteristics, but known compounds can be used without particular limitation. Examples of such a compound include a so-called positive type liquid crystal compound in which dielectric anisotropy is expressed in the direction of the long axis of the compound.

  The amount of the liquid crystal composition contained in the composition according to the present invention is in the range of 50% by weight to 99% by weight based on the total weight of the composition including the vertical alignment agent, the polymerizable compound and the liquid crystal composition. is there. A more desirable ratio is in the range of 55% by weight to 97% by weight. A particularly desirable ratio is in the range of 60% by weight to 95% by weight.

  Preferred liquid crystal compounds are shown. Preferred compound (10) is at least one selected from compound (10-1) to compound (10-33). In these compounds, at least one of the first components is compound (10-1), compound (10-2), compound (10-3), compound (10-4), compound (10-6), compound ( It is preferable that it is 10-7), a compound (10-8), or a compound (10-10). At least two of the first components are compound (10-1) and compound (10-6), compound (10-1) and compound (10-10), compound (10-3) and compound (10-6), The compound (10-3) and the compound (10-10), the compound (10-4) and the compound (10-6), or the combination of the compound (10-4) and the compound (10-10) is preferable.

In formulas (10-1) to (10-33), R ²⁰ and R ²¹ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and carbon. Alkenyloxy having 2 to 12 carbon atoms, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine, or alkenyl having 2 to 12 carbons having at least one hydrogen replaced in fluorine.

  Preferred compound (11) is at least one compound selected from compounds (11-1) to (11-22). In these compounds, at least one of the second components is compound (11-1), compound (11-3), compound (11-5), compound (11-6), compound (11-8), or compound. It is preferably (11-9). At least two of the second components are compound (11-1) and compound (11-5), compound (11-1) and compound (11-6), compound (11-1) and compound (11-8), compound. (11-1) and compound (11-9) compound (11-3) and compound (11-5), compound (11-3) and compound (11-6), compound (11-3) and compound (11 -8) or a combination of the compound (11-3) and the compound (11-9) is preferable.

In formulas (11-1) to (11-22), R ²² and R ²³ are independently at least alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least Alkyl having 1 to 12 carbons in which one hydrogen is replaced by fluorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine.

  The above-mentioned compounds used in the present invention are Organic Synthesis, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Synthesis, Comp. (Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen) and the like. The composition is prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and dissolved by heating.

-Other additives, etc. The composition according to the present invention may contain additives in addition to the vertical alignment agent, the polymerizable compound, and the liquid crystal composition. Examples of the additive include an optically active compound, an antioxidant, an ultraviolet absorber, a dye, a defoaming agent, a polymerization initiator and a polymerization inhibitor.

  For example, an optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compound (20-1) to compound (20-6). A desirable ratio of the optically active compound is 5% by weight or less based on the weight of the composition. A more desirable ratio is in the range of 0.01% by weight to 2% by weight.

In the formula (20-6), R ²⁵ is hydrogen or an alkyl group having 1 to 10 carbon atoms.
In order to prevent a decrease in the specific resistance due to heating in the air, or to maintain a large voltage holding ratio not only at room temperature but also at a temperature near the upper limit temperature after using the device for a long time, an antioxidant composition is used. Is added to the product. Preferred examples of the antioxidant include compounds (21) in which n is an integer of 1 to 9 and the like.

  In compound (21), preferred n is 1, 3, 5, 7, or 9. More desirable n is 7. Since the compound (21) in which n is 7 has low volatility, it is effective in maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time. In order to obtain the effect, the preferable ratio of the antioxidant is about 50 ppm or more based on the weight of the composition, and about 600 ppm or less so that the upper limit temperature is not lowered or the lower limit temperature is not raised. A more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.

  Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. The preferable ratio of these absorbents and stabilizers is about 50 ppm or more based on the weight of the composition to obtain the effect, and about 10000 ppm or less so as not to lower the upper limit temperature or to raise the lower limit temperature. Is. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

  A dichroic dye such as an azo dye, anthraquinone dye, or the like is added to the composition in order to adapt to a GH (guest host) mode device. A desirable ratio of the dye is in the range of 0.01% by weight to 10% by weight based on the weight of the composition. An antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition to prevent foaming. The preferable ratio of the defoaming agent is about ppm or more based on the weight of the composition in order to obtain its effect, and 1000 ppm or less to prevent display defects. A more desirable ratio is in the range of 1 ppm to 500 ppm.

  The polymerizable compound in the composition according to the present invention is polymerized by irradiation with ultraviolet rays. From the viewpoint of efficiency, it is preferable to polymerize in the presence of a polymerization initiator such as a photopolymerization initiator. Appropriate conditions for the polymerization, the appropriate type of initiator and the amount added to the composition are known to the person skilled in the art and are described in the literature. For example, based on the weight of the composition, 0.5 to 10% by weight is preferable, and 2 to 7% by weight is particularly preferable. Further, as the type of the photopolymerization initiator, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF) is suitable for radical polymerization.

  When the composition is stored, a polymerization inhibitor may be added to prevent polymerization of the polymerizable compound. Examples of the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like. The addition amount of the polymerization inhibitor is not particularly limited as long as it does not cause polymerization, but it is usually preferably used in the range of 10 to 1000 ppm with respect to the weight of the composition.

<Liquid crystal complex>
Finally, the structure of the liquid crystal composite will be described.
The liquid crystal composite is prepared by polymerizing the polymerizable compound in the composition. The polymer of the polymerizable compound undergoes phase separation with the liquid crystal composition to give a liquid crystal composite. Since this liquid crystal composite contains a vertical alignment agent, the liquid crystal composition is vertically aligned. Therefore, it is suitable for a reverse mode light control element that is transparent when no voltage is applied and becomes opaque when a voltage is applied. Increasing the difference between ne of the liquid crystal composition and the refractive index of the polymer increases the haze ratio of the liquid crystal light control device. By reducing the difference between the no of the liquid crystal composition and the refractive index of the polymer, the transparency of the liquid crystal light control device is improved. Since the no of the liquid crystal composition does not largely depend on the type of the liquid crystal composition, it is preferable to increase the haze rate by increasing ne, that is, increasing the optical anisotropy (Δn) of the liquid crystal composition. Δn is preferably 0.16 or more, more preferably 0.18 or more.

  Note that Δn is given as ne-no. Here, ne is the refractive index when the liquid crystal is horizontally aligned in one direction, and when linearly polarized light having a polarization axis in the alignment direction is applied to the liquid crystal from the vertical direction, no is orthogonal thereto. It is a refractive index for linearly polarized light having a polarization axis in the direction.

  When a device composed of a liquid crystal composite is prepared from the composition, the polymerizable compound is polymerized. Polymerization causes the polymer to phase separate from the composition. As a result, a light control layer made of a liquid crystal composite is formed between the substrates. This light control layer is classified into a polymer dispersion type, a polymer network type, and a mixed type of both. It is preferable that the mesh in the network structure is small. The preferable mesh size is 0.2 to 2 μm, more preferably 0.2 to 1 μm, and particularly preferably 0.3 to 0.7 μm.

  In a polymer dispersion type element, a liquid crystal composition is dispersed like droplets in a polymer. Each of the droplets is independent and not continuous. On the other hand, in the polymer network type device, the polymer has a three-dimensional network structure, and the liquid crystal composition is surrounded by the network but is continuous. In these devices, it is preferable that the proportion of the liquid crystal composition based on the liquid crystal composite is large in order to increase Haze and decrease the driving voltage. On the other hand, in order to improve the adhesion between the substrates of the device and increase the mechanical strength, it is preferable that the proportion of the polymer is large. For the purpose of increasing the response speed, it is preferable that the proportion of the polymer is large.

  The ratio of the liquid crystal composition in the liquid crystal composite does not change significantly from the ratio in the composition before polymerization, and the preferred ratio is in the range of 50% by weight to 99% by weight based on the weight of the liquid crystal composite. .. A more desirable ratio is in the range of 55% by weight to 97% by weight. A particularly desirable ratio is in the range of 60% by weight to 95% by weight. A preferred ratio of the polymer is 1% by weight to 50% by weight based on the weight of the liquid crystal composite. A more desirable ratio is in the range of approximately 3% to approximately 45% by weight. A particularly desirable ratio is in the range of approximately 5% to approximately 40% by weight.

  The detailed manufacturing method of the liquid crystal composite will be described below. First, the composition is sandwiched between a pair of transparent substrates, at least one of which has a transparent electrode, at a temperature higher than the upper limit temperature by a vacuum injection method or a liquid crystal dropping method.

The composition and device of the present invention are adjusted to have a predetermined contact angle with a substrate having a surface free energy of 28.31 ± 1.06 mJ / m ² .
Further, the composition and device of the present invention are adjusted to have a predetermined contact angle with a substrate having a surface free energy of 39.0 to 50.0 mJ / m ² .
Further, the composition and device of the present invention are adjusted to have a predetermined contact angle with respect to a substrate having a surface free energy of 27.25 to 50.0 mJ / m ² .
As long as the composition has a predetermined contact angle with the substrate, the substrate actually used is appropriately selected depending on the type of device. The substrate may be subjected to surface treatment such as UV cleaning or plasma treatment so as to have a predetermined contact angle.

  Specifically, all known substrates such as films made of polyethylene terephthalate, acrylic and polycarbonate, and plate-like substances such as glass and quartz can be used. Since the composition of the present invention has a specific contact angle with the substrate having the above surface free energy, it has good coatability. Among these substrates, it can be suitably used for plastic film substrates such as polyethylene terephthalate, acrylic, and polycarbonate. A transparent electrode is placed on these substrates to obtain an element. Examples of transparent electrodes are in-tin tin oxide (ITO) and conductive polymers. Although an alignment film may be provided on the transparent electrode, the composition of the present invention has a high self-vertical alignment property and thus can be suitably used for a substrate having no alignment film.

  The composition of the present invention may be applied on a substrate provided with an alignment film. As such an alignment film, a thin film such as polyimide or polyvinyl alcohol is suitable. For example, the polyimide alignment film can be obtained by applying a polyimide resin composition on a transparent substrate, thermally curing it at a temperature of 180 ° C. or higher, and rubbing it with a cotton cloth or rayon cloth if necessary.

  The pair of substrates are opposed to each other with the transparent electrode layer facing inside. A spacer may be added to make the thickness between the substrates uniform. Examples of spacers are glass particles, plastic particles, alumina particles, photo spacers and the like. The thickness of the light control layer is preferably 2 to 50 μm, more preferably 5 to 20 μm. A general-purpose sealant can be used to bond the pair of substrates together. An example of the sealing agent is an epoxy thermosetting composition.

  The polymerizable compound is polymerized by irradiation with heat or ultraviolet rays, and ultraviolet irradiation is particularly preferable for the polymerization of the polymerizable compound. Examples of the ultraviolet irradiation lamp are a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an LED lamp and the like. When a photopolymerization initiator is used, the wavelength of ultraviolet rays is preferably in the absorption wavelength region of the photopolymerization initiator. Avoid the absorption wavelength region of the liquid crystal composition. A preferred wavelength is 330 nm or more. A more preferable wavelength is 350 nm or more. The reaction may be carried out near room temperature or may be carried out by heating.

  In such an element, a light absorption layer, a diffuse reflection plate, or the like can be arranged on the back surface of the element, if necessary. Functions such as specular reflection, diffuse reflection, retroreflection, and hologram reflection can be added.

  Such an element has a function as an element for switching between a transparent state and a scattering state, for example, a light control film or a light control glass. When the element is in the form of a film, it can be attached to an existing window or sandwiched between a pair of glass plates to form a laminated glass. Such elements are used for windows installed on the outer wall or as a partition between the conference room and the corridor. That is, there are applications such as electronic blinds, dimming windows, and smart windows. Further, the function as an optical switch can be used for a liquid crystal shutter or the like.

The present invention will be described in more detail by way of examples. The invention is not limited by these examples. Unless otherwise specified, the examples are performed at room temperature (25 ° C).
<Measurement method>
It was measured and verified by the following method. Unless otherwise specified, JEITA ED-2521B relates to measurement methods not described in this specification.

<NMR>
NMR was measured by DRX-500 manufactured by Bruker BioSpin.
^{For 1} H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl ₃ . The measurement was performed at 500 MHz at room temperature. At this time, the number of times of integration is 16. The internal standard is tetramethylsilane.
^{In 19} F-NMR measurement, the number of times of integration is 24. The internal standard is CFCl ₃ .
Among the symbols of NMR, s means singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, and br is broad.

<Maximum temperature of nematic phase>
In the examples, “NI” is “upper limit temperature”.
The upper limit temperature is measured when the sample is placed on a hot plate of a melting point measuring device equipped with a polarization microscope and heated at a rate of 1 ° C / min, and a part of the sample changes from a nematic phase to an isotropic liquid. It is a value.

<Minimum temperature of nematic phase>
In the examples, "Tc" is the "lower limit temperature".
The lower limit temperature is determined by placing a sample having a nematic phase in a glass bottle, storing it in a freezer at 0 ° C, -10 ° C, -20 ° C, -30 ° C and -40 ° C for 10 days, and observing the phase.

<Refractive index anisotropy>
In the examples, the refractive index anisotropy is expressed as “Δn”.
Δn is measured by an Abbe refractometer in which a polarizing plate is attached to the eyepiece.
After rubbing the surface of the main prism in one direction, drop the sample on the main prism, measure the refractive index n⊥ as the polarization direction is perpendicular to the rubbing direction, and measure the polarization direction as parallel to the rubbing direction. The rate is measured as n /. Δn is calculated by Δn = n∥-n⊥. At this time, light with a wavelength of 589 nm is used, and the measurement temperature is 25 ° C.

<Dielectric anisotropy>
The value of the dielectric anisotropy is calculated from the formula of Δε = ε∥-ε⊥. The permittivity (ε ‖ and ε ⊥) is measured as follows.
(A) Measurement of dielectric constant (ε∥): A well-cleaned glass substrate is coated with a solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL). The glass substrate is rotated with a spinner and then heated at 150 ° C. for 1 hour. A sample is placed in a VA element having a distance of 4 μm between two glass substrates, and the element is sealed with an ultraviolet-curable adhesive. A sine wave (0.5 V, 1 kHz) is applied to this element, and after 2 seconds, the dielectric constant (ε∥) of the liquid crystal molecule in the major axis direction is measured.
(B) Measurement of dielectric constant (ε⊥): A polyimide solution is applied to a well-washed glass substrate. After firing this glass substrate, the obtained alignment film is subjected to rubbing treatment. The sample was injected into a TN device in which the distance between two glass substrates was 9 μm and the twist angle was 80 degrees. A sine wave (0.5 V, 1 kHz) is applied to this element, and after 2 seconds, the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecule is measured.

<Bulk viscosity>
In the examples, the bulk viscosity of the composition is designated as "η".
For the bulk viscosity, an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. is used. The measured temperature is 20 ° C.

<Contact angle>
The contact angle of the composition with respect to the substrate is measured by the sessile drop method. Unless otherwise specified, the measurement of the contact angle is based on the Japanese Industrial Standard R3257 sessile drop method. However, "substrate glass" in the standard shall be read as "substrate" in the present specification.

<Surface free energy>
The surface free energy of the substrate is determined by repeating the following procedure 5 times:
(1) The contact angle of water with respect to the substrate and the contact angle of diiodomethane with respect to the substrate are measured,
(2) Substituting values into γ _T (1 + cos θ) = 2 (γ _p γ _L ^d ) +2 (γ _d γ _L ^h ) for water and substrate and diiodomethane and substrate respectively, By solving, γ _T is obtained.

Where γ _T is the surface free energy of the substrate, θ is the contact angle of water and diiodomethane with respect to the substrate, γ _p is the nonpolar dispersive component of the surface free energy of the substrate, and γ _d is the surface free energy of the substrate. Of these, γ _L ^d is a polar hydrogen bond component, γ _L ^d is a non-polar dispersive force component of the surface free energy of water and diiodomethane, and γ _L ^h is a polar hydrogen bond component of the surface free energy of water and diiodomethane. The γ _L ^d of water is 21.8 mJm ^-2 , the γ _L ^h of water is 51 mJm ^-2 , the γ _L ^d of diiodomethane is 49.5 mJm ^-2 , and the γ _L ^h of diiodomethane is 1.3 mJm ^-2 .

The surface free energies of the film substrates with ITO used in the examples thus measured are shown in Table 2-1.
In addition, when the film thickness of the film was changed and the contact angle of water and diiodomethane with respect to the ITO surface was measured as shown in Table 2-2, which is the film substrate of the film substrate with ITO described later, the results shown in Table 2-3 were obtained. Became. Further, similarly to Table 2-1, when γ _T , γ _p and γ _d are obtained, Table 2-4 is obtained. As the film substrate with ITO, a commercially available product (registered trademark Fleclear, manufactured by TDK Corporation, PET base material) is used. The film contact angle and surface free energy values are considered to be almost the same after the film is manufactured, even if the production lots are different, but they are different values due to differences in storage period and storage conditions. Conceivable.

<UV exposure intensity>
The ultraviolet exposure intensity was measured with an ultraviolet integrating photometer UIT-150-A (manufactured by Ushio Inc.).

<Substrate for making dimming element>
The following two types of substrates were used for the measurement.
Glass substrate: Eagle (registered trademark) XG glass cut into 3 cm x 3 cm.
Film substrate with ITO: A transparent double-sided adhesive tape (MCS70, manufactured by Mikan Imaging Co., Ltd.) was used on the glass substrate, and an ITO transparent conductive film (registered trademark Fleclear, manufactured by TDK Corporation, PET substrate) was used. It was attached so that the ITO surface was located at the air interface.

<Method of preparing light control element and evaluation of cissing of composition>
A gap material (glass fiber, manufactured by Sumita Optical Glass Co., Ltd.) having a thickness of 11 μm was sprayed on one surface of each of the above-mentioned two kinds of substrates and a set of two substrates. The ITO-attached film substrate had a gap material scattered on the ITO surface. About 20 mg of the composition was dropped on the plane of the substrate on which the gap material was scattered. Further, the other substrate was placed on it so that the two diagonal sides were slightly displaced. The ITO-attached film substrate was arranged such that the ITO surfaces face each other and the composition was in contact with each ITO surface. Then, the substrate was manually pushed from the outside so that the liquid crystal would spread, and the two sides were fixed with clips. In this state, it was left standing for 20 minutes. Then, a set of substrates sandwiching the above composition was exposed to ultraviolet light to polymerize the polymerizable compound contained in the composition to obtain a light control device. The exposure was performed at room temperature using a 250 W ultra-high pressure mercury lamp (manufactured by USHIO INC., Multilight-250) at an exposure dose of 1 J / cm ² . At this time, the light intensity was 17 mW / cm ² (365 nm).
For cissing, the degree of cissing of the composition was evaluated when the entire area of the device was visually observed. The judgment was made as follows.

<Haze rate>
The haze ratio was measured with a haze meter NDH7000II manufactured by Nippon Denshoku Industries Co., Ltd.

<Compound>
The following were used as the vertical aligning agent represented by the formula (1) or (2). Compound (1-4-1) was synthesized in the same manner as the method described in WO 2016/129490.

Compound (2-M-1) was synthesized according to US Pat. No. 3,855,364. The ratio of structural isomers of this compound was 87:13 from the integrated value in NMR. The component in which Z ³⁰⁰ was OH was mainly.

In formula (2-M-1), Z ³⁰⁰ and Z ³⁰¹ represent OH or acryloyloxy, and are not the same group at the same time.
As 1-dodecanol, a commercially available compound was used as it was.

Compound (1-4-1), compound (2-M-1), and 1-dodecanol are vertical alignment agents or components of vertical alignment agents.
Compound (4-5-1) was synthesized according to Japanese Patent Application No. 2018-141672.

「Ｉｒｇａｃｕｒｅ６５１」は、ＢＡＳＦ株式会社製の光重合開始剤である。

"Irgacure 651" is a photopolymerization initiator manufactured by BASF Corporation.

<Liquid crystal composition>
The liquid crystal compounds of the components are shown according to the notation in Table 4. Unless otherwise specified, the 6-membered divalent groups in Table 4 are in the trans configuration. The number in parentheses after the symbolized compound in the liquid crystal composition represents the chemical formula to which the compound belongs. The ratio of the liquid crystal compound is a weight percentage based on the weight of the liquid crystal composition containing no additive.

[Liquid Crystal Composition (M21)]
2-HHB (2F, 3F) -O2 (10-6) 3%
3-HHB (2F, 3F) -O2 (10-6) 5%
5-HHB (2F, 3F) -O2 (10-6) 5%
3-HH2B (2F, 3F) -O2 (10-7) 9%
2-HH1OB (2F, 3F) -O2 (10-8) 16%
3-HH1OB (2F, 3F) -O2 (10-8) 16%
3-HDhB (2F, 3F) -O2 (10-16) 9%
3-HB (2F) B (2F, 3F) -O2 (10-20) 7%
5-HB-O2 (11-2) 10%
3-HHB-1 (11-5) 8%
3-HHB-O1 (11-5) 6%
3-HBB-2 (11-6) 6%
NI = 142.0 ° C .; Tc <−20 ° C .; Δn = 0.111; Δε = −5.7; η = 64.9 mPa · s.
[Liquid Crystal Composition (M22)]
3-HB (2F, 3F) -O2 (10-1) 7%
5-HB (2F, 3F) -O2 (10-1) 7%
3-HHB (2F, 3F) -O2 (10-6) 5%
5-HHB (2F, 3F) -O2 (10-6) 5%
V-HHB (2F, 3F) -O1 (10-6) 2%
V-HHB (2F, 3F) -O2 (10-6) 8%
V-HHB (2F, 3F) -O4 (10-6) 8%
3-HH2B (2F, 3F) -O2 (10-7) 7%
2-HBB (2F, 3F) -O2 (10-10) 3%
3-HBB (2F, 3F) -O2 (10-10) 6%
3-HH-4 (11-1) 10%
3-HB-O2 (11-2) 10%
5-HB-O2 (11-2) 10%
3-HHB-1 (11-5) 3%
3-HHB-3 (11-5) 4%
3-HHB-O1 (11-5) 3%
3-HBB-2 (11-6) 2%
NI = 102.0 ° C .; Tc <−40 ° C .; Δn = 0.101; Δε = −3.3; η = 25.8 mPa · s.
[Liquid Crystal Composition (M23)]
2-BB (2F, 3F) -O2 (10-4) 8%
3-BB (2F, 3F) -O2 (10-4) 13%
5-BB (2F, 3F) -O2 (10-4) 12%
2-HBB (2F, 3F) -O2 (10-10) 3%
3-HBB (2F, 3F) -O2 (10-10) 8%
4-HBB (2F, 3F) -O2 (10-10) 4%
5-B (F) BB-2 (11-7) 14%
5-B (F) BB-3 (11-7) 14%
3-HBTB-2 (11-17) 8%
3-HBTB-3 (11-17) 8%
3-HBTB-4 (11-17) 8%
NI = 100.0 ° C .; Tc <−20 ° C .; Δn = 0.219; Δε = −2.5; η = 42.2 mPa · s.
[Liquid Crystal Composition (M24)]
2-BB (2F, 3F) -O2 (10-4) 7%
3-BB (2F, 3F) -O2 (10-4) 13%
5-BB (2F, 3F) -O2 (10-4) 10%
2-HBB (2F, 3F) -O2 (10-10) 3%
3-HBB (2F, 3F) -O2 (10-10) 8%
4-HBB (2F, 3F) -O2 (10-10) 4%
5-HBB (2F, 3F) -O2 (10-10) 5%
3-dhBB (2F, 3F) -O2 (10-17) 8%
1-BB-3 (11-3) 4%
3-HBB-2 (11-6) 8%
5-B (F) BB-2 (11-7) 13%
5-B (F) BB-3 (11-7) 13%
3-BB (2F, 5F) B-3 (11-20) 4%
NI = 93.0 ° C .; Tc <−20 ° C .; Δn = 0.203; Δε = −3.3; η = 44.5 mPa · s.
[Liquid Crystal Composition (M25)]
3-H1OB (2F, 3F) -O2 (10-3) 5%
3-BB (2F, 3F) -O2 (10-4) 12%
5-BB (2F, 3F) -O2 (10-4) 12%
2-HH1OB (2F, 3F) -O2 (10-8) 4%
3-HH1OB (2F, 3F) -O2 (10-8) 5%
2-HBB (2F, 3F) -O2 (10-10) 3%
3-HBB (2F, 3F) -O2 (10-10) 9%
4-HBB (2F, 3F) -O2 (10-10) 4%
5-HBB (2F, 3F) -O2 (10-10) 9%
3-HDhB (2F, 3F) -O2 (10-16) 7%
3-dhBB (2F, 3F) -O2 (10-17) 10%
2-HH-3 (11-1) 10%
5-B (F) BB-2 (11-7) 10%
NI = 89.0 ° C .; Tc <−20 ° C .; Δn = 0.152; Δε = −5.7; η = 41.8 mPa · s.

<Preparation of composition>
[Examples 1 to 7 and Comparative Examples 1 and 2]
The liquid crystal composition, the vertical aligning agent or the components of the vertical aligning agent, and the polymerizable compound are mixed according to Table 5, Irgacure651 is further added, and the compositions (1) to (7) and the compositions (ref.1) and ( ref. 2) is prepared. The parts by weight in Table 2 indicate the amount based on the total weight of the liquid crystal composition as 100 parts by weight.

[Examples 11 to 17 and Comparative Examples 3 and 4]
The contact angles of the composition and the film substrate with ITO were measured and are shown in Table 6.

[Examples 21 to 27 and Comparative Examples 5 and 6]
Using the above composition, a light control device was prepared using the substrates shown in Table 7. The results are shown below.

  From the comparison between Examples 21 to 27 and Comparative Examples 5 and 6, the composition of the present invention exhibits higher wettability and less cissing on a film substrate having a surface free energy smaller than that of a glass substrate. Therefore, by using the composition of the present invention, a device can be produced with a good yield.

[Examples 31 to 37 and Comparative Example 7]
Table 8 shows the haze ratios of the light control elements 1 to 7. However, the "maximum applied voltage" is the applied voltage when the haze ratio in the light control element is maximum. The haze rate when the applied voltage is 0 V is a measured value after applying the maximum applied voltage.

  Since the relationship between the haze ratio and the voltage varies depending on the material, the maximum haze ratio and the voltage at which it is obtained are described. Further, in Example 26, once the element was driven, the haze ratio did not decrease even if the voltage was returned to 0V. Therefore, the values at the first driving are shown.

  As shown in Examples 31 to 37, it can be seen that the composition of the present invention has a low haze ratio when no voltage is applied and exhibits high transparency. Further, it can be seen that the light control element using the composition of the present invention exhibits a high haze ratio when a voltage is applied, and has excellent characteristics suitable for a reverse mode light control element.

  By using the composition of the present invention, a reverse mode light control device can be obtained without forming an alignment film on the substrate. Further, since the composition of the present invention has high wettability with respect to a film substrate, by using this, an element composed of a film substrate can be produced with a high yield. Furthermore, the produced liquid crystal light control device has a high transparency when no voltage is applied and a large haze ratio characteristic when a voltage is applied. Therefore, it can be practically used as a material for applications such as light control windows and smart windows.

Claims (17)

A composition comprising a liquid crystal composition and a vertical alignment agent, wherein the contact angle is 37 degrees or less and 27 degrees or more with respect to a substrate having a surface free energy of 28.31 ± 1.06 mJ / m ² . A composition comprising a liquid crystal composition and a vertical alignment agent, which has a contact angle of 37 degrees or less and 27 degrees or more with respect to a substrate having a surface free energy of 39.0 to 50.0 mJ / m ² . A composition comprising a liquid crystal composition and a vertical alignment agent, the composition having a contact angle of 37 degrees or less and 27 degrees or more with respect to a substrate having a surface free energy of 27.25 to 50.0 mJ / m ² .   The composition according to claim 1, wherein the component that increases the surface tension is a vertical aligning agent.   The composition of claim 4, wherein the vertical aligning agent has a polymerizing group.   The composition of claim 5, wherein the vertical aligning agent has OH and the polymerizing group is a radical polymerizing group. The composition according to claim 6, wherein the vertical aligning agent is a compound represented by formula (1) or a compound represented by formula (2).

(In formula (1),
R ¹ is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, alkyl having 1 to 20 carbons in which at least one hydrogen is replaced by fluorine, or carbon in which at least one hydrogen is replaced by fluorine. Is an alkoxy of the numbers 1 to 20,
Each ring M is 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,7-diyl,
Each Z ¹ is a single bond, alkylene having 2 to 10 carbons, or carbonyloxy, and CH _{2 which} is not adjacent to alkylene having 2 to 10 carbons may be replaced by O.
p is 0, 1, 2, or 3;
Ring L ¹ is a single bond, 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,7-diyl,
Z ² is a single bond or alkylene having 2 to 10 carbons, and CH _{2 which} is not adjacent to alkylene having 2 to 10 carbons may be replaced with O, and 1 H is hydroxy, (meth) acryloyl. Alternatively, it may be replaced with a group containing 2-hydroxymethylacryloyl. )

(In formula (2),
R ¹ is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, alkyl having 1 to 20 carbons in which at least one hydrogen is replaced by fluorine, or carbon in which at least one hydrogen is replaced by fluorine. Is an alkoxy of the numbers 1 to 20,
Each ring M is 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,7-diyl,
Each Z ¹ is a single bond, alkylene having 2 to 10 carbons, or carbonyloxy, and CH _{2 which} is not adjacent to alkylene having 2 to 10 carbons may be replaced by O.
p is 0, 1, 2, or 3;
Ring L ² is a single bond, 1,4-cyclohexylene, 1,4-phenylene, or naphthalene-2,7-diyl,
Z ³ is alkylene having 2 to 10 carbon atoms, at least one H of CH ₂ not adjacent to O is replaced with OH, and non-adjacent CH ₂ of alkylene having 2 to 10 carbon is replaced with O. Often,
Alternatively, when Z ³ is a direct bond and ring L ² has a structure other than a single bond, at least one H bonded to ring L ² is replaced with OH,
R ² is hydrogen or methyl. )   The composition according to any one of claims 4 to 7, comprising 6 parts by weight or more of a vertical alignment agent with respect to 100 parts by weight of the liquid crystal composition. The composition according to claim 7, which comprises at least one polymerizable compound selected from the group of compounds represented by formula (3), formula (4), and formula (5).

(In Formula (3), Formula (4), and Formula (5), each ring G is independently 1,4-cyclohexylene, 1,4-phenylene, 1,4-cyclohexenylene, pyridine- 2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl, or fluorene-2,7-diyl, wherein at least one hydrogen is fluorine, chlorine, cyano. , Hydroxy, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkoxycarbonyl having 1 to 12 carbons, or alkanoyl having 1 to 12 carbons. Z ¹⁰ may be independently a single bond, —O—, —COO—, —OCO—, or —OCOO—; Z ¹¹ is independently a single bond, —OCH ₂ —. _{, -CH 2 O -, - COO} -, - OCO -, - COS -, - SCO -, - OCOO -, - CONH -, - NHCO -, - CF 2 O -, - OCF 2 -, - CH 2 CH _{2 -, - CF 2 CF 2} -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH = CH -, - N = CH -, - CH = N -, - N = C (CH 3) -, - C (CH 3) = N -, - N = N-, or a -C≡C-; Z ¹² is a single bond, -O- or -COO-; X is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 20 carbons, alkenyl having 2 to 20 carbons, alkoxy having 1 to 20 carbons, or carbon. An alkoxycarbonyl of the number 1 to 20;
e is an integer of 1 to 4; f and g are independently an integer of 0 to 3; the sum of f and g is 1 to 4; h is an integer of 0 to 20 independently. R ² is independently hydrogen or CH ₃ . ) The composition according to any one of claims 7 to 9, comprising at least one polymerizable compound represented by formula (6).

In the formula (6), Z ¹² is a single bond or alkylene having 1 to 80 carbons, and in this alkylene, at least one hydrogen is alkyl having 1 to 20 carbons, fluorine, or the following formula (7). may be substituted with a group represented by at least one of -CH ₂ -, -O -, - CO -, - COO-, or --OCO -, - NH-, or -N (R ⁵⁾ - in When substituted with a plurality of —O—, these —O— are not adjacent to each other; R ⁵ is alkyl having 1 to 12 carbons; and at least one —CH ₂ —CH ₂ — is , -CH = CH-, or -C = C-;
R ¹⁰ is alkyl having 1 to 20 carbons, in which at least one hydrogen may be replaced by fluorine, and at least one —CH ₂ — is —O—, —CO—, —COO. -, or -OCO- may be replaced by; if Okikaeraru a plurality of -O-, these -O- is not adjacent; at least one of -CH ₂ -, a saturated aliphatic carbocyclic A compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, or a heterocyclic unsaturated aliphatic compound, which may be replaced by a divalent group formed by removing two hydrogens Well, in these divalent groups, the number of carbon atoms is 5 to 35, and at least one hydrogen may be replaced by alkyl having 1 to 12 carbon atoms, and in this alkyl, one —CH ₂ — is -O -, - CO -, - COO-, or may be replaced by -OCO-; R ² is hydrogen or CH _3.

In Formula (7), Z ¹³ is alkylene having 1 to 12 carbons, R ² is hydrogen or CH ₃ , and * represents a connecting position. The composition according to claim 1, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by formula (10).

In the formula (10), R ²⁰ and R ²¹ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen being replaced by fluorine. Alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine; each ring A is independently 1,4-cyclohexylene, 2,5-tetrahydro- 2H-pyranylene, 1,4-phenylene, monofluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, chloro-fluoro-1,4-phenylene, or 7,8-difluorochroman-2. , 6-diyl, 1,1,7-trifluoroindan-2,5-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 4,7-difluorochromene-3,8-diyl,
At least one is 2,3-difluoro-1,4-phenylene, chloro-fluoro-1,4-phenylene, 7,8-difluorochroman-2,6-diyl, 1,1,7-trifluoroindane-2. , 5-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 4,7-difluorochromene-3,8-diyl; Z ²⁰ is a single bond, -CH = CH-, -C [identical to] C-, methyleneoxy, or carbonyloxy; c is an integer of 1 to 4. The composition of claim 11, wherein the compound represented by formula (10) is at least one selected from the compounds represented by formula (10-1) to formula (10-33).

(In the formulas (10-1) to (10-33), R ²⁰ and R ²¹ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, (Alkenyloxy having 2 to 12 carbons, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine, or alkenyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine.) The composition according to any one of claims 1 to 11, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by formula (11).

(In the formula (11), R ²² and R ²³ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen being replaced by fluorine. A C1-C12 alkyl, or a C2-C12 alkenyl in which at least one hydrogen has been replaced by fluorine; each ring B is independently 1,4-cyclohexylene, 1,4-phenylene. , Monofluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ²¹ is a single bond, —CH═CH—, —C≡C—, methyleneoxy, or carbonyloxy. And c is an integer from 1 to 4.) The composition according to claim 13, wherein the compound represented by formula (11) is at least one selected from the group of compounds represented by formula (11-1) to formula (11-22).

(In formulas (11-1) to (11-22), R ²² and R ²³ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, (This is alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine.)   The composition according to any one of claims 1 to 14, wherein the composition contains a photopolymerization initiator as an additive.   An element for switching between a transparent state and a scattering state, which uses the composition according to any one of claims 1 to 15.   The device according to claim 16, wherein a plastic substrate is used.