CN112764312A

CN112764312A - Polymerizable composition for light control element, liquid crystal light control element, light control window, smart window, liquid crystal composite, and use thereof

Info

Publication number: CN112764312A
Application number: CN202011089014.7A
Authority: CN
Inventors: 平井吉治; 田辺真裕美; 长仓小桃; 宝蔵真由美
Original assignee: JNC Corp; JNC Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2019-10-21
Filing date: 2020-10-13
Publication date: 2021-05-07
Also published as: JP2021183686A; TW202116828A

Abstract

The present invention provides a polymerizable composition for a light control element, a liquid crystal light control element, a light control window, a smart window, which has good adhesion to a plastic film substrate with a transparent electrode and also has good light resistance and weather resistance. And liquid crystal composites using the compositions whose properties are balanced and suitable for dimming, and uses thereof. The precursors of the polymers included with the liquid crystal composition each contain at least one of a monofunctional polymerizable compound having an acyclic structure having a nitrogen atom, a monofunctional polymerizable compound having a cyclic structure, and a polyfunctional carbamic acid Ester (meth)acrylate oligomers.

Description

Polymerizable composition for light control element, liquid crystal light control element, light control window, smart window, liquid crystal composite, and use thereof

Technical Field

The present invention relates to a polymerizable composition for a light control element, a liquid crystal light control element, a light control window, a smart window, a liquid crystal composite, and uses thereof. More specifically, the present invention relates to a polymerizable composition for a light control element, which is obtained by combining a polymer precursor and a liquid crystal composition having positive dielectric anisotropy, a liquid crystal light control element using a liquid crystal composite obtained from the composition, and uses thereof.

Background

A method of scattering light or the like is used for the liquid crystal light control element. The element is used in building materials such as window glass or partitions of rooms, vehicle-mounted parts, and the like. In these devices, a soft substrate such as a plastic film is used in addition to a hard substrate such as a glass substrate.

In the liquid crystal composition sandwiched by these substrates, the arrangement of liquid crystal molecules is changed by adjusting the applied voltage. In this way, since light transmitted through the liquid crystal composition can be controlled, the liquid crystal light control element is widely used in a display, an optical shutter, a light control window (patent document 1), a smart window (patent document 2), and the like.

An example of the liquid crystal light control element is a polymer dispersed element of a light scattering mode. The liquid crystal composition is dispersed in a polymer (liquid crystal composite). The element has the following features. The element is easy to manufacture. Since the film thickness can be easily controlled over a large area, a device with a large screen can be manufactured. A polarizing plate is not required, and thus a clear display can be realized. The angle of view is wide due to light scattering. The element is expected to be used in a light control glass, a projection type display, a large-area display, and the like because of having the excellent properties.

Another example is a polymer network (polymer network) type liquid crystal dimming element. In elements of the type described, the liquid crystal composition is present in a three-dimensional network of polymers. The composition is continuous, an aspect that is different from the polymer dispersed type. The element of the type described also has the same characteristics as the element of the polymer dispersion type. There are also liquid crystal light control elements in which a polymer network type and a polymer dispersion type are mixed.

A liquid crystal composition having appropriate characteristics is used for the liquid crystal light control element. By improving the properties of the composition, elements with good properties can be obtained. The correlation between the properties of both is summarized in the following Table 1. The properties of the composition are further illustrated on an element basis. The temperature range of the nematic phase is associated with the temperature range in which the element can be used. The upper limit temperature of the nematic phase is preferably about 70 ℃ or higher, and the lower limit temperature of the nematic phase is preferably about-20 ℃ or lower. The viscosity of the composition correlates to the response time of the element. In order to control the transmittance of light, the response time is preferably short. Ideally a response time of 1 millisecond shorter than the other elements. Therefore, it is preferable that the viscosity of the composition is small. Further, it is preferable that the viscosity at low temperature is low. The elastic constant of the composition is correlated to the response time of the element. In order to achieve a short response time in the element, it is preferable that the elastic constant of the composition is large.

TABLE 1 characteristics of liquid crystal compositions and liquid crystal dimming elements

Numbering	Characteristics of liquid Crystal composition	Characteristics of liquid crystal light-adjusting element
			1	Wide temperature range of nematic phase	Wide temperature range
2	Low viscosity	Short response time
			3	Large optical anisotropy	High haze
4	Large positive or negative dielectric constant anisotropy	Low threshold voltage and low power consumption
			5	Has large specific resistance	High voltage holding ratio
6	Is stable to light and heat	Long service life
			7	Large elastic constant	Short response time

The optical anisotropy of the liquid crystal composition is correlated with the haze ratio of the liquid crystal dimming element. The haze ratio is a ratio of diffused light to total transmitted light. When light is blocked, the haze ratio is preferably high. It is preferable for a large haze ratio that the optical anisotropy is large. The large dielectric anisotropy of the composition contributes to a low threshold voltage or low power consumption in the device. Therefore, it is preferable that the dielectric anisotropy is large. The large specific resistance of the composition contributes to a large voltage holding ratio in the device. Therefore, a composition having a large specific resistance in the initial stage is preferable. A composition having a large specific resistance after a long-term use is preferable. The stability or weatherability of the composition to light or heat is correlated to the lifetime of the element. When the stability or heat resistance is good, the life is long. Poor display such as afterimages or drip marks are also associated with the life of the element. An element having high weather resistance and less prone to display defects is desired. (patent document 3)

The liquid crystal dimming element has a normal mode (normal mode) and a reverse mode (reverse mode). In the normal mode, the element is opaque when no voltage is applied and becomes transparent when a voltage is applied. The pattern is suitable for the partition of a room. In the reverse mode, the element is transparent when no voltage is applied and the element becomes opaque when a voltage is applied. In this mode, the transparent member becomes transparent when the failure occurs in the element, and thus is suitable for a window of an automobile. The following were also studied: in a light control window or a smart window having a liquid crystal light control element, both a front substrate and a rear substrate are manufactured by a roll-to-roll method using a flexible plastic film, rather than a rigid substrate (glass plate or plastic plate). In patent document 4, a transparent electrode (or an alignment film) is formed on the plastic plate or the plastic film, and adhesion to a polymer formed in the liquid crystal layer is required.

(patent document 5 to patent document 8)

Patent documents 5 to 8 do not disclose or suggest a combination of materials for improving the adhesion and weather resistance and light resistance which are supposed to be used outdoors.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent application laid-open No. H06-273725

[ patent document 2] International publication No. 2011-

[ patent document 3] International publication No. 2019-026621

[ patent document 4] Japanese patent laid-open publication No. 2019- & 105680

[ patent document 5] Japanese patent laid-open publication No. 2011-026526

[ patent document 6] Japanese patent laid-open publication No. 2011-

[ patent document 7] Japanese patent laid-open publication No. 2011- & 902

[ patent document 8] Japanese patent laid-open publication No. 2011-

Disclosure of Invention

[ problems to be solved by the invention ]

The invention provides a polymerizable composition for a light control element, which has good adhesion with a plastic film substrate with a transparent electrode and good light resistance and weather resistance.

Another object is to provide a liquid crystal composite having characteristics which are well-balanced and suitable for dimming.

[ means for solving problems ]

The present inventors considered that the characteristics of the liquid crystal light control element could be further improved, and conceived a method of using a liquid crystalline compound having a terphenyl structure or a liquid crystalline compound having a cyano group in a part of a liquid crystal composition. The reason is that a liquid crystal composite having a liquid crystal composition with a large optical anisotropy is expected to obtain a large haze ratio.

As a result of studying these possibilities, it has been found that when a specific liquid crystalline compound and a specific polymerizable compound are combined, a liquid crystal composite having both adhesion and stability (weather resistance and light resistance) to outdoor use and having balanced characteristics and suitable for light control can be obtained, and the present invention has been completed.

The present invention relates to a polymerizable composition for a light control element, which comprises a liquid crystal composition and a precursor of a polymer,

the liquid crystal composition contains at least one compound (as component A) selected from the compounds represented by formula (1),

the precursor of the polymer contains: at least one type of monofunctional polymerizable compound having a nitrogen atom and an acyclic structure, at least one type of monofunctional polymerizable compound having a cyclic structure, and at least one type of polyfunctional urethane (meth) acrylate oligomer.

The present invention also relates to a liquid crystal composite obtained by polymerizing a precursor, a liquid crystal light control element having the liquid crystal composite, and the like.

In the formula (1), R¹Is alkyl group with carbon number of 1 to 12, alkoxy group with carbon number of 1 to 12 or alkenyl group with carbon number of 2 to 12; ring a is 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or tetrahydropyran-2, 5-diyl; z¹Is a single bond, ethylene, ethenylene, ethynylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy; x¹And X²Each independently is hydrogen or fluorine; y is¹Is fluorine, chlorine, cyano, alkyl of carbon number 1 to 12 with at least one hydrogen substituted by fluorine or chlorine, alkoxy of carbon number 1 to 12 with at least one hydrogen substituted by fluorine or chlorine, or alkenyloxy of carbon number 2 to 12 with at least one hydrogen substituted by fluorine or chlorine; a is 1, 2,3 or 4.

[ Effect of the invention ]

According to the present invention, by combining a liquid crystal composition with a specific polymerizable compound, a polymerizable composition for a light control element can be obtained which, when a plastic film substrate having a transparent electrode formed thereon is used, has good adhesion between a polymer formed in a liquid crystal layer and the plastic film substrate having the transparent electrode and also has good light resistance and weather resistance.

Further, according to the present invention, a liquid crystal composite having characteristics such as a high upper limit temperature of a nematic phase, a low lower limit temperature of a nematic phase, a small viscosity, a large optical anisotropy, a large positive dielectric anisotropy, a large specific resistance, a high stability to light, a high stability to heat, and a large elastic constant, which are well-balanced and excellent, and having characteristics suitable for light control can be obtained.

The liquid crystal composite can provide a liquid crystal light-controlling element having characteristics such as a short response time, a high voltage holding ratio, a low threshold voltage, a high haze ratio, a high weather resistance, and a long life.

Drawings

Fig. 1 is a schematic view of a liquid crystal light control element (electrode layers are not shown) showing a state where light passes through a light control layer. When a voltage is applied between the upper and lower substrates, the liquid crystalline compound is aligned, and the difference in refractive index between the polymer as a transparent substance and the liquid crystal composition is small, thereby reducing scattering of incident light.

Fig. 2 is a schematic view (electrode layer not shown) of a liquid crystal light control element in which a liquid crystal compound is present in a non-aligned state when no voltage is applied between upper and lower substrates, and when light enters a light control layer, strong scattering of incident light occurs at an interface due to a difference in refractive index between a polymer as a transparent material and a liquid crystal composition.

Description of the symbols

1: substrate with electrode layer

2: liquid crystalline compound

3: transparent substance

Detailed Description

In the present specification, terms such as "liquid crystal compound", "polymerizable compound", "liquid crystal composition", "polymerizable composition", "liquid crystal composite", and "liquid crystal light control element" are used. The "liquid crystalline compound" is a general term for compounds having a liquid crystal phase such as a nematic phase or a smectic phase, and compounds which do not have a liquid crystal phase but are added to the composition for the purpose of adjusting the characteristics such as the temperature range, viscosity, and dielectric anisotropy of the nematic phase. The compound has, for example, a six-membered ring such as 1, 4-cyclohexylene or 1, 4-phenylene, and the molecule (liquid crystal molecule) thereof is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the liquid crystal composition. The liquid crystalline compound having an alkenyl group is not classified into a polymerizable compound in terms of its meaning.

The "liquid crystal composition" is prepared by mixing a plurality of liquid crystalline compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, delustering agents, pigments, defoaming agents, and polar compounds may be added to the liquid crystal composition as needed. Even in the case where an additive is added, the proportion of the liquid crystalline compound is represented by a mass percentage (mass%) based on the liquid crystal composition containing no additive. The proportion of the additive is represented by a mass percentage based on the liquid crystal composition containing no additive. That is, the ratio of the liquid crystalline compound or the additive is calculated based on the total amount of the liquid crystalline compound. In some cases, "mass" of "% by mass" is omitted.

The "polymerizable composition" is prepared by mixing a polymerizable compound into a liquid crystal composition. That is, the polymerizable composition is a mixture of at least one polymerizable compound and the liquid crystal composition. To the polymerizable compound, additives such as a polymerization initiator and a polymerization inhibitor are added as necessary. The proportions of the polymerization initiator and the polymerization inhibitor are represented by mass percentages based on the total amounts (total amounts) of the liquid crystal composition and the precursor of the polymer (polymerizable compound). Even in the case where an additive is added, the proportion of the polymerizable compound or the liquid crystal composition contained in the polymerizable composition is represented by the mass percentage based on the polymerizable composition containing no additive.

The "liquid crystal composite" is a composite of a polymer precursor and a liquid crystal composition, which is produced by polymerization treatment of a polymerizable composition.

The "liquid crystal light control element" is an element having a liquid crystal composite, and is a generic name of a liquid crystal panel and a liquid crystal module for light control.

The "upper limit temperature of the nematic phase" may be simply referred to as "upper limit temperature". The "lower limit temperature of the nematic phase" may be simply referred to as "lower limit temperature". The expression "improving the dielectric anisotropy" means that the value increases positively in a composition having a positive dielectric anisotropy and negatively in a composition having a negative dielectric anisotropy. The phrase "large voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. The properties of the composition or the element are sometimes investigated by time-varying tests.

The compound (1z) is exemplified. In formula (1z), symbols α and β surrounded by hexagons correspond to ring α and ring β, respectively, and represent a six-membered ring, a condensed ring, or the like. Where the subscript 'x' is 2, there are two rings α. The two groups represented by the two rings a may be the same or may be different. The rule applies to any two rings a where subscript 'x' is greater than 2. The rules also apply to other tokens such as the bonding base Z. The slash across one side of the loop β indicates that any hydrogen on the loop β may be substituted with a substituent (-Sp-P). The subscript 'y' indicates the number of substituents that are substituted. When subscript 'y' is 0, the substitution is absent. When the subscript 'y' is 2 or more, a plurality of substituents (-Sp-P) are present on the ring β. In this case, rules that may be the same or different may also apply. Furthermore, the rules also apply to the use of the notation of Ra in a variety of compounds.

In formula (1z), for example, the expression "Ra and Rb are alkyl, alkoxy or alkenyl" means that Ra and Rb are independently selected from the group of alkyl, alkoxy and alkenyl. That is, the group represented by Ra and Rb may be the same or different.

At least one compound selected from the compounds represented by the formula (1z) may be simply referred to as "compound (1 z)". The "compound (1 z)" means one compound, a mixture of two compounds or a mixture of three or more compounds represented by the formula (1 z). The same applies to the compounds represented by the other formulae. The expression "at least one compound selected from the group consisting of the compounds represented by the formula (1z) and the formula (2 z)" means at least one compound selected from the group consisting of the compound (1z) and the compound (2 z).

"principal component" means the component that occupies the greatest proportion of the mixture or composition. For example, in a mixture of 40% of the compound (1z), 35% of the compound (2z) and 25% of the compound (3z), the compound (1z) is the main component. When the component (1) is only the compound (1z), the compound (1z) is also referred to as a main component. When the compound (1z) is a single compound, the compound is also referred to as a main component.

The expression "at least one 'a'" means that the number of 'a's is arbitrary. With respect to the expression "at least one 'a' may be substituted with 'B', when the number of 'a' is one, the position of 'a' is arbitrary, and when the number of 'a' is two or more, the positions of 'a' may be selected without limitation. Sometimes using "at least one-CH₂-may be substituted by-O-. In said case, -CH₂-CH₂-CH₂Can pass through non-contiguous-CH₂-conversion to-O-CH by-O-substitution₂-O-. However, adjacent-CH₂-is not substituted by-O-. The reason for this is that: in the substitution, the formation of-O-CH₂- (peroxides).

The alkyl group of the liquid crystalline compound contained in the liquid crystal composition is a linear or branched chain and does not contain a cyclic alkyl group. Straight chain alkyl is preferred over branched chain alkyl. The same applies to terminal groups such as alkoxy groups and alkenyl groups. In order to increase the upper limit temperature, the steric configuration associated with the 1, 4-cyclohexylene group is a trans configuration rather than a cis configuration.

Since 2-fluoro-1, 4-phenylene is asymmetric in the left-right direction, it is present in the left (L) and right (R) directions.

The same applies to divalent radicals such as tetrahydropyran-2, 5-diyl. The same applies to a bonding group (-COO-or-OCO-) such as a carbonyloxy group. In the present invention, any of them can be used.

The composition "based on the total mass" indicates a mass ratio of each component in the total mass of all the components in the composition or the mixture, and is a ratio of a so-called "internal ratio". On the other hand, "to the total mass" is a mass ratio of the components to the total mass of the composition or the mixture, and is a ratio of a so-called "external ratio".

The present invention is as follows.

Item 1.

A polymerizable composition for a light control element, comprising a liquid crystal composition, a polymer precursor and a photopolymerization initiator,

the liquid crystal composition contains a liquid crystalline compound represented by the formula (1) as a component A,

the precursors of said polymers each contain

At least one monofunctional polymerizable compound selected from the compounds represented by the formula (M-1),

At least one monofunctional polymerizable compound selected from compounds represented by the formula (M-2) having a cyclic structure, and

at least one selected from urethane (meth) acrylate oligomers having two or more (meth) acryloyl groups as the polyfunctional polymerizable compound;

(in the formula (1), R¹Is alkyl group with carbon number of 1 to 12, alkoxy group with carbon number of 1 to 12 or alkenyl group with carbon number of 2 to 12; ring A is 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyrimidine-2, 5-diyl, 1, 3-diylDioxane-2, 5-diyl or tetrahydropyran-2, 5-diyl; z¹Is a single bond, ethylene, ethenylene, ethynylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy; x¹And X²Each independently is hydrogen or fluorine; y is¹Is fluorine, chlorine, cyano, alkyl of carbon number 1 to 12 with at least one hydrogen substituted by fluorine or chlorine, alkoxy of carbon number 1 to 12 with at least one hydrogen substituted by fluorine or chlorine, or alkenyloxy of carbon number 2 to 12 with at least one hydrogen substituted by fluorine or chlorine; a is 1, 2,3 or 4;

in the formula (M-1),

M¹⁰⁰is hydrogen, fluorine, alkyl of carbon number 1 to 5 or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted by fluorine or chlorine;

R¹⁰⁰and R¹⁰¹Each independently hydrogen or C1-C12 alkyl or hydroxyalkyl,

at least one of-CH in these alkyl or hydroxyalkyl groups₂May be substituted by-O-, -N (R)¹⁰²) -, -CO-, -COO-or-OCO-substituted, R¹⁰²Hydrogen, alkyl of carbon number 1 to 12;

in the formula (M-2),

M¹⁰¹is hydrogen, fluorine, alkyl of carbon number 1 to 5 or alkyl of carbon number 1 to 5 wherein at least one hydrogen is substituted by fluorine or chlorine;

Z¹⁰⁰is a single bond or an alkylene group having 1 to 10 carbon atoms, in which alkylene group at least one hydrogen may be substituted by fluorine or chlorine, at least one-CH₂-may be substituted by-O-, -CO-, -COO-or-OCO-;

R¹⁰³is prepared from carbocyclic saturated aliphatic compound, heterocyclic saturated aliphatic compound, carbocyclic unsaturated aliphatic compound, heterocyclic unsaturated aliphatic compound orA monovalent group having 5 to 35 carbon atoms which is formed by removing one hydrogen from a carbocyclic or heterocyclic aromatic compound and which may be substituted with an alkyl group having 1 to 12 carbon atoms, at least one-CH group being present in the monovalent group₂-may be substituted by-O-, -CO-, -COO-or-OCO-.

Item 2.

The polymerizable composition for a light control element according to item 1, wherein the compound represented by formula (1) is at least one compound selected from the group consisting of compounds represented by formulae (1-1) to (1-48);

(in formulae (1-1) to (1-48), R¹Is alkyl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms or alkenyl group with 2 to 12 carbon atoms, X¹And X²Each independently is hydrogen or fluorine; y is¹Is fluorine, chlorine, cyano, alkyl of 1 to 12 carbon atoms with at least one hydrogen substituted by fluorine or chlorine, alkoxy of 1 to 12 carbon atoms with at least one hydrogen substituted by fluorine or chlorine or at least one hydrogen substituted by fluorine or chlorineAlkenyloxy of 2 to 12 carbon atoms in the generation).

Item 3.

The polymerizable composition for a light control element according to item 1 or item 2, wherein the proportion of the component a is in the range of 5 to 90 mass% based on the mass of the liquid crystal composition.

Item 4.

The polymerizable composition for a light control element according to any one of claims 1 to 3, wherein the liquid crystal composition further contains a liquid crystalline compound represented by formula (2) as a component B;

(in the formula (2), R³Is a radical bonded to a carbon atom of the ring C, R²And R³Each independently is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine;

ring B and ring C are each independently 1, 4-cyclohexylene, 1, 3-phenylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene or pyrimidine-2, 5-diyl;

Z²is a single bond, ethylene, ethenylene, ethynylene, methyleneoxy or carbonyloxy;

b is 1, 2 or 3).

Item 5.

The polymerizable composition for a light control element according to item 4, wherein the liquid crystal composition contains at least one compound selected from the group consisting of liquid crystal compounds represented by formulae (2-1) to (2-23) as a component B;

(in formulae (2-1) to (2-23), R²And R³An alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine).

Item 6.

The polymerizable composition for a light control element according to item 4 or item 5, wherein the proportion of the component B is in the range of 5 to 90 mass% based on the mass of the liquid crystal composition.

Item 7.

The polymerizable composition for a light control element according to any one of claims 1 to 6, wherein the liquid crystal composition contains a liquid crystalline compound represented by formula (3) as a component C;

(in the formula (3), R⁴And R⁵Each independently is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms or alkenyloxy having 2 to 12 carbon atoms; ring D and ring F are each independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chromane-2, 6-diyl or chromane-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; ring E is 2, 3-difluoro-1, 4-phenylene, 2-chloro-3-fluoro-1, 4-phenylene, 2, 3-difluoro-5-methyl-1, 4-phenylene, 3,4, 5-trifluoronaphthalene-2, 6-diyl, 7, 8-difluorochromane-2, 6-diyl, 3,4,5, 6-tetrafluorofluorene-2, 7-diyl, 4, 6-difluorodibenzofuran-3, 7-diyl, 4, 6-difluorodibenzothiophene-3, 7-diyl, or 1,1,6, 7-tetrafluoroindan-2, 5-diyl; z³And Z⁴Each independently a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 0, 1, 2 or 3, d is 0 or 1; the sum of c and d is 3 or less).

Item 8.

The polymerizable composition for a light-modulating element according to item 7, wherein component C is at least one compound selected from the group consisting of compounds represented by formulae (3-1) to (3-35);

(in formulae (3-1) to (3-35), R⁴And R⁵Each independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms).

Item 9.

The polymerizable composition for a light control element according to item 7 or item 8, wherein the proportion of the component C is in a range of 3 to 25 mass% based on the mass of the liquid crystal composition.

Item 10.

The polymerizable composition for a light control element according to item 1, wherein in the compound represented by the formula (M-1),

M¹⁰⁰is hydrogen or methyl;

R¹⁰⁰and R¹⁰¹Each independently is hydrogen, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, or a linear hydroxyalkyl group having 1 to 10 carbon atoms or a branched hydroxyalkyl group having 3 to 10 carbon atoms;

at least one of-CH in these alkyl or hydroxyalkyl groups₂May be-O-or-N (R)¹⁰²) -substituted, R¹⁰²Hydrogen or a linear alkyl group having 1 to 10 carbon atoms;

the compound represented by the formula (M-2) is at least one compound selected from the group consisting of compounds represented by the formulae (M-2-1) to (M-2-10),

the urethane (meth) acrylate oligomer is at least one selected from the group consisting of a polyester urethane (meth) acrylate oligomer and a polyether urethane (meth) acrylate oligomer, and has a weight average molecular weight in the range of 2,000 to 30,000;

(in the formula, M¹⁰¹Is hydrogen or methyl; n is¹⁰⁰Is 0, 1 or 2, and m100 is an integer of 2 to 6).

Item 11.

The polymerizable composition for a light control element according to any one of claims 1 to 10, further comprising at least one polymerizable compound having a phosphoric acid moiety selected from the group consisting of compounds represented by formulae (M-3) and (M-4) as a precursor of the polymer;

(in formulae (M-3) to (M-4), M¹⁰²Is hydrogen or methyl; n is¹⁰¹、n¹⁰²And n¹⁰³Independently 1 to 4).

Item 12.

The polymerizable composition for a light control element according to any one of claims 1 to 11, further comprising at least one polymerizable compound selected from the group consisting of compounds represented by the formulae (M-5-E) and (M-5-P), and at least one polymerizable compound selected from hydroxyalkyl (meth) acrylates as a precursor of the polymer;

(formula (M-5-E) and in formula (M-5-P), M⁵⁰¹Is hydrogenOr methyl, R⁵⁰²Is alkyl with 1 to 6 carbon atoms, n is 1 to 30;

hydrogen in the ethylene glycol structure of the formula (M-5-E) and the propylene glycol structure of the formula (M-5-P) may be substituted with an alkyl group having 1 to 3 carbon atoms;

the alkyl group in the hydroxyalkyl (meth) acrylate is a linear alkylene group having 2 to 10 carbon atoms or a branched alkylene group having 3 to 10 carbon atoms).

Item 13.

The polymerizable composition for a light control element according to any one of claims 1 to 12, further comprising at least one polymerizable compound selected from the group consisting of compounds represented by formula (7), formula (8), and formula (9) as a precursor of the polymer;

in the formulae (7), (8) and (9), ring G, ring I, ring J, ring K, ring L and ring M are each 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, and at least one hydrogen contained in these groups may be substituted with fluorine, chlorine, cyano, hydroxyl, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or an alkanoyl group having 1 to 5 carbon atoms; z⁸、Z¹⁰、Z¹²、Z¹³And Z¹⁷Each independently is a single bond, -O-, -COO-, -OCO-or-OCOO-; z⁹、Z¹¹、Z¹⁴And Z¹⁶Each independently is a single bond, -OCH₂-、-CH₂O-、-COO-、-OCO-、-COS-、-SCO-、-OCOO-、-CONH-、-NHCO-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂-、-CH＝CHCOO-、-OCOCH＝CH-、-CH₂CH₂COO-、-OCOCH₂CH₂-、-CH＝CH-、-N＝CH-、-CH＝N-、-N＝C(CH₃)-、-C(CH₃) N-, -N-or-C ≡ C-; z¹⁵Is a single bond, -O-or-COO-;Y²hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, a linear alkyl group having a carbon number of 1 to 20, a linear alkenyl group having a carbon number of 2 to 20, a linear alkoxy group having a carbon number of 1 to 20, or a linear alkyloxycarbonyl group having a carbon number of 2 to 20; f and h are each independently an integer from 1 to 4; k and m are each independently an integer of 0 to 3; the sum of k and m is 1 to 4; e. g, i, j, l and n are each independently an integer of 0 to 20; m⁷To M¹²Each independently hydrogen or methyl.

Item 14.

The polymerizable composition for a light control element according to any one of items 1 to 13, wherein the proportion of the liquid crystal composition is in the range of 30% by mass to 95% by mass and the proportion of the precursor of the polymer is in the range of 5% by mass to 70% by mass, based on the total mass of the liquid crystal composition and the precursor of the polymer.

Item 15.

The polymerizable composition for a light control element according to any one of claims 1 to 14, wherein the polymerizable composition is a polymerizable composition for a light control element,

the proportion of the compound (M-1) is in the range of 3 to 25% by mass,

the proportion of the compound (M-2) is in the range of 3 to 30% by mass,

the ratio of the polyfunctional urethane (meth) acrylate oligomer is in the range of 5 to 25% by mass, wherein the total ratio of the precursors of the polymers is not more than 70% by mass,

the proportion of the photopolymerization initiator is in the range of 0.1 to 5% by mass based on the total mass of the liquid crystal composition and the precursor of the polymer.

Item 16.

The polymerizable composition for a light control element according to any one of claims 11 to 15, wherein the polymerizable composition is a polymerizable composition for a light control element,

the ratio of the compound (M-3) to the compound (M-4) is in the range of 0.001 to 0.5% by mass.

Item 17.

The polymerizable composition for a light control element according to any one of claims 12 to 16, wherein the polymerizable composition is a liquid crystal composition,

the total ratio of the compound (M-5-E) and/or the compound (M-5-P) to the hydroxyalkyl (meth) acrylate is in the range of 2 to 30% by mass.

Item 18.

A liquid crystal light-modulating element, wherein a light-modulating layer is sandwiched between a pair of transparent substrates, the transparent substrates having transparent electrodes, and the light-modulating layer is a liquid crystal composite obtained by polymerizing the polymerizable composition for a light-modulating element according to any one of items 1 to 17.

Item 19.

The liquid crystal dimming element according to item 18, wherein the transparent substrate comprises a glass plate, a plastic plate, or a plastic film.

Item 20.

The liquid crystal dimming element of item 18 or item 19, wherein at illuminance (180W/m)²) And a haze change rate before and after a weather resistance test performed under conditions of an irradiation time (100 hours) and an in-tank temperature (35 ℃) of 20% or less.

Item 21.

A dimming window using the liquid crystal dimming element according to any one of items 18 to 20.

Item 22.

A smart window using the liquid crystal dimming element of any one of items 18 to 20.

Item 23.

A liquid crystal composite obtained by polymerizing the polymerizable composition for a light control element according to any one of items 1 to 17.

Item 24.

Use of a liquid crystal composite according to item 23 in a liquid crystal dimming element.

Item 25.

Use of the liquid crystal composite according to item 23 in a liquid crystal dimming element in which a transparent substrate comprises a plastic plate or a plastic film.

Item 26.

Use of a liquid crystal composite according to item 23 in a light control window.

Item 27.

Use of a liquid crystal composite according to item 23 in a smart window.

Item 28.

Use of a liquid crystal composite obtained by polymerizing the polymerizable composition for a light controlling element according to any one of items 1 to 17 in a liquid crystal light controlling element in which a transparent substrate comprises a plastic plate or a plastic film.

The present invention also includes the following items.

(a) The polymerizable composition or liquid crystal composite for a light controlling device as described above, wherein the liquid crystal composition contains Y in the compound (1) described in the item 1¹At least one compound which is fluorine is used as component A.

(b) The polymerizable composition or liquid crystal composite for a light controlling device as described above, wherein the liquid crystal composition contains Y in the compound (1) described in the item 1¹At least one compound which is a cyano group is used as component A.

The present invention also includes the following items.

(c) The polymerizable composition for a light control element or the liquid crystal composite as described above, wherein the liquid crystal composition contains at least one compound selected from the group consisting of the compound (1-1), the compound (1-2), the compound (1-3), the compound (1-9), the compound (1-13), the compound (1-16), the compound (1-21), the compound (1-22), the compound (1-23), the compound (1-24), the compound (1-27), the compound (1-28), the compound (1-33), the compound (1-36), the compound (1-41), the compound (1-42) and the compound (1-48) described in item 2 as the component A.

The present invention also includes the following items.

(d) The polymerizable composition for a light control element or the liquid crystal composite as described above, wherein the liquid crystal composition contains at least one compound selected from the group consisting of the compound (2-1), the compound (2-2), the compound (2-3), the compound (2-4), the compound (2-6), the compound (2-9), the compound (2-10), the compound (2-12), the compound (2-13), the compound (2-14), the compound (2-16), the compound (2-17), the compound (2-19) and the compound (2-21) described in the above item 5 as the component B.

The present invention also includes the following items.

(e) The polymerizable composition for a light control element or the liquid crystal composite as described above, wherein the liquid crystal composition contains at least one compound selected from the group consisting of the compound (3-1), the compound (3-5), the compound (3-6), the compound (3-7), the compound (3-8), the compound (3-12), the compound (3-14), the compound (3-19) and the compound (3-34) described in item 8 as the component C.

The present invention also includes the following items.

(f) The liquid crystal composite as described above, wherein the proportion of the polymer is in the range of 5 to 10 mass% and the proportion of the liquid crystal composition is in the range of 95 to 90 mass% based on the liquid crystal composite.

The present invention also includes the following items.

(g) The liquid crystal composite as described above, wherein the proportion of the polymer is in the range of 5 to 70 mass% and the proportion of the liquid crystal composition is in the range of 95 to 30 mass% based on the liquid crystal composite.

(h) The liquid crystal composite as described above, wherein the proportion of the polymer is in the range of 20 to 60 mass% and the proportion of the liquid crystal composition is in the range of 80 to 40 mass% based on the liquid crystal composite.

(i) The liquid crystal composite as described above, wherein the proportion of the polymer is in the range of 30 to 45 mass% and the proportion of the liquid crystal composition is in the range of 70 to 55 mass% based on the liquid crystal composite.

The ratio of the polymer to the liquid crystal composition in the liquid crystal composite corresponds to the ratio of the precursor of the polymer to the liquid crystal composition in the polymerizable composition.

The present invention also includes the following items.

(j) The liquid crystal composite as described above, wherein the precursor of the liquid crystal composite is a polymerizable composition for a light control element, and the polymerizable composition contains a liquid crystal composition, a polymerizable compound and a photopolymerization initiator.

The present invention relates to a liquid crystal composite containing a polymer and a liquid crystal composition having a nematic phase, and a liquid crystal light control element having the composite. The liquid crystal composite comprises a nematic liquid crystal composition and a polymer.

The present invention will be explained in the following order.

First, a polymerizable composition will be described.

Second, a liquid crystal composition will be explained.

Third, the main characteristics of the liquid crystalline compound and the main effects of the compound on the liquid crystal composition or the device will be described.

Fourth, a combination or a preferable ratio of the liquid crystalline compounds will be described.

Fifth, a preferred embodiment of the liquid crystalline compound will be described.

Sixth, preferred liquid crystalline compounds will be described.

Seventh, a preferred embodiment of the precursor of the polymer and an example thereof will be described.

Eighth, a method for synthesizing the component compound will be explained.

Ninth, a photopolymerization initiator to be added to the polymerizable composition will be described.

Tenth, other additives that can be added to the polymerizable composition will be described.

Finally, the liquid crystal composite and the liquid crystal light control element will be explained.

First, a polymerizable composition will be described. The polymerizable composition of the present invention is a polymerizable composition for a light control element. Hereinafter, the polymerizable composition may be simply referred to as "polymerizable composition".

The polymerizable composition is a precursor of a liquid crystal composite, and the liquid crystal composite is produced by polymerization of a polymer precursor.

The polymerizable composition is a mixture of a polymer precursor, a liquid crystal composition, and a photopolymerization initiator. When the polymerizable composition is put into an element and polymerized, a polymer produced by the polymerization undergoes phase separation to provide a liquid crystal composite. The amount of the polymer in the liquid crystal composite corresponds to the amount of the polymerizable precursor in the polymerizable composition. Furthermore, the quality of the photopolymerization initiator does not affect the quality of the polymer.

The element having a liquid crystal composite is classified into a polymer stable alignment type, a polymer network type, and a polymer dispersion type according to polymerization of a polymer.

When the proportion of the polymer is small, a polymer stabilized alignment type (polymer stabilized alignment) element is produced. It is simply referred to as a PSA element. In example 1 of International publication No. 2012-050178, "the monomer is added in an amount of 0.5 wt% based on the liquid crystal material" (paragraph 0105). As is clear from the above description, a small amount of a polymerizable compound is added to a liquid crystal material (liquid crystal composition) in a PSA element. In the PSA element, the polymer adjusts the pretilt angle of the liquid crystal molecules. By optimizing the pretilt angle, the liquid crystal molecules are stabilized, and the response time of the element is shortened.

When the proportion of the polymer is large, a polymer-dispersed device is produced. In the element of the type described, the liquid crystal composition is dispersed in the polymer as droplets. Each droplet is microencapsulated and discontinuous. The liquid crystal molecules are aligned along the inner wall of the capsule and thus in a random state. Since the refractive index of the polymer is different from that of the liquid crystal molecules, incident light is scattered. The elements are opaque. When a voltage is applied to the element, the refractive index of the liquid crystal molecules changes. If the refractive index is the same as the refractive index of the polymer, the incident light passes through the element, and the element becomes transparent.

On the other hand, when the proportion of the polymer is moderate, an element of a polymer network type is produced. In elements of said type, the polymer has a three-dimensional network structure, the liquid crystal composition being surrounded by said network and being continuous. The liquid crystal molecules are in a random state and the element is opaque. When a voltage is applied to the element, liquid crystal molecules are aligned in the direction of the electric field, and thus the element becomes transparent. In order to efficiently generate light scattering, the ratio of the liquid crystal composition based on the liquid crystal composite is preferably large. When the droplet or grid is large, the drive voltage is low. Therefore, the proportion of the polymer is preferably small from the viewpoint of low driving voltage. The response time is short when the drop or grid is small. Therefore, the proportion of the polymer is preferably large from the viewpoint of short response time.

In order to scatter incident light and improve adhesion between the light modulation layer (liquid crystal composite) and the substrate, the preferable proportion of the polymer precursor is in the range of 5 to 70 mass% based on the mass of the polymerizable composition. A further preferable ratio is in the range of 20 to 60% by mass based on the polymerizable composition. A particularly preferred ratio is in the range of 30 to 50% by mass based on the polymerizable composition.

When the proportion of the polymer precursor is in the range of 5 to 70% by mass, a polymer network type element or a polymer dispersion type element is produced. The polymer network type and the polymer dispersion type are mixed according to the ratio of the polymer. In these elements, a polarizing plate is not required unlike the PSA element. In the polymer network type element, an orientation film is used as necessary.

It is preferable that the ratio of the liquid crystal composition is in the range of 30 to 95% by mass and the ratio of the polymer precursor is in the range of 5 to 70% by mass based on the mass in the polymerizable composition.

Second, a liquid crystal composition will be explained. The composition contains a plurality of liquid crystalline compounds. The composition may also contain additives. The additive is optically active compound, antioxidant, ultraviolet absorbent, delustering agent, pigment, defoaming agent, polymerization initiator, polymerization inhibitor, polar compound, etc. From the viewpoint of the liquid crystalline compound, the compositions are classified into composition a and composition B. The composition a may contain other liquid crystalline compounds, additives, and the like, in addition to the liquid crystalline compound selected from the compound represented by the formula (1), and optionally the compound represented by the formula (2) and the compound represented by the formula (3) (each referred to as the compound (1), the compound (2), and the compound (3)). The "other liquid crystalline compound" is a liquid crystalline compound different from the compound (1), the compound (2) and the compound (3). The compounds are mixed in the composition for the purpose of further adjusting the properties.

The composition B substantially contains only a liquid crystalline compound selected from the compound (1) and, if necessary, the compounds (2) and (3). "substantially" means that the composition B may contain additives but does not contain other liquid crystalline compounds. The amount of ingredients of composition B is small compared to composition a. From the viewpoint of cost reduction, composition B is superior to composition a. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystalline compounds, the composition a is superior to the composition B.

Third, the main characteristics of the liquid crystalline compound and the main effects of the compound on the liquid crystal composition or the device will be described. The main properties of the liquid crystalline compounds are summarized in table 2. In the notation of Table 2, L means large or high, M means moderate, and S means small or low. The symbol L, symbol M, and symbol S are classified based on qualitative comparison between the component compounds, and 0 (zero) means extremely small.

TABLE 2 Properties of liquid crystalline Compounds

Compound (I)	Compound (1)	Compound (2)	Compound (3)
				Upper limit temperature	S～L	S～L	S～L
Viscosity of the oil	M～L	S～M	M～L
				Optical anisotropy	M～L	S～L	M～L
Anisotropy of dielectric constant	S～L	0	M～L¹⁾
				Specific resistance	L	L	L

1) The value of the dielectric anisotropy is negative, and the symbol indicates the magnitude of the absolute value

The main effects of the liquid crystalline compounds on the characteristics of the liquid crystal composition are as follows.

The compound (1) can be used as the component A and improves the dielectric anisotropy.

The compound (2) can be used as the component B with the upper limit temperature being raised or the lower limit temperature being lowered.

The compound (3) can be used as the component C and increases the dielectric constant in the short axis direction of the liquid crystal molecules.

Fourth, a combination or a preferable ratio of the liquid crystalline compounds will be described. Preferred combinations are component a + component B, component a + component C or component a + component B + component C. Further preferred combinations are component A + component B or component A + component B + component C. It is also possible to combine a specific one or two compounds selected from the component A with the component B (or the component C). The same applies to the component B or the component C.

The preferred proportion of the component A is 5% by mass or more in order to improve the dielectric anisotropy based on the mass of the liquid crystal composition, and 90% by mass or less in order to lower the lower limit temperature. Further, the preferable ratio is in the range of 10 to 85 mass%. A particularly preferred ratio is in the range of 20 to 80 mass%.

The preferred proportion of the component B is 5% by mass or more in order to raise the upper limit temperature or lower the lower limit temperature, and 90% by mass or less in order to improve the dielectric anisotropy, based on the mass of the liquid crystal composition. Further, the preferable ratio is in the range of 10 to 85 mass%. A particularly preferred ratio is in the range of 20 to 80 mass%.

The preferred proportion of the component C is 3 mass% or more in order to increase the dielectric constant of the liquid crystal molecules in the short axis direction, and 25 mass% or less in order to lower the lower limit temperature, based on the mass of the liquid crystal composition. Further, the preferable ratio is in the range of 5 to 20% by mass. A particularly preferred ratio is in the range of 5 to 15 mass%.

Fifth, a preferred embodiment of the liquid crystalline compound will be described. In the formula (1), R¹Is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms or alkenyl group having 2 to 12 carbon atoms. Preferred R is for improving stability to light or heat¹Is an alkyl group having 1 to 12 carbon atoms. In the compounds (compound (1) to (1-48), etc.) which are preferable examples of the compound (1), R¹The same applies to the definitions, suitable forms and the like.

In the formula (2), R²And R³Is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms or alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. For increasing the upper limit temperature or decreasing the lower limit temperature, R is preferably²Or R³R is an alkenyl group having 2 to 12 carbon atoms, and is preferably selected from the group consisting of²Or R³Is an alkyl group having 1 to 12 carbon atoms.In the compounds (such as the compounds (2-1) to (2-23)) as preferable examples of the compound (2), R²And R³The same applies to the definitions, suitable forms and the like.

In the formula (3), R⁴And R⁵Is hydrogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms or alkenyloxy group having 2 to 12 carbon atoms. Preferred R is for improving stability to light or heat⁴Or R⁵R is preferably an alkyl group having 1 to 12 carbon atoms for increasing the dielectric constant in the minor axis direction of the liquid crystal molecules⁴Or R⁵Is alkoxy with 1 to 12 carbon atoms. In the compounds (such as the compounds (3-1) to (3-35)) as preferable examples of the compound (3), R⁴And R⁵The same applies to the definitions, suitable forms and the like.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. Further preferred alkyl groups for reducing the viscosity are methyl, ethyl, propyl, butyl or pentyl.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. Further preferred alkoxy groups for reducing the viscosity are methoxy or ethoxy.

Preferred alkenyl groups 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. Further preferred alkenyl groups for reducing the viscosity are vinyl, 1-propenyl, 3-butenyl or 3-pentenyl. The preferred steric configuration of-CH ═ CH-in these alkenyl groups depends on the position of the double bond. In order to reduce viscosity and the like, the trans configuration is preferable among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl. Among alkenyl groups such as 2-butenyl, 2-pentenyl, 2-hexenyl, the cis configuration is preferred.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. Further preferred alkenyloxy groups for reducing the viscosity are allyloxy or 3-butenyloxy.

Preferred examples of alkyl groups in which at least one hydrogen is substituted by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl or 8-fluorooctyl. Further preferable examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl and 5-fluoropentyl for improving the dielectric anisotropy.

Preferred examples of alkenyl groups in which at least one hydrogen is substituted by fluorine or chlorine are 2, 2-difluorovinyl, 3-difluoro-2-propenyl, 4-difluoro-3-butenyl, 5-difluoro-4-pentenyl or 6, 6-difluoro-5-hexenyl. Further preferable examples for lowering the viscosity are 2, 2-difluorovinyl group or 4, 4-difluoro-3-butenyl group.

Ring a is 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or tetrahydropyran-2, 5-diyl. For the purpose of enhancing the optical anisotropy, ring A is preferably 1, 4-phenylene, 2-fluoro-1, 4-phenylene or 3-fluoro-1, 4-phenylene. In order to increase the upper limit temperature, the steric configuration associated with the 1, 4-cyclohexylene group is a trans configuration rather than a cis configuration. Tetrahydropyran-2, 5-diyl as

Preferably, it is

The ring B and the ring C are 1, 4-cyclohexylene, 1, 3-phenylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2, 5-difluoro-1, 4-phenylene or pyrimidine-2, 5-diyl. For increasing the upper temperature limit or for decreasing the lower temperature limit, ring B or ring C is preferably a 1, 4-cyclohexylene group, and for decreasing the lower temperature limit, ring B or ring C is preferably a 1, 4-phenylene group.

Ring D and ring F are 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chroman-2, 6-diyl or chroman-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine. For lowering the lower limit temperature or for raising the upper limit temperature, ring D or ring F is preferably 1, 4-cyclohexylene, and for lowering the lower limit temperature, ring D or ring F is preferably 1, 4-phenylene.

Ring E is 2, 3-difluoro-1, 4-phenylene, 2-chloro-3-fluoro-1, 4-phenylene, 2, 3-difluoro-5-methyl-1, 4-phenylene, 3,4, 5-trifluoronaphthalene-2, 6-diyl, 7, 8-difluorochromane-2, 6-diyl, 3,4,5, 6-tetrafluorofluorene-2, 7-diyl (FLF4), 4, 6-difluorodibenzofuran-3, 7-diyl (DBTF2), 4, 6-difluorodibenzothiophene-3, 7-diyl (DBTF2), or 1,1,6, 7-tetrafluoroindan-2, 5-diyl (InF 4).

The ring E is preferably 2, 3-difluoro-1, 4-phenylene for lowering the viscosity, and 4, 6-difluorodibenzothiophene-3, 7-diyl for increasing the dielectric constant in the short axis direction of the liquid crystal molecule.

Z¹Is a single bond, ethylene, ethenylene, ethynylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy. For raising the upper limit temperature, preferred is Z¹Is a single bond, and Z is preferably a bond for improving dielectric anisotropy¹Is difluoromethyleneoxy. Particularly preferred Z¹Is a single bond. Z²Is a single bond, ethylene, ethenylene, ethynylene, methyleneoxy or carbonyloxy. Preferred Z is Z for improving stability to light or heat²Is a single bond. Z³And Z⁴Each independently a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. For lowering the lower limit temperature, Z is preferable³Or Z⁴Is a single bond, and Z is preferably a single bond in order to increase the dielectric constant in the short axis direction of the liquid crystal molecules³Or Z⁴Is a methyleneoxy group. Particularly preferred Z³Or Z⁴Is a single bond.

Divalent radicals such as methyleneoxy are asymmetric to the left and right. In the methyleneoxy group, -CH₂O-is superior to-OCH₂-. Among the carbonyloxy groups, -COO-is preferable to-OCO-. Of difluoromethyleneoxy, -CF₂O-is superior to-OCF₂-。

a is 1, 2,3 or 4. In order to lower the lower limit temperature, a is preferably 2, and in order to improve the dielectric anisotropy, a is preferably 3. b is 1, 2 or 3. For lowering the lower limit temperature, b is preferably 1, and for raising the upper limit temperature, b is preferably 2 or 3. c is 0, 1, 2 or 3, d is 0 or 1, and the sum of c and d is 3 or less. For lowering the lower limit temperature, c is preferably 1, and for raising the upper limit temperature, c is preferably 2 or 3. D is preferably 0 in order to increase the dielectric constant of the liquid crystal molecules in the short axis direction, and d is preferably 1 in order to lower the lower limit temperature.

X¹And X²Is hydrogen or fluorine. For raising the upper limit temperature, X is preferable¹Or X²X is preferably hydrogen for improving dielectric anisotropy¹Or X²Is fluorine.

Y¹Is fluorine, chlorine, cyano, alkyl of carbon number 1 to 12 with at least one hydrogen substituted by fluorine or chlorine, alkoxy of carbon number 1 to 12 with at least one hydrogen substituted by fluorine or chlorine, or alkenyloxy of carbon number 2 to 12 with at least one hydrogen substituted by fluorine or chlorine. For reducing the viscosity, Y is preferred¹Fluorine, Y is preferred for improving dielectric anisotropy or refractive index anisotropy¹Is cyano.

A preferred example of an alkyl group in which at least one hydrogen is substituted with fluorine or chlorine is trifluoromethyl. A preferred example of an alkoxy group wherein at least one hydrogen is substituted by fluorine or chlorine is trifluoromethoxy. A preferred example of an alkenyloxy group in which at least one hydrogen is substituted by fluorine or chlorine is a trifluorovinyloxy group.

Sixth, a preferred liquid crystalline compound is shown. Preferred compounds (1) usable as the component A are compounds represented by the formulae (1-1) to (1-48) described in the item 2 (provided as the compounds (1-1) to (1-48), respectively).

The compound (1) usable as the component A is preferably at least one of the compound (1-1), the compound (1-2), the compound (1-6), the compound (1-7), the compound (1-9), the compound (1-13), the compound (1-16), the compound (1-17), the compound (1-23), the compound (1-24), the compound (1-28), the compound (1-29), the compound (1-30), the compound (1-33), the compound (1-34), the compound (1-41), the compound (1-42) or the compound (1-48).

In addition, it is preferable that at least two of the components A are

Compound (1-1) and compound (1-6),

Compound (1-1) and compound (1-9),

Compound (1-2) and compound (1-9),

Compound (1-2) and compound (1-16),

Compounds (1-9) and compounds (1-16),

Compound (1-9) and compound (1-24),

Compound (1-9) and compound (1-41),

Compounds (1-13) and compounds (1-16),

Compounds (1-16) and compounds (1-24),

Compounds (1-16) and compounds (1-41),

Compound (1-16) and compound (1-42), or

A combination of the compounds (1-16) and the compounds (1-48).

Furthermore, a plurality of compounds (1-6), a plurality of compounds (1-9), a plurality of compounds (1-16), a plurality of compounds (1-29), and a plurality of compounds (1-41) may be combined.

By containing Y in the compound (1)¹At least one compound that is fluorine is used as the component a, and the dielectric anisotropy or refractive index anisotropy of the liquid crystal composition tends to be improved. By containing Y in the compound (1)¹At least one compound that is a cyano group tends to improve the compatibility of the polymerizable compound with the liquid crystalline compound as the component a.

The compound (2) which is preferable as the component B is a compound represented by the formula (2-1) to the formula (2-23) described in the item 5 (provided as the compound (2-1) to the compound (2-23), respectively). Of these compounds, it is preferable that at least one of the components B is a compound (2-1), a compound (2-2), a compound (2-3), a compound (2-6), a compound (2-9), a compound (2-10), a compound (2-11), a compound (2-12), a compound (2-13), a compound (2-16), a compound (2-20) or a compound (2-21).

Preferably at least two of the components B are

Compound (2-2) and compound (2-9),

Compound (2-2) and compound (2-10),

Compound (2-2) and compound (2-12),

Compound (2-9) and compound (2-10),

Compound (2-9) and compound (2-12),

Compound (2-9) and compound (2-13),

Compound (2-10) and compound (2-12), or

Compound (2-12) and compound (2-13)

Combinations of (a) and (b).

Furthermore, a plurality of compounds (2-9) and a plurality of compounds (2-12) may be combined.

By using a compound having a terphenyl structure, the upper limit temperature of the liquid crystal phase tends to be increased. Further, the liquid crystalline compound having a fluorine-substituted terphenyl structure tends to have improved compatibility with other liquid crystalline compounds.

Preferred compounds (3) usable as the component C are compounds represented by the formulae (3-1) to (3-35) described in the item 8 (provided as the compounds (3-1) to (3-35), respectively).

Of these compounds, it is preferable that at least one of the components C is the compound (3-1), the compound (3-3), the compound (3-6), the compound (3-8), the compound (3-10), the compound (3-14) or the compound (3-34). Preferably, at least two of the components C are a combination of the compound (3-1) and the compound (3-8), the compound (3-1) and the compound (3-14), the compound (3-3) and the compound (3-8), the compound (3-3) and the compound (3-14), the compound (3-3) and the compound (3-34), the compound (3-6) and the compound (3-8), the compound (3-6) and the compound (3-10), or the compound (3-6) and the compound (3-14).

Seventh, a preferred embodiment of the polymer precursor and an example thereof will be described. The polymer is derived from a polymer precursor by polymerization. The precursor of the polymer is a polymerizable compound.

The precursor of the polymer for ensuring the adhesion between the electrode-carrying plastic film and the liquid crystal composite is preferably a combination of a monofunctional polymerizable compound (M-1) having no cyclic structure, a monofunctional polymerizable compound (M-2) having a cyclic structure, and a polyfunctional urethane (meth) acrylate oligomer.

Each of the polymerizable compound and the urethane (meth) acrylate oligomer may be used alone or as a mixture of a plurality of compounds.

A preferable monofunctional polymerizable compound is a compound represented by the formula (M-1) (compound (M-1)).

In the formula (M-1),

M¹⁰⁰hydrogen, fluorine, alkyl having 1 to 5 carbon atoms or alkyl having 1 to 5 carbon atoms wherein at least one hydrogen is substituted by fluorine or chlorine, preferably hydrogen or methyl.

R¹⁰⁰And R¹⁰¹Each independently hydrogen, a C1-12 linear or branched alkyl group, a C1-12 linear or branched hydroxyalkyl group, at least one-CH group in these alkyl or hydroxyalkyl groups₂May be substituted by-O-, -N (R)¹⁰²) -, -CO-, -COO-or-OCO-substituted, R¹⁰²Hydrogen, straight chain alkyl or branched alkyl of carbon number 1 to 12,

preferably, it is

Each independently hydrogen, a C1-10 linear alkyl group or a C3-10 branched alkyl group, a C1-10 linear hydroxyalkyl group, or a C3-10 branched hydroxyalkyl group,

at least one of-CH in these alkyl or hydroxyalkyl groups₂May be-O-or-N (R)¹⁰²) -substituted, R¹⁰²Hydrogen, straight chain alkyl with carbon number of 1 to 10.

The following examples are preferred for the compound (M-1).

Is N, N-dimethylacrylamide,

N, N-diethylacrylamide,

Isopropyl acrylamide,

N- (butoxymethyl) acrylamide,

N- (2-hydroxyethyl) acrylamide,

N- [3- (dimethylamino) ethyl ] acrylamide,

N- [3- (dimethylamino) propyl ] acrylamide.

The monofunctional polymerizable compound having a cyclic structure is a compound represented by the formula (M-2) (compound (M-2)).

In the formula (M-2),

M¹⁰¹is hydrogen, fluorine, alkyl of 1 to 5 carbon atoms or alkyl of 1 to 5 carbon atoms wherein at least one hydrogen is substituted by fluorine or chlorine, Z¹⁰⁰Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which alkylene group at least one hydrogen may be substituted by fluorine or chlorine, at least one-CH₂May be substituted by-O-, -CO-, -COO-or-OCO-,

R¹⁰³is a monovalent group having 5 to 35 carbon atoms formed by removing one hydrogen from a carbocyclic saturated aliphatic compound, heterocyclic saturated aliphatic compound, carbocyclic unsaturated aliphatic compound, heterocyclic unsaturated aliphatic compound or carbocyclic or heterocyclic aromatic compound, wherein R is a monovalent group¹⁰³At least one hydrogen contained in (A) may be substituted by an alkyl group having 1 to 12 carbon atoms, and at least one-CH₂-may be substituted by-O-, -CO-, -COO-or-OCO-.

Preferably at least one compound selected from the group consisting of the compounds represented by the formulae (M-2-1) to (M-2-10).

M¹⁰¹Is hydrogen or methyl, n¹⁰⁰Is 0, 1 or 2, m¹⁰⁰Is an integer of 2 to 6.

The urethane (meth) acrylate oligomer having two or more (meth) acryloyl groups used as the polyfunctional polymerizable compound is preferably a polyester urethane (meth) acrylate oligomer or a polyether urethane (meth) acrylate oligomer, and more preferably a polyether urethane (meth) acrylate oligomer.

The weight average molecular weight is preferably in the range of 2,000 to 30,000, more preferably in the range of 5,000 to 15,000, and further preferably in the range of 7,000 to 12,000.

The reason for this is that: when the weight average molecular weight is too small, the influence of curing shrinkage becomes large and the adhesiveness tends to be lowered. On the other hand, when the weight average molecular weight is too large (the chain length of the monomer unit becomes too long), the density of the network structure becomes low, and the liquid crystal molecules easily enter between the molecular chains of the oligomer, so that the interaction between the polymer interface and the liquid crystalline compound is reduced, and the driving voltage of the liquid crystal composition contained in the liquid crystal composite tends to become low.

When the adhesion is further enhanced, a polymerizable compound (M-3) or a compound (M-4) having a phosphoric acid moiety may be additionally used as a polymer precursor.

In the formulae (M-3) to (M-4),

M¹⁰²is hydrogen or a methyl group,

n¹⁰¹、n¹⁰²and n¹⁰³Independently 1 to 4.

Preferred n is¹⁰¹、n¹⁰²And n¹⁰³Independently 2.

Here, the action of the precursor of the polymer will be explained.

The monofunctional polymerizable compound (M-1) having a nitrogen atom and an acyclic structure can control the glass transition temperature of the resulting polymer. The polymerizable compound (M-1) has a linear structure such as a linear alkyl group or a branched alkyl group, and the glass transition temperature of the obtained polymer tends to be low. If the glass transition temperature of the polymer is low, the driving temperature range of the liquid crystal composition contained in the liquid crystal composite can be reduced. In addition, since a strong interaction with a substrate interface or an electrode interface or a strong interaction with urethane (meth) acrylate described later is considered, it is expected that the contribution to the improvement of the adhesion is large.

The monofunctional polymerizable compound (M-2) having a cyclic group can also control the glass transition temperature of the resulting polymer. The polymerizable compound (M-2) tends to increase the glass transition temperature of the resulting polymer. It is considered that the elastic modulus of the polymer obtained from the polymerizable compound (M-2) tends to be higher than that of the polymer using the polymerizable compound (M-1). The adhesion was evaluated in a peeling test in which the aggregate peeling occurred in the light control layer and the interface peeling occurred in the interface. It is considered that when the elastic modulus is increased, aggregation and peeling occurring in the light control layer can be suppressed, and the adhesion to the support substrate tends to be improved.

In the urethane (meth) acrylate oligomer having a polymer comprising a monomeric unit having a linear structure group, when the chain length of the monomeric unit is long, the interaction between the polymer interface and the liquid crystalline compound is reduced, and the driving voltage of the liquid crystal composition contained in the liquid crystal composite tends to be reduced. When the ether structure is contained in the monomer structure having a linear group, the driving voltage of the liquid crystal composition contained in the liquid crystal composite obtained tends to be low.

When the liquid crystal composite of the present application is used as a light control layer of a liquid crystal light control element, the adhesion between the light control layer and an electrode (for example, a plastic film with Indium Tin Oxide (ITO)) tends to be high, particularly by combining a monofunctional polymerizable compound (M-1) having an acyclic structure of a nitrogen atom, a monofunctional polymerizable compound (M-2) having a group having a cyclic structure, and a urethane (meth) acrylate oligomer.

In order to increase the peel strength of the liquid crystal composite at the interface of the support substrate (for example, at the interface with the plastic film with an ITO electrode), a polymerizable compound containing a non-liquid crystalline phosphoric acid moiety having a polar group, which is thought to cause hydrogen bonding with a hydroxyl group present on the surface of the ITO electrode and to strongly interact with the hydroxyl group, may be used in combination.

Based on the total mass of the liquid crystal composition and the precursor of the polymer,

the proportion of the compound (M-1) is in the range of 3 to 25% by mass, preferably 5 to 25% by mass, and more preferably 10 to 25% by mass,

the proportion of the compound (M-2) is in the range of 3 to 30% by mass, preferably 10 to 25% by mass,

the proportion of the polyfunctional urethane (meth) acrylate oligomer is preferably in the range of 5 to 25 mass%.

Wherein the total proportion of the precursors of the polymers is not more than 70% by mass.

In order to improve the adhesion between the light modulation layer and the interface of the electrode (for example, a plastic film with ITO (indium tin oxide)), the following mass ratio is preferably used.

The mass ratio of the polymerizable compound (M-1) to the urethane (meth) acrylate oligomer ((M-1)/urethane (meth) acrylate oligomer) is preferably 3/1 to 1/3, and more preferably 2/1 to 1/2.

Further, the mass ratio ((M-1)/(M-2)) of the polymerizable compound (M-1) to the polymerizable compound (M-2) is preferably 3/1 to 1/3, more preferably 2/1 to 1/2. The preferable amount of addition (the total amount thereof when both are used) of the polymerizable compound (M-3) or the compound (M-4) is 0.001 to 0.5% by mass, more preferably 0.01 to 0.3% by mass, based on the total mass of the liquid crystal composition and the precursor of the polymer.

In the present invention, a monofunctional polymerizable compound having a linear structure such as a linear alkyl group or a branched alkyl group represented by the formula (M-5), the formula (M-5-E) and/or the formula (M-5-P) or an ether structure, which is different from the compound (M-1), the compound (M-2) and the urethane (meth) acrylate oligomer, may be contained. Further, a polyfunctional polymerizable compound having a linear structure such as a linear alkyl group or a branched alkyl group ((formula (M-6)) may be contained.

A plurality of monofunctional polymerizable compounds may be used alone or in combination.

A plurality of polyfunctional polymerizable compounds may be used alone or in combination.

The monofunctional polymerizable compound and the polyfunctional polymerizable compound may be used in combination, or may be used alone or in combination of two or more.

The main function of the monofunctional polymerizable compound having a linear structure such as a linear alkyl group or a branched alkyl group in the side chain or an ether structure is to improve the solubility of the compound (M-1), the compound (M-2), or the urethane (meth) acrylate oligomer in the liquid crystal composition. Further, by maintaining the uniformity of the polymerizable composition, the liquid crystal composite (for example, a light control layer of a liquid crystal light control element) after polymerization can have uniform scattering properties. The polymerizable compound can control the glass transition temperature of the resulting polymer. The glass transition temperature of a polymer having a linear structure or an ether structure, such as a linear alkyl group or a branched alkyl group, in a side chain tends to be low. If the glass transition temperature of the polymer is low, the driving temperature range of the liquid crystal composition contained in the liquid crystal composite can be reduced. The reason for this is not clear, but is considered to be because if the chain length of the side chain of the polymer becomes long or the polymer has an ether structure, the interaction between the surface of the polymer and the liquid crystalline compound is reduced. Further, when the chain length of the side chain of the polymer is long or the side chain has an ether structure, the driving voltage of the liquid crystal composition contained in the liquid crystal composite to be obtained tends to be low. The reason for this is also not clear, but is considered to be due to a decrease in the interaction between the polymer surface and the liquid crystalline compound.

In the formula (M-5), the metal salt,

M⁵⁰¹is hydrogen or a methyl group,

R⁵⁰¹is hydrogen or an alkyl group having 1 to 20 carbon atoms, in which at least one hydrogen may be substituted by an alkyl group having 1 to 12 carbon atoms, fluorine or chlorine, and at least one-CH₂-may be substituted by-O-, -CO-, -COO-, -OCO-, -CH ═ CH-, or-C ≡ C-.

In the formulae (M-5-E) and (M-5-P),

M⁵⁰¹is hydrogen or a methyl group,

R⁵⁰²is an alkyl group having a carbon number of 1 to 6,

n is 1 to 30.

Hydrogen in the ethylene glycol structure of the formula (M-5-E) and the propylene glycol structure of the formula (M-5-P) may be substituted with an alkyl group having 1 to 3 carbon atoms.

In the formula (M-6), M⁶⁰¹Independently of the other substituents, is hydrogen or methyl,

R⁶⁰¹is an alkylene group having 1 to 40 carbon atoms, in which at least one hydrogen may be substituted by an alkyl group having 1 to 20 carbon atoms, an alkyl (meth) acrylate having 1 to 20 carbon atoms, an alkoxy (meth) acrylate having 1 to 20 carbon atoms, an alkyl (meth) acrylate having 1 to 20 carbon atoms, fluorine or chlorine, and at least one-CH group₂-may be substituted by-O-, -CO-, -COO-or-OCO-.

Examples of the preferable compounds represented by the formula (M-5) include compounds represented by the following formulae (M-5-1) to (M-5-5).

In the case of the preferred compound represented by the formula (M-5-E),

M⁵⁰¹preferably hydrogen or a methyl group, more preferably hydrogen,

R⁵⁰²preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl, ethyl or propyl group,

n is preferably 1 to 30, more preferably 2 to 25.

Preferred specific examples include the following compounds.

Examples of preferred compounds represented by the formula (M-6) are compounds represented by the following formulae (M-6-1) to (M-6-18).

Here, a and b represent the number of bases described on the right side of these characters, respectively. The following formulae (M-6-17) and (M-6-18) are also synonymous.

The main role of the polyfunctional polymerizable compound having a linear structure such as a linear alkyl group or a branched alkyl group is to increase the crosslink density of the obtained polymer. When the crosslinking density is increased, the reliability such as moisture resistance, heat resistance, light resistance, weather resistance and the like is improved.

The glass transition temperature of a polymer containing a polyfunctional polymerizable compound having a linear structure such as a linear alkyl group or a branched alkyl group tends to be high. When the crosslinking density is increased and the glass transition temperature of the polymer is increased, the interaction with the liquid crystalline compound is also increased, and the driving voltage of the light control layer may be increased. In order to perform low-voltage driving while maintaining reliability, it is desirable not to excessively increase the crosslinking density. From the above viewpoint, a polyfunctional polymerizable compound having a relatively large molecular weight or a polyfunctional polymerizable compound containing a large number of ether bonds, which is likely to have a low glass transition temperature after polymerization, is preferable.

The amount of the monofunctional polymerizable compound having a linear structure such as a linear alkyl group or a branched alkyl group or the like and the polyfunctional polymerizable compound having a linear structure such as a linear alkyl group or a branched alkyl group is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, and still more preferably 3 to 20% by mass, based on the total amount of the polymer precursor.

In the present invention, a polymerizable compound having a liquid crystal structure (mesogen structure) may be further contained for the purpose of controlling scattering properties or improving heat resistance. The polymerizable compound having a liquid crystal structure is copolymerized with a precursor of the polymer to form a polymer.

The polymerizable compound having a preferable liquid crystal structure is a compound represented by formula (7), formula (8) or formula (9) (referred to as compound (7), compound (8) and compound (9), respectively).

The polymerizable compound having a liquid crystal structure may be a mixture of compounds selected from the group consisting of the compound (7), the compound (8) and the compound (9).

The mixture may contain a polymerizable compound different from the compound (7), the compound (8) or the compound (9).

In the compounds (7), (8) and (9), the ring G, the ring I, the ring J, the ring K, the ring L and the ring M are 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, and here, at least one hydrogen may be substituted with fluorine, chlorine, cyano, hydroxyl, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or an alkanoyl group having 1 to 5 carbon atoms. Among the compounds (7), (8) and (9), preferred rings are 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 2-methyl-1, 4-phenylene, 2-methoxy-1, 4-phenylene or 2-trifluoromethyl-1, 4-phenylene. Further preferred rings are 1, 4-cyclohexylene or 1, 4-phenylene.

Z⁸、Z¹⁰、Z¹²、Z¹³And Z¹⁷Is a single bond, -O-, -COO-, -OCO-or-OCOO-. Z⁹、Z¹¹、Z¹⁴And Z¹⁶Is a single bond, -OCH₂-、-CH₂O-、-COO-、-OCO-、-COS-、-SCO-、-OCOO-、-CONH-、-NHCO-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂-、-CH＝CHCOO-、-OCOCH＝CH-、-CH₂CH₂COO-、-OCOCH₂CH₂-、-CH＝CH-、-N＝CH-、-CH＝N-、-N＝C(CH₃)-、-C(CH₃) N-, -N-or-C ≡ C-. Z¹⁵Is a single bond, -O-or-COO-. Preferred Z⁸、Z¹⁰、Z¹²、Z¹³Or Z¹⁷Is a single bond or-O-. Preferred Z⁹、Z¹¹、Z¹⁴Or Z¹⁶Is a single bond, -OCH₂-、-CH₂O-、-COO-、-OCO-、-CH₂CH₂-、-CH₂CH₂COO-or-OCOCH₂CH₂-。

Y²Hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, a linear alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms, a linear alkoxy group having 1 to 20 carbon atoms, or a linear alkoxycarbonyl group having 2 to 20 carbon atoms. Preferred is Y²Cyano, straight-chain alkyl or straight-chain alkoxy.

f and h are integers from 1 to 4; k and m are integers from 0 to 3, and the sum of k and m is from 1 to 4; e. g, i, j, l and n are integers from 0 to 20.

M⁷To M¹²Is hydrogen or methyl.

Examples of the compound (7) are as follows.

In formulae (7-1) to (7-24), M⁷Is hydrogen orMethyl, e is an integer from 1 to 20.

Examples of the compound (8) are as follows.

In formulae (8-1) to (8-31), M⁸And M⁹Is hydrogen or methyl, g and i are integers from 1 to 20.

Examples of the compound (9) are as follows.

In formulae (9-1) to (9-10), M¹⁰、M¹¹And M¹²Is hydrogen or methyl, j, l and n are integers from 1 to 20.

The compound (7), the compound (8) and the compound (9) have at least one acryloyloxy group (-OCO-CH ═ CH)₂) Or methacryloyloxy (-OCO- (CH)₃)C＝CH₂). The liquid crystalline compounds have a mesogen (a site that induces rigidity of liquid crystallinity), and these compounds also have a mesogen. Therefore, these compounds are aligned in the same direction together with the liquid crystalline compound by the action of the alignment film. The orientation is also maintained after polymerization.

The liquid crystal composite obtained by polymerizing the polymerizable composition for a light control element has high transparency. In order to improve other characteristics, a polymerizable compound different from the compound (7), the compound (8) and the compound (9) may be used in combination.

The preferable addition amount of the compounds (7) to (9) is 3 to 50% by mass, more preferably 5 to 30% by mass, relative to the total amount of the precursor of the polymer.

Eighth, a method for synthesizing the component compound will be explained. These compounds can be synthesized using known methods. A synthesis method is exemplified. The compounds (1-9) and (1-16) were synthesized by the method described in Japanese patent laid-open No. 2-233626. The compound (2-1) is synthesized by the method described in Japanese patent laid-open publication No. 59-176221. The compound (3-1) is synthesized by the method described in Japanese patent laid-open No. Hei 2-503441. Antioxidants are commercially available. The compound (11-1) described later can be obtained from Sigma Aldrich Corporation. The compound (11-2) and the like were synthesized by the method described in the specification of U.S. Pat. No. 3660505. The polymerizable compound is commercially available or synthesized by a known method.

Compounds not described in the synthesis method can be synthesized by the methods described in the following written description: organic Synthesis (Organic Synthesis), Inc. (John Wiley & Sons, Inc.), (Organic Reactions), Inc. (John Wiley & Sons, Inc.)), (Organic Synthesis), Integrated Circuit (Pergeman Press), New Experimental chemistry lecture (Bolus), etc. The compositions are prepared from the compounds obtained in the manner described, using existing methods. For example, the component compounds are mixed and then dissolved in each other by heating.

Ninth, a photopolymerization initiator to be added to the polymerizable composition will be described. The polymerizable composition of the present invention contains a photopolymerization initiator as an essential component. Suitable conditions for carrying out the photopolymerization, or suitable types and amounts of initiators, are known to those skilled in the art and are described in the literature. For example, ornirade (Omnirad)651 (registered trademark; IGM Resins), ornirade (Omnirad)184 (registered trademark; IGM Resins), or ornirade (Omnirad)1173 (registered trademark; IGM Resins) as photopolymerization initiators are suitable for radical polymerization.

As for the preferable addition amount, the proportion of the photopolymerization initiator is 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total mass of the liquid crystal composition and the precursor of the polymer. When the liquid crystal polymerizable compound is contained together with the liquid crystal composition and the polymer precursor, the total amount is the total amount of the liquid crystal composition, the polymer precursor, and the liquid crystal polymerizable compound.

Tenth, additives that can be added to the polymerizable composition will be described.

The additives include antioxidants, ultraviolet absorbers, delusterants, pigments, defoaming agents, polymerization initiators other than photopolymerization initiators, polymerization inhibitors, polar compounds, and the like. The additive may be added to the liquid crystal composition or the polymerizable compound in advance.

The preferable addition amount is 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total amount of the liquid crystal composition and the precursor of the polymer. When the polymerizable compound having a liquid crystal structure is contained, the ratio is based on the total amount of the liquid crystal composition, the precursor of the polymer, and the polymerizable compound having a liquid crystal structure.

In addition, an optically active compound may be added to the polymerizable composition for the purpose of inducing a helical structure of liquid crystal molecules and imparting a twist angle (torsion angle). Examples of the compounds are compounds (10-1-1) to (10-7-1) represented by the following formulae. The preferable proportion of the optically active compound is 5% by mass or less with respect to the liquid crystal composition. Further, the preferable ratio is in the range of 0.01 to 2% by mass.

In order to prevent a decrease in specific resistance due to heating in the atmosphere or to maintain a large voltage holding ratio at room temperature and at a temperature close to the upper limit temperature even after the device is used for a long time, an antioxidant such as a compound (11-1) to a compound (11-3) represented by the following formulae may be added to the polymerizable composition.

The compound having a small volatility is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device is used for a long time. In order to obtain the above-mentioned effects, the preferable ratio of the antioxidant is 50 mass ppm or more with respect to the total amount of the liquid crystal composition, and the preferable ratio of the antioxidant is 600 mass ppm or less so as not to lower the upper limit temperature or not to raise the lower limit temperature. Further, the preferable ratio is in the range of 100 to 300 mass ppm.

Preferable 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. Preferable examples of the light stabilizer include compounds (12-1) to (12-16) represented by the following formulae. In order to obtain the above-mentioned effects, the preferable ratio of these absorbers or stabilizers is 50 mass ppm or more relative to the total amount of the liquid crystal composition, and the preferable ratio of these absorbers or stabilizers is 10000 mass ppm or less so as not to lower the upper limit temperature or not to raise the lower limit temperature. Further, the preferable ratio is in the range of 100 mass ppm to 10000 mass ppm.

The matting agent is a compound that receives light energy absorbed by the liquid crystalline compound and converts the light energy into thermal energy to prevent decomposition of the liquid crystalline compound. Preferable examples of the matting agent are a compound (13-1) to a compound (13-7) and the like. In order to obtain the above-mentioned effects, the preferable proportion of these matting agents is 50 mass ppm or more, and in order not to raise the lower limit temperature, the preferable proportion of these matting agents is 20000 mass ppm or less with respect to the total amount of the liquid crystal composition. Further, the preferable ratio is in the range of 100 mass ppm to 10000 mass ppm.

In order to be suitable for a guest-host (GH) mode element, a dichroic dye (dichromatic dye) as a dye is added to the composition. Liquid crystal light adjusting elements are sometimes used for partitioning a room. In this case, a coloring matter is added to the polymerizable composition for the purpose of absorbing specific light. Various pigments can be added. Liquid crystal dimming elements are sometimes used to block sunlight. In this case, a black (or blackish colored) dichroic dye is added to the liquid crystal composition. Black is prepared by mixing cyan (cyan), magenta (magenta), and yellow (yellow) dichroic pigments. In example 42 of Japanese patent laid-open No. 2006-193742, a black dichroic dye is described. The pigment is prepared by mixing three azo compounds with anthraquinones.

Examples of dichroic pigments are: benzothiadiazoles (benzothiazoles), diketopyrrolopyrroles (diketopyrrolopyrroles), azo compounds (azo compounds), azomethine compounds (azomethine compounds), methine compounds (methine compounds), anthraquinones (anthraquinones), cyanines (merocyanines), naphthoquinones (naphthoquinones), tetrazines (tetrazines), pyrromethenes (pyrromethenes), and rylenes (rylenes) such as perylenes or terrylenes (terrylenes).

The dichroic dye has at least some of the following characteristics.

a) The molecules of the dye are linear.

b) A skeleton unique to dichroic dyes such as a benzothiadiazole ring or a diketopyrrolopyrrole ring is present in the central part of the molecule.

c) The benzene or thiophene rings that together with the unique backbone form the molecule are located on the same plane.

d) The side chain is alkyl or alkoxy.

e) Has a conjugated double bond in the central part.

Preferred dichroic dyes are benzothiadiazoles, diketopyrrolopyrroles, azo compounds, anthraquinones and rylenes. Particularly preferred dichroic dyes are benzothiadiazoles, diketopyrrolopyrroles, azo compounds and rylenes. The skeletons of the four pigments are shown below. For example, benzothiadiazoles refer to dichroic pigments having a benzothiadiazole ring.

R and R' represent C1-30 hydrocarbon group which may have substituent, and may have azo group in the structure.

Examples of commercially available dichroic dyes are G-207, G-241, G-305, G-470, G-471, G-472, LSB-278, LSB-335, NKX-1366, NKX-3538, NKX-3540, NKX-3622, NKX-3739, NKX-3742, NKX-3773, NKX-4010 and NKX-4033, and S-428, SI-426, SI-486, M-412 and M-483 manufactured by Mitsui Fine Chemicals, manufactured by the tradename hand-May.

The preferable ratio of the dichroic pigment ranges from 0.01 to 25 mass% based on the weight of the liquid crystal composition. Further, the preferable ratio is in the range of 0.02 to 20% by mass. A particularly preferable ratio is in the range of 0.03 to 15 mass%.

In order to prevent foaming, an antifoaming agent such as dimethylsilicone oil or methylphenylsilicone oil may be added to the polymerizable composition. In order to obtain the above-mentioned effects, the preferable ratio of the defoaming agent is 1 mass ppm or more with respect to the total amount of the polymerizable composition, and the preferable ratio of the defoaming agent is 1000 mass ppm or less in order to prevent display failure. Further, the preferable ratio is in the range of 1 to 500 mass ppm.

The polymerizable compound is preferably irradiated with ultraviolet light during polymerization. Examples of the Ultraviolet irradiation lamp include a metal halide lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, an Ultraviolet-light emitting diode (UV-LED) lamp that can irradiate a single wavelength, 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. Avoiding the absorption wavelength region of the liquid crystal composition. The preferred wavelength is 330nm or more. A further preferred wavelength is 350nm or more, for example 365 nm. The reaction may be carried out at around room temperature, or may be carried out with heating.

In general, when a polymerizable compound is stored, a polymerization inhibitor may be added to prevent polymerization. Therefore, the precursor of the polymer used in the present invention is usually mixed into the liquid crystal composition in a state where the polymerization inhibitor is not removed. Examples of the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methyl hydroquinone, 4-t-butyl catechol, 4-methoxyphenol, phenothiazine and the like.

The polar compound is an organic compound having a polarity different from that of the compound (M-1), the compound (M-2), the compound (M-3) or the compound (M-4). May have a polymerizable group. Here, a compound having an ionic bond is not included. Atoms such as oxygen, sulfur and nitrogen are negatively charged and tend to have a partial negative charge. Carbon and hydrogen are neutral or tend to have a partial positive charge. Polarity arises because part of the charge is distributed unequally among the atoms of different species in the compound. For example, the polar compound has-OH, -COOH, -SH, -NH₂、>NH、>At least one of partial structures such as N-, or isocyanurate group or sulfo group.

Preferable examples of the compound include the following compound (14) and hydroxyalkyl (meth) acrylate.

Specific examples of the hydroxyalkyl (meth) acrylate include

2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,

2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and mixtures thereof,

3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, and mixtures thereof,

2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, and mixtures thereof,

4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and mixtures thereof,

2-hydroxypentyl acrylate and 2-hydroxypentyl methacrylate.

The preferable proportion of the compound (14) is in the range of 1 to 10% by mass, more preferably in the range of 1 to 7% by mass, based on the total mass of the liquid crystal composition and the precursor of the polymer.

The preferable proportion of the hydroxyalkyl (meth) acrylate is in the range of 1 to 20 mass%, more preferably in the range of 3 to 15 mass%, based on the total mass of the liquid crystal composition and the precursor of the polymer. It is considered that the glass transition temperature of the polymer is lowered by using a combination of a hydroxyalkyl (meth) acrylate and the compound (M-5-E) and/or the compound (M-5-P), and therefore, it is expected that the polymer can be driven even in a lower temperature environment.

Preferred hydroxyalkyl (meth) acrylates in combination

2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate or 4-hydroxybutyl methacrylate, more preferably 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate or 4-hydroxybutyl acrylate.

In the case of using a hydroxyalkyl (meth) acrylate in combination with the compound (M-5-E) and/or the compound (M-5-P), the hydroxyalkyl (meth) acrylate is in the range of 5 to 10% by mass, and the compound (M-5-E) and/or the compound (M-5-P) is in the range of 1 to 10% by mass, based on the total mass of the liquid crystal composition and the precursor of the polymer.

The polar group has a non-covalently bonded interaction with the surface of the glass substrate, the metal oxide film, or the like. The compound is adsorbed on the substrate surface by the action of polar groups, and controls the orientation of liquid crystal molecules. The polar compound may control not only the liquid crystalline compound but also the polymerizable compound. The effect is expected for polar compounds.

The liquid crystal composite is prepared by polymerizing the polymerizable composition.

In the case where the liquid crystal composite is used as a liquid crystal light-adjusting layer of a liquid crystal light-adjusting element, the liquid crystal light-adjusting element can be prepared using the polymerizable composition, for example, in the following manner. First, a polymerizable composition is sandwiched between a pair of substrates. In this case, the polymerizable composition is preferably dropped or applied by a vacuum injection method, a liquid crystal dropping method, or the like at a temperature higher than the upper limit temperature. It is preferable that the polymerizable composition is in a uniform isotropic phase state during a period from the start of the dropping or coating to the polymerization of the polymerizable composition. In the case of dropping or coating, the polymer dispersed liquid crystal composition can be sandwiched between two substrates by a method of sandwiching two substrates by a laminator or the like. The substrate was sandwiched between two substrates, and then the polymerizable compound was polymerized by light. In this case, as described above, the polymerization is preferably performed by ultraviolet irradiation. Upon polymerization, the polymer phase separates from the polymerizable composition. Thereby, a light modulation layer is formed between the substrates, the light modulation layer having the following layers: a layer containing a liquid crystal composition having a light-adjusting function; and a layer comprising a polymer. The light modulation layer is classified into a polymer dispersion type, a polymer network type, and a mixed existence type of the two. The grid in the network structure is preferably small. The preferred mesh is 0.2 μm to 2 μm, more preferably 0.2 μm to 1 μm, and particularly preferably 0.3 μm to 0.7 μm.

Finally, the application of the liquid crystal composite and the liquid crystal light control element will be described. An example of a preferable application of the liquid crystal composite obtained as described above is a liquid crystal light control element. The liquid crystal light control element includes a light control layer including a liquid crystal composite and a pair of substrates, and the light control layer is sandwiched between the pair of substrates. The substrate has an electrode which is generally disposed so as to face the side (inner side) of the light control layer. The substrate included in the liquid crystal light control element is preferably a transparent substrate, and preferably a pair of transparent substrates is included in the liquid crystal light control element so as to sandwich the light control layer. The electrode provided on the substrate is preferably a transparent electrode.

Examples of the transparent substrate included in the liquid crystal light control element include a plate made of a material that is hard to deform, such as a plastic plate (typically, a transparent plastic plate) typified by a glass plate, a quartz plate, and an acrylic plate. Examples of the preferred transparent substrate include a glass plate and a plastic plate (typically, a transparent plastic plate).

Other examples of the preferred transparent substrate are plastic films such as a Polyethylene Terephthalate (PET) film, an acryl film, and a polycarbonate film, and typically a flexible transparent plastic film. Depending on the application, one of the substrates may be an opaque material such as silicone resin.

The substrate has electrodes, typically transparent electrodes, thereon. The transparent electrode may have an alignment film or the like. Examples of transparent electrodes are Indium Tin Oxide (ITO) or conductive polymers.

As the alignment layer which can be provided on the substrate, a film such as polyimide or polyvinyl alcohol is suitable. For example, a polyimide alignment film can be obtained by coating a polyimide resin composition on a transparent substrate, and thermally hardening at a temperature of 180 ℃ or higher, and optionally subjecting to a rubbing treatment with cotton cloth or rayon cloth.

The pair of substrates are typically opposed so that the transparent electrode layers are on the inner side (light control layer side). Spacers may also be placed in order to make the thickness uniform between the substrates. Examples of spacers are glass particles, plastic particles, alumina particles, photo spacers (photo spacers), etc. The spacer is contained in the polymerizable composition of the present invention, and can be used as a raw material of the liquid crystal light-controlling element. The thickness of the light modulation layer is preferably 2 μm to 50 μm, and more preferably 5 μm to 20 μm. The spacers may be dispersed on the substrate in advance, or may be mixed into the polymerizable composition in advance and coated on the substrate simultaneously with coating of the polymerizable composition. When a pair of substrates is bonded, a general-purpose sealant can be used. An example of the sealant is an epoxy thermosetting composition.

The method of applying the polymerizable composition to the film substrate may be either a discontinuous batch method or a continuous roll-to-roll (roll) method.

For example, a polymerizable composition is applied between a film substrate and a film substrate, and then polymerized by UV irradiation to form a light-adjusting film. Examples of the coating method include a micro gravure method and a slit die (slot die) method. By selecting an appropriate coating method, a light-adjusting film can be manufactured.

Alternatively, the substrate may be produced by printing such as flexographic printing, gravure printing, UV offset printing, and screen printing. In this case, a light-adjusting film having a texture such as a frame, a stripe, a woven fabric, gradation, or a dot may be produced by masking (masking) or other methods.

The viscosity (25 ℃) of the polymerizable composition is 10 to 1000 mPas, depending on the coating method, although the optimum viscosity is different. When a film substrate is used, it is preferably 50 to 500 mPas, more preferably 100 to 300 mPas. If the viscosity is too low, the film tends to sag, and if the viscosity is too high, the film thickness is difficult to control.

In the element, a light absorbing layer, a diffusion reflection plate, and the like may be disposed on the back surface of the element as necessary. The functions of mirror reflection, diffuse reflection, regressive reflection, holographic reflection and the like can also be added.

The liquid crystal dimming element of the present invention can be used as an element for switching between a transparent state and a scattering state. For example, a liquid crystal dimming element can be used as a switching element by switching in a transparent state when no voltage is applied and in an opaque (light scattering state) state when a voltage is applied.

According to the present invention, a liquid crystal light control element having high durability to external light and low driving voltage can be obtained. The liquid crystal dimming element is described below with reference to the drawings. Fig. 1 and 2 show an example of a liquid crystal light control element driven in a normal mode. In the normal mode, when no voltage is applied between the substrates as shown in fig. 2, the liquid crystalline compound exists in an unoriented form. When light enters the light control layer, strong scattering of the incident light occurs at the interface due to a difference in refractive index between the polymer as a transparent substance and the liquid crystal composition. Therefore, the transmission of light is blocked. When a voltage is applied between the substrates as shown in fig. 1, the liquid crystalline compound is aligned. In this case, the difference in refractive index between the polymer as a transparent substance and the liquid crystal composition becomes small, scattering of incident light becomes small, and light passes through the light modulation layer.

In the reverse mode, an alignment film is provided at an electrode interface, and a state in which a liquid crystalline compound is aligned is shown when no voltage is applied. In this case, the difference in refractive index between the polymer as the transparent substance and the liquid crystal composition is small, scattering of light incident on the light control layer is small, and light passes through the light control layer. In the reverse mode, when a voltage is applied between the substrates, the orientation of the liquid crystal is disturbed, a difference in refractive index from the polymer is generated, and incident light is scattered, thereby blocking the transmission of light.

The element has a function as a light control film or a light control glass. When the element is in the form of a film, the element can be attached to an existing window or laminated glass can be produced by sandwiching a pair of glass plates. The element is used for the partition of a window or a conference room arranged on the outer wall from the corridor. That is, there are applications such as electronic blinds, light control windows, smart windows, and the like. Further, the function as an optical switch can be applied to a liquid crystal shutter or the like.

The device may change with time due to long-term use. The haze ratio may be changed from the initial stage. The change in the haze ratio is preferably small. When the haze change rate is small, a good transparent/opaque state can be maintained. Under illumination (180W/m)²) The haze change rate before and after the weather resistance test under the conditions of the irradiation time (100 hours) and the in-tank temperature (35 ℃) is preferably 20% or less. The haze change rate before and after the weather resistance test is more preferably 10% or less, and particularly preferably 5% or less.

The rate of change of the haze is an important factor for the long life of the liquid crystal dimming element. When the element is tested for weather resistance, the haze change rate before and after the element is preferably small. In order to achieve a small haze change ratio, it is important to select the type of liquid crystalline compound, combine it with a specific polymerizable compound, and examine the ratio of each component compound. In order to obtain better results, it is useful to investigate the kind or amount of additives, polymerization conditions, and the like.

[ examples ]

The present invention will be further described in detail by way of examples. The present invention is not limited to these examples. In the examples, the composition (M1), the composition (M2), and the like are described. The examples do not describe mixtures of composition (M1) with composition (M2). However, it is considered that the mixtures are also disclosed. Mixtures of at least two compositions selected from the examples are considered to be disclosed as well. The synthesized compound is identified by Nuclear Magnetic Resonance (NMR) analysis or the like. The properties of the compounds, compositions and devices were measured by the following methods.

The determination method comprises the following steps: the characteristics were measured by the following methods. These methods are mostly described in JEITA standard (JEITA. ED-2521B) examined and established by the society of electronic Information Technology Industries (Japan Electronics and Information Technology Industries Association; referred to as JEITA), or modified. In a Twisted Nematic (TN) cell used for measurement, a Thin Film Transistor (TFT) is not mounted.

(1) Upper limit temperature of nematic phase (NI;. degree. C.): the sample was placed on a hot plate of a melting point measuring apparatus including a polarizing microscope, and heated at a rate of 1 ℃ per minute. The temperature at which a part of the sample changes from nematic phase to isotropic liquid was measured. The upper limit temperature of the nematic phase may be simply referred to as "upper limit temperature".

(2) Lower limit temperature of nematic phase (TC;): the nematic phase was observed after the sample was placed in a glass bottle and kept in a freezer at 0 ℃, -10 ℃, -20 ℃, -30 ℃ and-40 ℃ for 10 days. For example, when a sample maintains a nematic phase at-20 ℃ and changes to a crystalline or smectic phase at-30 ℃, TC is reported as ≦ 20 ℃. The lower limit temperature of the nematic phase may be simply referred to as "lower limit temperature".

(3-1) viscosity (bulk viscosity;. eta.; measured at 20 ℃ C.;. mPas) of the composition: for the measurement, an E-type rotational viscometer manufactured by tokyo counter gmbh was used.

(3-2) viscosity (bulk viscosity;. eta.;. measured at 25 ℃ C.;. mPas) of the polymerizable composition: for the measurement, an E-type rotational VISCOMETER (VISCOMETER) TV-25 type) manufactured by eastern industries, Ltd was used.

(4) Viscosity (rotational viscosity; γ 1; measured at 25 ℃; mPas): the measurement was carried out according to the method described in M.Imai et al, Molecular Crystals and Liquid Crystals (Molecular Crystals and Liquid Crystals), 259, page 37 (1995). A sample was placed in a TN cell having a twist angle of 0 DEG and a gap (cell gap) of 5 μm between two glass substrates. In the range of 16V to 19.5V, a voltage is applied to the element in stages in units of 0.5V. After 0.2 seconds of no voltage application, the application was repeated with only one square wave (square pulse; 0.2 seconds) and no voltage application (2 seconds). The peak current (peak current) and peak time (peak time) of the transient current (transient current) generated by the application are measured. The value of the rotational viscosity is obtained from these measured values and the calculation formula (10) described on page 40 of the paper by M. The value of the dielectric anisotropy required for the calculation was determined by the following method using an element obtained by measuring the rotational viscosity.

(5) Optical anisotropy (refractive index anisotropy; Δ n; measured at 25 ℃): the measurement was performed using light having a wavelength of 589nm by an Abbe refractometer having a polarizing plate attached to an eyepiece lens. After rubbing the surface of the main prism in one direction, the sample was dropped on the main prism. The refractive index n/is measured when the direction of polarization is parallel to the direction of rubbing. The refractive index n ″) is measured when the direction of the polarized light is perpendicular to the direction of the friction. The value of the optical anisotropy is calculated from the formula Δ n ═ n/n ″.

(6) Dielectric anisotropy (. DELTA.. di-elect cons.; measured at 25 ℃): a sample was placed in a TN cell having a cell gap of 9 μm between two glass substrates and a twist angle of 80 degrees. A sine wave (10V, 1kHz) was applied to the element, and the dielectric constant (. epsilon. /) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. Sine wave (0.5V, 1kHz) was applied to the element, and the dielectric constant (∈ ∈ in the short-axis direction of the liquid crystal molecules was measured after 2 seconds. The value of the dielectric anisotropy is calculated from the formula Δ ∈/∈ j.

Method for measuring physical properties of liquid crystal light control element: the physical properties were measured by the following methods.

(1) Measurement of haze (%) of cell

A cell (liquid crystal dimming element) was set in a HAZE METER (HAZE METER) NDH5000 manufactured by NIPPON DENSHOKU INDUSTRIES co., LTD) in such a manner that light source light was perpendicular to a cell surface, and HAZE (%) was measured at room temperature.

(2) Percent change in haze (%)

The unit obtained in each of examples and comparative examples was placed in a Xenon weather meter (Xenon weather meter) under the conditions described later and irradiated with ultraviolet rays a (ultraviolet a), and haze (%) was measured at room temperature for the unit.

From the haze (%) of the cell before UVA irradiation and the haze (%) after UVA irradiation, the change rate of haze was calculated as follows.

Change rate of haze (((haze (%) before UVA irradiation)) - (haze (%) after UVA irradiation)/(haze (%) before UVA irradiation) /)) 100

(3) Rate of change in color (%)

(3-1) confirmation of color difference of cell

The cell transmittance was measured at each wavelength by irradiating the cell with a spectrophotometer model V-650 of Jasco (JASCO) manufactured by Nippon spectral analysis (Kyowa) at a wavelength of 380nm to 780 nm. Then, b based on L a b color system was calculated by spectral analysis using color calculation program software (Kagaku V-600for windows) conforming to the calculation formula described in Japanese Industrial Standard (JIS) Z8729-2004. The color difference value used to calculate the percent change in color difference of the cell described later is a value obtained when an electric field of 60V is applied to the cell at room temperature.

(3-2) method for calculating color difference change rate (%) of unit

The cells obtained in each of examples and comparative examples were placed in a xenon weather meter under the conditions described below, and UVA was irradiated thereto, and the color difference of the cells (room temperature, 60V applied electric field) was measured with respect to the cells.

The rate of change of the chromatic aberration is calculated as shown below.

Change rate of chromatic aberration (((chromatic aberration before UVA irradiation) - (chromatic aberration after UVA irradiation))/(chromatic aberration before UVA irradiation)) /) 100

(3-3) weather resistance test of element: the haze (%) was measured before and after the test, and the haze change rate was calculated. The test was carried out in accordance with Japanese Industrial Standard (JIS) K5600-7-7, accelerated weather resistance and accelerated light resistance (xenon lamp method). For the measurement, a super xenon weather meter (super xenon weather meter) SX75 model manufactured by shiga tester (stock) was used. The measurement conditions were illuminance (UVA; 180W/m)²) The irradiation time (100 hours), the blackboard temperature (63 ℃ C. + -. 2 ℃ C.), the in-tank temperature (35 ℃ C.), and the in-tank relative humidity (40% RH). UVA refers to ultraviolet A (ultraviolet A).

(4) Confirmation of actuation

Unless otherwise stated, the case where voltage was applied at room temperature (25 ℃) from a state where no voltage was applied and the haze (%) was 10% or less at 100V or less was evaluated as drivable.

(5) Evaluation of adhesion

For the test of adhesion evaluation, storograft VESO5D manufactured by toyo seiki corporation was used. A sheet of plastic having a width of 25.0mm and a length of 200mm was attached over the entire width to NWBB-N30 manufactured by Nickeck, Nichiban, Inc. A light-adjusting film having a width of 25mm and a length of 350mm was attached to the test piece. The test piece was mounted on a testing machine, and the average peel force was obtained when one side of the test piece was peeled in the 180 ° direction under an environment of a tensile speed of 100 mm/min and 25 ℃. For each test piece, the average peel force was calculated from the force-grip movement curve over a peel length of at least 100mm, except for the first 25 mm. The test was continued until the adhesive length was peeled off by at least 125mm, and the number of test pieces was set to 3 or more, and the average value was obtained and evaluated. Here, when the peel force is 0.3N/cm (in inches, 0.1N/inch) or more, the adhesion is evaluated as good.

Examples of compositions are shown below. The liquid crystalline compound is represented by a symbol based on the definition in table 3 below. In Table 3, the configuration of the 1, 4-cyclohexylene group-related stereo-configuration is trans. The numbers in parentheses following the marked compounds indicate the chemical formula to which the compound belongs. The symbol (-) indicates other liquid crystalline compounds. Finally, the values of the properties of the composition are summarized.

TABLE 3 formulation of Compounds Using symbols

R-(A₁)-Z₁-·····-Z_n-(A_n)-R’

The following compositions were used in the examples.

[ composition (M1) ]

NI＝96.1℃；η＝28.3mPa·s；Δn＝0.176；Δε＝9.8

[ composition (M2) ]

NI＝104.5℃；η＝41.5mPa·s；Δn＝0.216；Δε＝12.5

[ composition (M3) ]

NI＝95.4℃；η＝35.5mPa·s；Δn＝0.178；Δε＝10.5

[ composition (M4) ]

NI＝90.4℃；Δn＝0.193；Δε＝7.9

[ composition (M5) ]

NI＝120.9℃；Δn＝0.213；Δε＝10.2

[ composition (M6) ]

NI＝102.2℃；Δn＝0.098；Δε＝7.1

[ composition (M7) ]

NI＝98.2℃；Δn＝0.156；Δε＝7.4

[ composition (M8) ]

NI＝89.3℃；Δn＝0.171；Δε＝9.5

[ composition (M9) ]

NI＝89.0℃；Δn＝0.199；Δε＝18.3

[ composition (M10) ]

NI＝119.3℃；Δn＝0.201；Δε＝8.4

[ composition (M11) ]

NI＝134.1℃；Δn＝0.199；Δε＝15.2

The polymerizable compound is suitably selected from the following compounds.

The monofunctional monomer (M-1) includes the following compounds.

N, N-dimethylacrylamide, N-diethylacrylamide, N- (butoxymethyl) acrylamide, N- (2-hydroxyethyl) acrylamide, N- [3- (dimethylamino) propyl ] acrylamide.

The monofunctional monomer (M-2) having a cyclic structure includes the following compounds.

In this example, (M-2-2-1), (M-2-7-1) and (M-2-10-1) were used.

As the polyfunctional urethane (meth) acrylate oligomer,

a polyether urethane acrylate oligomer UN6202 (manufactured by Kokai Co., Ltd.) having a weight average molecular weight of about 11,000 and a polyether urethane acrylate oligomer UN6207 (manufactured by Kokai Co., Ltd.) having a weight average molecular weight of 27,000 were used.

As the polymerizable compound (M-3) having a phosphoric acid moiety, a compound represented by the formula (M-3) wherein M is¹⁰²Is methyl, n¹⁰¹Lyte Ester (Light Ester) P-1M (manufactured by Kyoeisha chemical Co., Ltd.) was 2.

As the hydroxyalkyl (meth) acrylate as the polar compound, 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate is used.

As the monofunctional polymerizable compound (formula (M-5-E)) having a linear structure such as a linear alkyl group or a branched alkyl group, a compound (M-5-E-1), a compound (M-5-E-2), a compound (M-5-E-3) or a compound (M-5-E-4) can be used.

In this example, Biscoat #190, CBA and EEEA (manufactured by Dabanian chemical industry) were used as the compound (M-5-E-1), and NK ester AM-130G (manufactured by Ninghamu chemical industry) was used as the compound (M-5-E-4).

[ example 1]

(1) Manufacture of liquid crystal light-regulating element

The composition (M4) had positive dielectric constant anisotropy.

60% by mass of the composition (M4),

10 mass% of N, N-diethylacrylamide,

20% by mass of urethane acrylate oligomer UN6202, and

10% by mass of a polymerizable compound (M-2-7-1),

a polymeric composition is prepared. An ornirade (Omnirad)651 (photopolymerization initiator; registered trademark; IGM resin (IGM Resins)) was added at a ratio of 0.4 mass% based on the total mass of the mixture of the liquid crystal composition and the polymerizable compound to prepare a polymerizable composition for a light control element. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25 ℃). The polymerizable composition for a light control element was coated with a 15 μm spacer and an ITO-coated PET film (film thickness 125 μm), and was laminated with another film using a laminator.

Next, the resultant was irradiated at room temperature (25 ℃ C.) for 3J/cm using a UV-LED exposure apparatus (manufactured by Acx (AKS) Co., Ltd., LED exposure apparatus AMU-35-DU/LED)²Wavelength of 365nm and illumination intensity of 15mW/cm²The ultraviolet ray of (2) to produce an element having a liquid crystal composite. The resulting element is opaque. The element was transparent when irradiated with light by applying a voltage of 60V. From the results, the element is in the normal mode.

(2) Evaluation of adhesion

The element was measured for peel force under the conditions described in measurement (5), and the peel force was 0.6N/cm.

(3) Evaluation of haze Change Rate after weather resistance test

The resulting element was disposed in the haze meter such that the element was perpendicular to the incident light. The haze ratio was measured by applying a voltage ranging from 0V to 60V to the element. Then, the haze ratio after the weather resistance test under the conditions described in measurement (3-3) was measured, and the haze change ratio was calculated to be about 5%.

[ example 2]

60% by mass of the composition (M4),

10 mass% of N, N-diethylacrylamide,

20% by mass of urethane acrylate oligomer UN6202, and

10% by mass of a polymerizable compound (M-2-2-1),

a polymerizable composition was prepared, and a photopolymerization initiator was added in the same manner as in example 1 to prepare a polymerizable composition for a light control device. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25 ℃). An element having a liquid crystal composite was produced in the same manner as in example 1, except that the polymerizable composition for a light control element was used. The resulting element is opaque. The element was transparent when irradiated with light by applying a voltage of 60V. From the results, the element is in the normal mode.

The peel force of the element was measured in the same manner as in example 1, and as a result, the peel force was 1.3N/cm.

The haze change rate after the weather resistance test was calculated in the same manner as in example 1, and the result was about 4%.

[ example 3]

60% by mass of the composition (M4),

15 mass% of N, N-diethylacrylamide,

Urethane acrylate oligomer UN6202 in an amount of 15 mass%, and

10% by mass of a polymerizable compound (M-2-2-1),

The peel force of the element was measured in the same manner as in example 1, and as a result, the peel force was 1.8N/cm.

The haze change rate after the weather resistance test was calculated in the same manner as in example 1, and the result was about 5%.

[ example 4]

55% by mass of a composition (M4),

22.5% by mass of N, N-diethylacrylamide,

11.25% by mass of urethane acrylate oligomer UN6202, and

11.25% by mass of a polymerizable compound (M-2-2-1),

The peel force of the element was measured in the same manner as in example 1, and as a result, the peel force was 2.3N/cm.

[ example 5]

The composition (M5) had positive dielectric constant anisotropy.

60% by mass of the composition (M5),

20 mass% of N, N-diethylacrylamide,

10% by mass of urethane acrylate oligomer UN6202, and

10% by mass of a polymerizable compound (M-2-7-1),

[ example 6]

60% by mass of the composition (M5),

10 mass% of N, N-diethylacrylamide,

10% by mass of urethane acrylate oligomer UN6202, and

20% by mass of a polymerizable compound (M-2-7-1),

[ example 7]

60% by mass of the composition (M5),

15 mass% of N, N-diethylacrylamide,

Urethane acrylate oligomer UN6202 in an amount of 15 mass%, and

10% by mass of a polymerizable compound (M-2-7-1),

[ example 8]

60% by mass of the composition (M5),

10 mass% of N, N-diethylacrylamide,

10% by mass of urethane acrylate oligomer UN6202, and

20% by mass of a polymerizable compound (M-2-2-1),

The peel force of the element was measured in the same manner as in example 1, and as a result, the peel force was 1.5N/cm.

[ example 9]

60% by mass of the composition (M5),

20 mass% of N, N-diethylacrylamide,

10% by mass of urethane acrylate oligomer UN6202, and

10% by mass of a polymerizable compound (M-2-2-1),

The peel force of the element was measured in the same manner as in example 1, and as a result, the peel force was 2.5N/cm.

[ example 10]

60% by mass of the composition (M4),

10 mass% of N, N-diethylacrylamide,

19.8% by mass of urethane acrylate oligomer UN6202,

10% by mass of a polymerizable compound (M-2-7-1), and

0.2 mass% of Light Ester (Light Ester) P-1M,

The peel force of the element was measured in the same manner as in example 1, and as a result, the peel force was 11.4N/cm.

[ example 11]

60% by mass of the composition (M4),

10 mass% of N, N-diethylacrylamide,

19.8% by mass of urethane acrylate oligomer UN6202,

10% by mass of a polymerizable compound (M-2-2-1), and

0.2 mass% of Light Ester (Light Ester) P-1M,

The peel force of the element was measured in the same manner as in example 1, and as a result, the peel force was 10.2N/cm.

[ example 12]

60% by mass of the composition (M1),

15 mass% of N, N-diethylacrylamide,

Urethane acrylate oligomer UN6202 in an amount of 15 mass%, and

10% by mass of a polymerizable compound (M-2-7-1),

The peel force of the element was measured in the same manner as in example 1, and as a result, the peel force was 1.9N/cm.

The haze change rate after the weather resistance test was calculated in the same manner as in example 1, and the result was about 2%.

[ example 13]

60% by mass of the composition (M2),

15 mass% of N, N-diethylacrylamide,

Urethane acrylate oligomer UN6202 in an amount of 15 mass%, and

10% by mass of a polymerizable compound (M-2-7-1),

The peel force of the element was measured in the same manner as in example 1, and as a result, the peel force was 1.7N/cm.

The haze change rate after the weather resistance test was calculated in the same manner as in example 1, and the result was about 3%.

[ example 14]

60% by mass of the composition (M3),

15 mass% of N, N-diethylacrylamide,

Urethane acrylate oligomer UN6202 in an amount of 15 mass%, and

10% by mass of a polymerizable compound (M-2-7-1),

[ example 15]

The composition (M10) had positive dielectric constant anisotropy.

60% by mass of the composition (M10),

5% by mass of N, N-diethylacrylamide,

10% by mass of urethane acrylate oligomer UN6202,

15 mass% of a polymerizable compound (M-2-2-1),

5% by mass of 4-hydroxybutyl acrylate, and

5% by mass of the compound (M-5-E-4),

a polymerizable composition was prepared, and a photopolymerization initiator was added in the same manner as in example 1 to prepare a polymerizable composition for a light control device. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25 ℃). An element having a liquid crystal composite was produced in the same manner as in example 1, except that the polymerizable composition for a light control element was used. The resulting element is opaque. The element was transparent when irradiated with light by applying a voltage of 60V. Further, it was confirmed that the element was transparent even when irradiated with light when the temperature during driving was set to 110 ℃ or-40 ℃ and a voltage of 60V was applied to the element. From the results, the element is in the normal mode.

[ example 16]

60% by mass of the composition (M10),

5% by mass of N, N-diethylacrylamide,

10% by mass of urethane acrylate oligomer UN6202,

15 mass% of a polymerizable compound (M-2-2-1),

5% by mass of 2-hydroxyethyl acrylate, and

5% by mass of the compound (M-5-E-1),

a polymerizable composition was prepared, and a photopolymerization initiator was added in the same manner as in example 1 to prepare a polymerizable composition for a light control device. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25 ℃). An element having a liquid crystal composite was produced in the same manner as in example 1, except that the polymerizable composition for a light control element was used. The resulting element is opaque. The element was transparent when irradiated with light by applying a voltage of 60V. Further, it was confirmed that the element was transparent even when irradiated with light when the temperature during driving was 110 ℃ or-30 ℃ and a voltage of 60V was applied to the element. From the results, the element is in the normal mode.

[ example 17]

60% by mass of the composition (M10),

5% by mass of N, N-diethylacrylamide,

10% by mass of urethane acrylate oligomer UN6202,

7% by mass of a polymerizable compound (M-2-2-1),

9 mass% of 2-hydroxyethyl acrylate, and

9% by mass of the compound (M-5-E-1) was mixed,

The peel force of the element was measured in the same manner as in example 1, and as a result, the peel force was 1.2N/cm.

[ example 18]

60% by mass of the composition (M11),

5% by mass of N, N-diethylacrylamide,

10% by mass of urethane acrylate oligomer UN6207,

10 mass% of a polymerizable compound (M-2-2-1),

5% by mass of a polymerizable compound (M-2-10-1),

2 mass% of 4-hydroxybutyl acrylate, and

8% by mass of the compound (M-5-E-1),

a polymerizable composition was prepared, and a photopolymerization initiator was added in the same manner as in example 1. The polymerizable composition is in an isotropic phase state at room temperature (25 ℃). An element having a liquid crystal composite was produced in the same manner as in example 1, except that the polymerizable composition was used. The resulting element is opaque. The element was transparent when irradiated with light by applying a voltage of 60V. Further, it was confirmed that the element was transparent even when irradiated with light when the temperature during driving was 110 ℃ or-30 ℃ and a voltage of 60V was applied to the element. From the results, the element is in the normal mode.

The peel force of the element was measured in the same manner as in example 1, and as a result, the peel force was 1.0N/cm.

Comparative example 1

60% by mass of the composition (M4),

20% by mass of urethane acrylate oligomer UN6202, and

20% by mass of a polymerizable compound (M-2-7-1),

On the other hand, the peel force of the device was measured in the same manner as in example 1, and as a result, the peel force was 0.1N/cm or less.

Comparative example 2

60% by mass of the composition (M4),

20% by mass of N, N-diethylacrylamide, and

20% by mass of a polymerizable compound (M-2-7-1),

From the above results, it is clear that the elements of examples 1 to 18 had a normal mode, good adhesion, and also the haze change rate after the weather resistance test was 10% or less and the change with time was small. Therefore, we have concluded that a liquid crystal composite obtained by combining a specific nematic composition with a specific polymer can be suitably used for a liquid crystal light control element.

[ industrial applicability ]

The liquid crystal light control element containing the liquid crystal composite obtained by polymerizing the polymerizable composition for a light control element of the present invention is useful for a light control window, a smart window, and the like.

Claims

1. A polymerizable composition for a light control element, comprising a liquid crystal composition, a polymer precursor and a photopolymerization initiator,

the precursors of said polymers each contain

in the formula (1), R¹Is alkyl group with carbon number of 1 to 12, alkoxy group with carbon number of 1 to 12 or alkenyl group with carbon number of 2 to 12; ring A is 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene, 3-fluoro-1, 4-phenylene, 2, 3-difluoro-1, 4-phenylene, 2, 6-difluoro-1, 4-phenylene, pyrimidine-2, 5-diyl, 1, 3-dioxane-2, 5-diyl or tetraylHydropyran-2, 5-diyl; z¹Is a single bond, ethylene, ethenylene, ethynylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy; x¹And X²Each independently is hydrogen or fluorine; y is¹Is fluorine, chlorine, cyano, alkyl of carbon number 1 to 12 with at least one hydrogen substituted by fluorine or chlorine, alkoxy of carbon number 1 to 12 with at least one hydrogen substituted by fluorine or chlorine, or alkenyloxy of carbon number 2 to 12 with at least one hydrogen substituted by fluorine or chlorine; a is 1, 2,3 or 4;

in the formula (M-1),

in the formula (M-2),

R¹⁰³is prepared from carbocyclic saturated aliphatic compound, heterocyclic saturated aliphatic compound, carbocyclic unsaturated aliphatic compound, heterocyclic unsaturated aliphatic compound or carbocyclic ringA monovalent group having 5 to 35 carbon atoms which is formed by removing one hydrogen from an aromatic compound of the formula (I) or (II) or (III) and which may be substituted with an alkyl group having 1 to 12 carbon atoms, at least one-CH group being present in the monovalent group₂-may be substituted by-O-, -CO-, -COO-or-OCO-.

2. The polymerizable composition for a light control element according to claim 1, wherein the liquid crystalline compound represented by formula (1) is at least one compound selected from the group consisting of compounds represented by formulae (1-1) to (1-48);

in the formulae (1-1) to (1-48), R¹Is alkyl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms or alkenyl group with 2 to 12 carbon atoms, X¹And X²Each independently is hydrogen or fluorine; y is¹Is fluorine, chlorine, cyano, at least one hydrogen being substituted by fluorine or chlorineAn alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine, or an alkenyloxy group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

3. The polymerizable composition for a light control element according to claim 1 or 2, wherein the proportion of the component a is in a range of 5 to 90 mass% based on the mass of the liquid crystal composition.

4. The polymerizable composition for a light control element according to claim 1 or 2, wherein the liquid crystal composition further contains a liquid crystalline compound represented by formula (2) as a component B;

in the formula (2), R³Is a radical bonded to a carbon atom of the ring C, R²And R³Each independently is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine;

b is 1, 2 or 3.

5. The polymerizable composition for a light control element according to claim 4, wherein the liquid crystal composition contains at least one compound selected from the group consisting of compounds represented by formulae (2-1) to (2-23) as the component B;

in the formulae (2-1) to (2-23), R²And R³Is alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms or alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

6. The polymerizable composition for a light control element according to claim 4, wherein the proportion of the component B is in a range of 5 to 90 mass% based on the mass of the liquid crystal composition.

7. The polymerizable composition for a light control element according to claim 1 or 2, wherein the liquid crystal composition contains a liquid crystalline compound represented by formula (3) as component C;

in the formula (3), R⁴And R⁵Each independently is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms or alkenyloxy having 2 to 12 carbon atoms; ring D and ring F are each independently 1, 4-cyclohexylene, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chromane-2, 6-diyl or chromane-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; ring E is 2, 3-difluoro-1, 4-phenylene, 2-chloro-3-fluoro-1, 4-phenylene, 2, 3-difluoro-5-methyl-1, 4-phenylene, 3,4, 5-trifluoronaphthalene-2, 6-diyl, 7, 8-difluorochromane-2, 6-diyl, 3,4,5, 6-tetrafluorofluorene-2, 7-diyl, 4, 6-difluorodibenzofuran-3, 7-diyl, 4, 6-difluorodibenzothiophene-3, 7-diyl, or 1,1,6, 7-tetrafluoroindan-2, 5-diyl; z³And Z⁴Each independently a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 0, 1, 2Or 3, d is 0 or 1; the sum of c and d is 3 or less.

8. The polymerizable composition for a light control element according to claim 7, wherein component C is at least one compound selected from the group consisting of liquid crystalline compounds represented by formulae (3-1) to (3-35);

in the formulae (3-1) to (3-35), R⁴And R⁵Each independently is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms.

9. The polymerizable composition for a light control element according to claim 7, wherein the proportion of the component C is in a range of 3 to 25 mass% based on the mass of the liquid crystal composition.

10. The polymerizable composition for a light control element according to claim 1, wherein in the compound represented by the formula (M-1),

M¹⁰⁰is hydrogen or methyl;

R¹⁰⁰and R¹⁰¹Each independently hydrogen, C1-10 linear alkyl or C3-10 branched alkyl, or C1-10A straight chain hydroxyalkyl group or a branched hydroxyalkyl group having 3 to 10 carbon atoms;

in the formula, M¹⁰¹Is hydrogen or methyl; n is¹⁰⁰Is 0, 1 or 2, m¹⁰⁰Is an integer of 2 to 6.

11. The polymerizable composition for a light control element according to claim 1 or 2, further comprising at least one polymerizable compound having a phosphate moiety selected from the group consisting of compounds represented by the formulae (M-3) and (M-4) as a precursor of the polymer;

in formulae (M-3) to (M-4), M¹⁰²Is hydrogen or methyl; n is¹⁰¹、n¹⁰²And n¹⁰³Independently 1 to 4.

12. The polymerizable composition for a light control element according to claim 1 or 2, further comprising at least one polymerizable compound selected from the group consisting of compounds represented by the formulae (M-5-E) and (M-5-P), and at least one polymerizable compound selected from hydroxyalkyl (meth) acrylates as a precursor of the polymer;

in the formulae (M-5-E) and (M-5-P), M⁵⁰¹Is hydrogen or methyl, R⁵⁰²Is alkyl with 1 to 6 carbon atoms, n is 1 to 30;

13. The polymerizable composition for a light control element according to claim 1 or 2, further comprising at least one polymerizable compound selected from the group consisting of compounds represented by formula (7), formula (8), and formula (9) as a precursor of the polymer;

in the formulae (7), (8) and (9), ring G, ring I, ring J, ring K, ring L and ring M are each 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, and at least one hydrogen contained in these groups may be substituted with fluorine, chlorine, cyano, hydroxyl, formyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 2 to 5 carbon atoms or an alkanoyl group having 1 to 5 carbon atoms; z⁸、Z¹⁰、Z¹²、Z¹³And Z¹⁷Each independently is a single bond, -O-, -COO-, -OCO-or-OCOO-; z⁹、Z¹¹、Z¹⁴And Z¹⁶Each independently is a single bond, -OCH₂-、-CH₂O-、-COO-、-OCO-、-COS-、-SCO-、-OCOO-、-CONH-、-NHCO-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂-、-CH＝CHCOO-、-OCOCH＝CH-、-CH₂CH₂COO-、-OCOCH₂CH₂-、-CH＝CH-、-N＝CH-、-CH＝N-、-N＝C(CH₃)-、-C(CH₃) N-, -N-or-C ≡ C-; z¹⁵Is a single bond, -O-or-COO-; y is²Hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, a linear alkyl group having a carbon number of 1 to 20, a linear alkenyl group having a carbon number of 2 to 20, a linear alkoxy group having a carbon number of 1 to 20, or a linear alkyloxycarbonyl group having a carbon number of 2 to 20; f and h are each independently an integer from 1 to 4; k and m are each independently an integer of 0 to 3; the sum of k and m is 1 to 4; e. g, i, j, l and n are each independently an integer of 0 to 20; m⁷To M¹²Each independently hydrogen or methyl.

14. The polymerizable composition for a light control element according to claim 1 or 2, wherein the ratio of the liquid crystal composition is in a range of 30 to 95% by mass and the ratio of the precursor of the polymer is in a range of 5 to 70% by mass, based on the total mass of the liquid crystal composition and the precursor of the polymer.

15. The polymerizable composition for a light control element according to claim 1 or 2, wherein the polymerizable composition is a liquid crystal composition having a liquid crystal phase,

the proportion of the compound (M-1) is in the range of 3 to 25% by mass,

the proportion of the compound (M-2) is in the range of 3 to 30% by mass,

16. The polymerizable composition for a light control element according to claim 11, wherein the polymerizable composition is a liquid crystal composition having a liquid crystal phase,

17. The polymerizable composition for a light control element according to claim 12, wherein the polymerizable composition is a liquid crystal composition having a liquid crystal phase,

18. A liquid crystal light-modulating element, wherein a light-modulating layer is sandwiched between a pair of transparent substrates, the transparent substrates having transparent electrodes, and the light-modulating layer is a liquid crystal composite obtained by polymerizing the polymerizable composition for a light-modulating element according to any one of claims 1 to 17.

19. The liquid crystal dimming element according to claim 18, wherein the transparent substrate comprises a glass plate, a plastic plate or a plastic film.

20. The liquid crystal dimming element according to claim 18 or 19, wherein the illuminance is 180W/m²And a haze change rate of 20% or less before and after a weather resistance test conducted under conditions in which the irradiation time is 100 hours and the in-cell temperature is 35 ℃.

21. A dimming window using the liquid crystal dimming element as claimed in any one of claims 18 to 20.

22. A smart window using the liquid crystal dimming element of any one of claims 18 to 20.

23. A liquid crystal composite obtained by polymerizing the polymerizable composition for a light control element according to any one of claims 1 to 17.

24. Use of the liquid crystal composite according to claim 23 in a liquid crystal dimmer element.

25. Use of the liquid crystal composite according to claim 23 in a liquid crystal dimming element in which the transparent substrate comprises a plastic plate or a plastic film.

26. Use of a liquid crystal composite according to claim 23 in a light control window.

27. Use of a liquid crystal composite according to claim 23 in a smart window.