TW202116828A - Polymerizable composition for dimming element, liquid crystal dimming element, dimming window, smart window, liquid crystal composite and uses thereof having good adhesion to a plastic film substrate with a transparent electrode, and having good light resistance and weather resistance - Google Patents

Abstract

The present invention provides a polymerizable composition for a dimming element that has good adhesion to a plastic film substrate with a transparent electrode and has good light resistance and weather resistance, a liquid crystal dimming element, a dimming window, a smart window, and a liquid crystal composite using the balanced characteristics of the composition and suitable for dimming, and uses thereof. Each of precursors of polymers contained together with the liquid crystal composition includes at least one monofunctional polymerizable compound having a non-cyclic structure of nitrogen atom, a monofunctional polymerizable compound with a cyclic structure and a multifunctional urethane (meth)acrylate oligomer.

Description

Polymerizable composition for dimming element, liquid crystal dimming element, dimming window, smart window, liquid crystal composite and its use

The present invention mainly relates to a polymerizable composition for a dimming element, and a liquid crystal dimming element. In more detail, it relates to a polymerizable composition for a light-adjusting element obtained by combining a polymer precursor and a liquid crystal composition having a positive dielectric constant anisotropy, and the use of the composition obtained Liquid crystal dimming element of liquid crystal composite and its use.

In the liquid crystal dimming element, there are methods using light scattering and the like. The elements are used in building materials such as window glass or room partitions, automotive parts, and the like. In these components, in addition to hard substrates such as glass substrates, soft substrates such as plastic films are also used. In the liquid crystal composition sandwiched by these substrates, the arrangement of the liquid crystal molecules is changed by adjusting the applied voltage. By this method, the light transmitted through the liquid crystal composition can be controlled, so liquid crystal dimming elements are widely used in displays, optical shutters, dimming windows (Patent Document 1), smart windows (Patent Document 2), etc. in.

An example of a liquid crystal dimming element is a polymer dispersion type element in a light scattering mode. The liquid crystal composition is dispersed in the polymer (liquid crystal composite). The element has the following characteristics. The production of components is easy. It is easy to control the film thickness in a large area, so it is possible to produce a device with a large screen. There is no need for a polarizing plate, so a clear display can be achieved. Due to the use of light scattering, the field of view is wide. The element can be expected to be used in dimming glass, projection type displays, large-area displays, etc., because of its excellent properties.

Another example is a polymer network type liquid crystal dimming element. In the element of this type, a liquid crystal composition is present in the three-dimensional network of the polymer. The composition is continuous, and the aspect is different from the polymer dispersion type. The element of the aforementioned type also has the same characteristics as the element of the polymer dispersion type. There are also liquid crystal dimming 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 dimming element. By improving the characteristics of the composition, a device with good characteristics can be obtained. The relationship between the two characteristics is summarized in Table 1 below. The characteristics of the composition will be further explained based on the element. The temperature range of the nematic phase is related to the temperature range in which the element can be used. The preferable upper limit temperature of the nematic phase is about 70°C or higher, and the preferable lower limit temperature of the nematic phase is about -20°C or lower. The viscosity of the composition is related to the response time of the device. In order to control the transmittance of light, it is preferable that the response time be short. Ideally, the response time is 1 millisecond shorter than other components. Therefore, it is preferable that the viscosity of the composition is small. More preferably, the viscosity at low temperature is small. The elastic constant of the composition is related 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 be large.

Table 1. Characteristics of liquid crystal composition and liquid crystal dimming element Numbering Characteristics of liquid crystal composition Characteristics of liquid crystal dimming components 1 Wide temperature range of nematic phase Wide range of usable temperature 2 Low viscosity Short response time 3 Large optical anisotropy Haze rate is large 4 Positive or negative dielectric constant anisotropy Low threshold voltage, low power consumption 5 Specific resistance High voltage holding rate 6 Stable to light and heat long 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 the ratio of diffused light to total transmitted light. When blocking light, it is preferable that the haze ratio is large. For a large haze ratio, it is preferable that the optical anisotropy is large. The high dielectric anisotropy of the composition contributes to low threshold voltage or low power consumption in the device. Therefore, it is preferable that the dielectric constant anisotropy is large. The high specific resistance of the composition contributes to the high voltage retention rate in the element. Therefore, it is preferably a composition having a large specific resistance in the initial stage. It is preferably a composition having a large specific resistance after long-term use. The stability or weather resistance of the composition to light or heat is related to the life of the element. When the stability or heat resistance is good, the life is long. Display failures such as after-images or dripping marks are also related to the life of the device. A device with high weather resistance and low display defects is desired. (Patent Document 3)

There are normal mode and reverse mode in the liquid crystal dimming element. In the normal mode, the device is opaque when no voltage is applied, and becomes transparent when a voltage is applied. The pattern is suitable for room partitioning. In the reverse mode, the element becomes transparent when no voltage is applied, and becomes opaque when voltage is applied. In this mode, since it becomes transparent when the component fails, it is suitable for the window of a car. There are also researches: In dimming windows or smart windows with liquid crystal dimming elements, the front substrate and the back substrate are not rigid substrates (glass plates, plastic plates), but use flexible plastic films, and use roll-to-roll ( roll to roll). (Patent Document 4) A transparent electrode (or an alignment film is further formed) is formed on the plastic plate or the plastic film, and adhesiveness with the polymer formed in the liquid crystal layer is required. (Patent Document 5～Patent Document 8)

In Patent Document 5 to Patent Document 8, there is no disclosure or suggestion regarding the combination of materials for improving the adhesion and weather resistance and light resistance expected to be used outdoors. [Prior Art Literature]

[Patent Literature] [Patent Document 1] Japanese Patent Laid-Open No. 06-273725 [Patent Document 2] International Publication No. 2011-096386 [Patent Document 3] International Publication No. 2019-026621 [Patent Document 4] Japanese Patent Laid-Open No. 2019-105680 [Patent Document 5] Japanese Patent Laid-Open No. 2011-026526 [Patent Document 6] Japanese Patent Laid-Open No. 2011-074304 [Patent Document 7] Japanese Patent Laid-Open No. 2011-105902 [Patent Document 8] Japanese Patent Laid-Open No. 2011-105908

[The problem to be solved by the invention] The subject of the present invention is to provide a polymerizable composition for a dimming element that has good adhesion to a plastic film substrate with a transparent electrode and has good light resistance and weather resistance. Another problem is to provide a liquid crystal composite with balanced and suitable for dimming characteristics. [Technical means to solve the problem]

The inventors of the present invention considered the possibility of further improving the characteristics of the liquid crystal dimming element, and conceived a method of using a liquid crystal compound having a terphenyl structure or a liquid crystal compound having a cyano group in a part of the liquid crystal composition. The reason is that a liquid crystal composite in which the liquid crystal composition has a large optical anisotropy is expected to obtain a large haze ratio.

Furthermore, as a result of investigating the above possibilities, it was found that when a specific liquid crystal compound and a specific polymerizable compound are combined, it is possible to achieve both adhesion and stability for outdoor use (weather resistance and light resistance). A liquid crystal composite with balanced characteristics and suitable for dimming can be obtained, thereby completing the present invention.

The present invention relates to a polymerizable composition for a dimming element, the polymerizable composition for a dimming element contains a liquid crystal composition and a polymer precursor, The liquid crystal composition contains at least one compound (as component A) selected from the compounds represented by formula (1), The polymer precursor contains: at least one of a monofunctional polymerizable compound having a nitrogen atom and a non-cyclic structure, at least one of a monofunctional polymerizable compound having a cyclic structure, and a polyfunctional carbamate (methyl ) At least one of acrylate oligomers.

In addition, the present invention relates to a liquid crystal composite obtained by polymerizing a precursor, and a liquid crystal dimming element having the liquid crystal composite, and the like.

In formula (1), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons or an alkenyl group having 2 to 12 carbons; 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-di Fluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z ¹ is a single Bond, ethylene, ethylene, ethynylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy; X ¹ and X ² are each independently hydrogen or fluorine; Y ¹ is fluorine, Chlorine, cyano, alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, alkoxy group having 1 to 12 in carbon numbers in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is replaced by fluorine or chlorine Is an alkenyloxy group having 2 to 12 carbons; a is 1, 2, 3 or 4. [Effects of the invention]

According to the present invention, by combining a liquid crystal composition and a specific polymerizable compound, a polymerizable composition for a dimming element can be obtained. When a plastic film substrate formed with a transparent electrode is used, the polymer formed in the liquid crystal layer and The adhesiveness of the plastic film substrate with the transparent electrode is good, and the light resistance and weather resistance are also good.

In addition, according to the present invention, a liquid crystal composite can be obtained in which the upper limit temperature of the nematic phase is high, the lower limit temperature of the nematic phase is low, the viscosity is small, the optical anisotropy is large, the positive dielectric constant anisotropy is large, and the High electrical resistance, high stability to light, high stability to heat, and large elastic constant are well-balanced and have characteristics suitable for dimming.

If the liquid crystal composite is used, it is possible to provide a liquid crystal dimming element with the characteristics of short response time, high voltage holding rate, low threshold voltage, high haze rate, high weather resistance, and long life.

In this specification, terms such as "liquid crystal compound", "polymerizable compound", "liquid crystal composition", "polymerizable composition", "liquid crystal composite", and "liquid crystal dimming element" are used. A "liquid crystal compound" is a compound that has a liquid crystal phase such as a nematic phase and a smectic phase, and although it does not have a liquid crystal phase, it is used for the purpose of adjusting the temperature range, viscosity, and dielectric anisotropy of the nematic phase. The general term for the compounds added to the composition. The compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecules (liquid crystal molecules) are rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the liquid crystal composition. The liquid crystal compound having an alkenyl group is not classified as a polymerizable compound in terms of its meaning.

The "liquid crystal composition" is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, and polar compounds are added to the liquid crystal composition as necessary. Even when an additive is added, the ratio of the liquid crystal compound is represented by the mass percentage (mass %) based on the liquid crystal composition that does not contain the additive. The ratio of the additive is expressed by the mass percentage based on the liquid crystal composition that does not contain the additive. That is, the ratio of liquid crystal compounds or additives is calculated based on the total amount of liquid crystal compounds. In addition, the "quality" of "mass%" is sometimes omitted.

The "polymerizable composition" is prepared by mixing a polymerizable compound with a liquid crystal composition. That is, the polymerizable composition is a mixture of at least one polymerizable compound and a liquid crystal composition. To the polymerizable compound, additives such as a polymerization initiator and a polymerization inhibitor are added as necessary. The ratio of the polymerization initiator and the polymerization inhibitor is expressed by the mass percentage based on the total amount (total amount) of the liquid crystal composition and the polymer precursor (polymerizable compound). Even when an additive is added, the ratio of the polymerizable compound or the liquid crystal composition contained in the polymerizable composition is expressed by the mass percentage based on the polymerizable composition that does not contain the additive.

The "liquid crystal composite" is a composite of a polymer of a polymer precursor and a liquid crystal composition produced by the polymerization treatment of the polymerizable composition. "Liquid crystal dimming element" is an element having a liquid crystal composite, and is a general term for liquid crystal panels and liquid crystal modules used for dimming.

The "upper limit temperature of the nematic phase" is sometimes referred to simply as the "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as the "lower limit temperature". The expression "increasing dielectric anisotropy" refers to a composition with a positive dielectric anisotropy, which means that its value increases positively, and a composition with a negative dielectric anisotropy means Its value increases negatively. "High voltage retention rate" means that the device not only has a large voltage retention rate at room temperature in the initial stage, but also has a large voltage retention rate at a temperature close to the upper limit temperature, and not only at room temperature after long-term use The element has a large voltage holding rate, and at a temperature close to the upper limit temperature, the element also has a large voltage holding rate. Sometimes the characteristics of the composition or element are studied through time-varying tests.

Take the compound (1z) as an example for description. In the formula (1z), the symbols α and β surrounded by a hexagon correspond to the ring α and the ring β, respectively, and represent a ring such as a six-membered ring or a condensed ring. When the subscript'x' is 2, there are two rings α. The two groups represented by the two rings α may be the same or different. The rule is applicable to any two rings α when the subscript'x' is greater than 2. The rules also apply to other symbols such as the bond base Z. The oblique line crossing one side of the ring β indicates that any hydrogen on the ring β can be replaced by a substituent (-Sp-P). The subscript'y' indicates the number of substituted substituents. When the subscript'y' is 0, there is no such substitution. When the subscript'y' is 2 or more, there are multiple substituents (-Sp-P) on the ring β. In such cases, the rule of "may be the same or different" may also be applied. In addition, the above-mentioned rules also apply to the case where the symbol of Ra is used 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 the group represented by Rb may be the same or different.

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

"Main ingredient" refers to the ingredient that occupies the largest proportion in 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 main component is the compound (1z). When the component is only the compound (1z), the compound (1z) is also called the 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. Regarding the expression "at least one'A' can be replaced by'B'", when the number of'A' is one, the position of'A' is arbitrary, and when the number of'A' is two or more, there is no need to Select these'A' positions restrictedly. The expression "at least one -CH ₂ -may be substituted by -O-" is sometimes used. In this case, -CH ₂ -CH ₂ -CH ₂ -can be converted to -O-CH ₂ -O- by substitution of non-adjacent -CH ₂ -with -O-. However, the adjacent -CH ₂ -will not be substituted by -O-. The reason is that -OO-CH _2- (peroxide) is generated in the substitution.

The alkyl group of the liquid crystal compound contained in the liquid crystal composition is linear or branched, and does not include a cyclic alkyl group. Straight-chain alkyl is better than branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. In order to increase the maximum temperature, the three-dimensional configuration related to 1,4-cyclohexylene is the trans configuration better than the cis configuration.

Since 2-fluoro-1,4-phenylene is left-right asymmetric, there are leftward (L) and rightward (R) directions.

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

In addition, with regard to the composition, "based on the total mass" means the mass ratio of each component in the total mass of all components in the composition or mixture, which is the ratio of the so-called "internal ratio". On the other hand, "relative to the total mass" is the mass ratio of the components to the total mass of the composition or mixture, and is the ratio of the so-called "external ratio".

The present invention includes the following items and so on. Item 1. A polymerizable composition for dimming elements, containing a liquid crystal composition, a polymer precursor, and a photopolymerization initiator, The liquid crystal composition contains a liquid crystal compound represented by formula (1) as component A, The precursors of the polymer contained At least one monofunctional polymerizable compound selected from the compounds represented by formula (M-1), At least one monofunctional polymerizable compound selected from compounds represented by formula (M-2) having a cyclic structure, and At least one selected from the group consisting of urethane (meth)acrylate oligomers having two or more (meth)acrylic groups as a multifunctional polymerizable compound;

(In formula (1), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons or an alkenyl group having 2 to 12 carbons; 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; Z ¹ is Single bond, ethylene, ethylene, ethynylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy; X ¹ and X ² are each independently hydrogen or fluorine; Y ¹ is fluorine , Chlorine, cyano, alkyl group with 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, alkoxy group with 1 to 12 in carbons in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is replaced by fluorine or chlorine Substituted alkenyloxy having 2 to 12 carbons; a is 1, 2, 3 or 4;

In the formula (M-1), M ¹⁰⁰ is hydrogen, fluorine, an alkyl group with 1 to 5 carbons or an alkyl group with 1 to 5 carbons in which at least one hydrogen is substituted by fluorine or chlorine; R ¹⁰⁰ and R ¹⁰¹ are each independently Is hydrogen or an alkyl group or a hydroxyalkyl group having 1 to 12 carbon atoms. Among these alkyl group or hydroxyalkyl group, at least one -CH ₂ -can be controlled by -O-, -N(R ¹⁰² )-, -CO-,- Substituted by COO- or -OCO-, R ¹⁰² is hydrogen and an alkyl group having 1 to 12 carbon atoms;

In the formula (M-2), M ¹⁰¹ is hydrogen, fluorine, an alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ¹⁰⁰ is a single bond or carbon number An alkylene group of 1 to 10, in which at least one hydrogen may be substituted by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO-, -COO- or -OCO-; R ¹⁰³ is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, or a carbocyclic or heterocyclic A monovalent group with a carbon number of 5 to 35, which can be substituted by an alkyl group with a carbon number of 1 to 12, is generated by removing one hydrogen from the aromatic compound. At least one of the monovalent groups -CH ₂ -can be -O -, -CO-, -COO- or -OCO- substitution.

Item 2. The polymerizable composition for a light control element according to item 1, wherein the compound represented by formula (1) is selected from the group consisting of compounds represented by formula (1-1) to formula (1-48) At least one compound in the group;

(In formulas (1-1) to (1-48), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons or an alkenyl group having 2 to 12 carbons, X ¹ and X ^{2 is} each independently hydrogen or fluorine; Y ¹ is fluorine, chlorine, cyano, an alkyl group of 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, and a carbon number of 1 in which at least one hydrogen is replaced by fluorine or chlorine. To 12 alkoxy or alkenyloxy having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine).

Item 3. The polymerizable composition for a light control element according to Item 1 or Item 2, wherein the ratio of Component A is in the range of 5% by mass to 90% by 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 items 1 to 3, wherein the liquid crystal composition further contains a liquid crystal compound represented by formula (2) as component B;

(In formula (2), R ³ is a group bonded to a carbon atom of ring C, R ² and R ³ are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and carbon Alkenyl having 2 to 12 or alkenyl having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; ring B and ring C are each independently 1,4-cyclohexylene and 1,3-phenylene , 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene or pyrimidine-2,5-diyl; Z ² is a single bond , Ethylene, ethylene, 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 selected from the group consisting of liquid crystal compounds represented by formula (2-1) to formula (2-23) Compound as component B;

(In formulas (2-1) to (2-23), R ² and R ³ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, or (Alkenyl groups having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine).

Item 6. The polymerizable composition for a light control element according to item 4 or item 5, wherein the ratio of component B is in the range of 5 mass% 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 items 1 to 6, wherein the liquid crystal composition contains a liquid crystal compound represented by formula (3) as component C;

(In formula (3), R ⁴ and R ⁵ are each independently hydrogen, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an alkyl group having 2 to 12 carbons. 12 alkenyloxy group; ring D and ring F are each independently 1,4-cyclohexenyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4- Phenylene, 1,4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chromogen Alkane-2,6-diyl or chroman-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-Difluorochroman-2,6-diyl, 3,4,5,6-tetrafluoro-2,7-diyl, 4,6-difluorodibenzofuran-3,7 -Diyl, 4,6-difluorodibenzothiophene-3,7-diyl or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ³ and Z ⁴ are each independently Is a single bond, ethylene, ethylene, 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 control element according to item 7, wherein component C is at least one compound selected from the group consisting of compounds represented by formula (3-1) to formula (3-35);

(In formulas (3-1) to (3-35), R ⁴ and R ⁵ are each independently hydrogen, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and a carbon number of 2 to 12 alkenyl or alkenyloxy having 2 to 12 carbons).

Item 9. The polymerizable composition for a light control element according to Item 7 or Item 8, wherein the ratio of Component C is in the range of 3% by mass to 25% by 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 formula (M-1), M ¹⁰⁰ is hydrogen or methyl; R ¹⁰⁰ and R ¹⁰¹ are each independently Hydrogen, a linear alkyl group with 1 to 10 carbons or a branched alkyl group with 3 to 10 carbons or a linear hydroxyalkyl group with 1 to 10 carbons or a branched hydroxyalkyl group with 3 to 10 carbons; these alkanes In the group or hydroxyalkyl group, at least one -CH ₂ -may be substituted with -O- or -N(R ¹⁰² )-, R ¹⁰² is hydrogen or a linear alkyl group having 1 to 10 carbons; the formula (M- 2) The compound represented is at least one compound selected from the group consisting of compounds represented by formula (M-2-1) to formula (M-2-10), and the carbamate (methyl ) Acrylate oligomer is at least selected from the group consisting of polyester-based urethane (meth)acrylate oligomer and polyether-based urethane (meth)acrylate oligomer One kind, and its weight average molecular weight is in the range of 2,000 to 30,000;

(In the formula, M ¹⁰¹ is hydrogen or methyl; n ¹⁰⁰ is 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 items 1 to 10, further containing a compound selected from the group consisting of compounds represented by formula (M-3) and formula (M-4) At least one polymerizable compound having a phosphoric acid site as a precursor of the polymer;

(In formulas (M-3) to (M-4), M ¹⁰² is hydrogen or methyl; n ¹⁰¹ , n ¹⁰² and n ^{103 are} independently 1 to 4).

（式（M-5-E）及式（M-5-P）中，M⁵⁰¹ 為氫或甲基，R⁵⁰² 為碳數1至6的烷基，n為1至30； 式（M-5-E）的乙二醇結構中及式（M-5-P）的丙二醇結構中的氫可經碳數1至3的烷基取代； (甲基)丙烯酸羥基烷基酯中的烷基是具有碳數2至10的直鏈或碳數3至10的支鏈的伸烷基）。Item 12. The polymerizable composition for a light control element according to any one of items 1 to 11, further containing a compound selected from the group consisting of formula (M-5-E) and formula (M-5-P) At least one polymerizable compound in the group consisting of and at least one polymerizable compound selected from the group consisting of hydroxyalkyl (meth)acrylate as the precursor of the polymer;

(In formula (M-5-E) and formula (M-5-P), M ⁵⁰¹ is hydrogen or methyl, R ⁵⁰² is an alkyl group having 1 to 6 carbons, and n is 1 to 30; formula (M- The hydrogen in the ethylene glycol structure of 5-E) and the propylene glycol structure of formula (M-5-P) can be substituted by an alkyl group having 1 to 3 carbon atoms; the alkyl group in the hydroxyalkyl (meth)acrylate Is a straight-chain or branched alkylene group with a carbon number of 2 to 10 or a branched chain with a carbon number of 3 to 10).

Item 13. The polymerizable composition for a dimmer element according to any one of items 1 to 12, further containing selected from the group consisting of compounds represented by formula (7), formula (8), and formula (9) At least one polymerizable compound as the precursor of the polymer;

In formula (7), formula (8) and formula (9), ring G, ring I, ring J, ring K, ring L and ring M are each independently 1,4-cyclohexyl, 1,4-cyclohexyl Phenyl, 1,4-cyclohexenylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl or pyri-2, 7-diyl group, where at least one hydrogen contained in these groups can be fluorine, chlorine, cyano, hydroxyl, methanoyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, carbon number Substitution with 1 to 5 alkyl group, carbon number 1 to 5 alkoxy group, carbon number 2 to 5 alkoxycarbonyl group or carbon number 1 to 5 alkanoyl group; Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ And Z ¹⁷ are each independently a single bond, -O-, -COO-, -OCO- or -OCOO-; Z ⁹ , Z ¹¹ , Z ¹⁴ and Z ¹⁶ are each independently a single bond, -OCH ₂ -,- CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH _2- , -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH= N-, -N=C(CH ₃ )-, -C(CH ₃ )=N-, -N=N- or -C≡C-; Z ¹⁵ is a single bond, -O- or -COO-; Y ² is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, linear alkyl with 1 to 20 carbons, linear alkenyl with 2 to 20 carbons, and 1 to 20 carbons Linear alkoxy or linear alkoxycarbonyl having 2 to 20 carbons; f and h are each independently an integer from 1 to 4; k and m are each independently an integer from 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 from 0 to 20; M ⁷ to M ¹² are each 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 ratio of the liquid crystal composition is 30% to 95% by mass based on the total mass of the liquid crystal composition and the polymer precursor The ratio of the polymer precursor is in the range of 5% by mass to 70% by mass.

Item 15. The polymerizable composition for a light control element according to any one of items 1 to 14, wherein based on the total mass of the liquid crystal composition and the polymer precursor, The ratio of the compound (M-1) is in the range of 3% by mass to 25% by mass, The ratio of the compound (M-2) is in the range of 3% by mass 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 polymer precursor does not exceed 70% by mass, Based on the total mass of the liquid crystal composition and the polymer precursor, the ratio of the photopolymerization initiator is in the range of 0.1% by mass to 5% by mass.

Item 16. The polymerizable composition for a light control element according to any one of items 11 to 15, wherein based on the total mass of the liquid crystal composition and the polymer precursor, The ratio of the compound (M-3) and the compound (M-4) is in the range of 0.001% by mass to 0.5% by mass.

Item 17. The polymerizable composition for a light control element according to any one of items 12 to 16, wherein based on the total mass of the liquid crystal composition and the polymer precursor, The total ratio of the compound (M-5-E) and/or the compound (M-5-P) and the hydroxyalkyl (meth)acrylate is in the range of 2% by mass to 30% by mass. Item 18. A liquid crystal dimming element, wherein a dimming layer is sandwiched by a pair of transparent substrates, the transparent substrate has a transparent electrode, and the dimming layer is a polymerizable light modulating element according to any one of items 1 to 17 A liquid crystal composite obtained by polymerizing the composition.

Item 19. The liquid crystal dimming device according to item 18, wherein the transparent substrate includes a glass plate, a plastic plate, or a plastic film.

Item 20. The liquid crystal dimming element according to Item 18 or Item 19, wherein ^{the weather resistance test is conducted under the conditions of illuminance (180 W/m 2} ), irradiation time (100 hours), and tank temperature (35°C) The rate of change of haze before and after is 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 according to 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. A use of a liquid crystal composite, which is the liquid crystal composite according to Item 23, which is used in a liquid crystal dimming element.

Item 25. A use of a liquid crystal composite, which is the liquid crystal composite according to item 23, which is used in a liquid crystal dimming element whose transparent substrate includes a plastic plate or a plastic film.

Item 26. A use of a liquid crystal composite, which is the liquid crystal composite according to Item 23, which is used in a dimming window. Item 27. A use of a liquid crystal composite, which is the liquid crystal composite according to Item 23, which is used in a smart window. Item 28. A use of a liquid crystal composite obtained by polymerizing the polymerizable composition for a dimming element according to any one of items 1 to 17, which is used for a transparent substrate including a plastic plate or a plastic film In the liquid crystal dimming element.

The present invention also includes the following items. (A) The polymerizable composition or liquid crystal composite for a light control element as described above, wherein the liquid crystal composition contains at least one compound ^{in which Y 1 is fluorine in the compound (1) described in Item 1 as the component A.} (B) The polymerizable composition or liquid crystal composite for a light control element as described above, wherein the liquid crystal composition contains ^{at least one compound in which Y 1} is a cyano group in the compound (1) described in Item 1 as the component A.

The present invention also includes the following items. (C) The polymerizable composition or liquid crystal composite for a light control element as described above, wherein the liquid crystal composition contains the compound (1-1), the compound (1-2), and the compound (1- 3), compound (1-9), compound (1-13), compound (1-16), compound (1-21), compound (1-22), compound (1-23), compound (1-24) ), compound (1-27), compound (1-28), compound (1-33), compound (1-36), compound (1-41), compound (1-42) and compound (1-48) At least one compound in it is used as component A.

The present invention also includes the following items. (D) The polymerizable composition or liquid crystal composite for a light control element as described above, wherein the liquid crystal composition contains a compound (2-1), a compound (2-2), and a compound (2- 3), compound (2-4), compound (2-6), compound (2-9), compound (2-10), compound (2-12), compound (2-13), compound (2-14) ), at least one of compound (2-16), compound (2-17), compound (2-19), and compound (2-21) is used as component B.

The present invention also includes the following items. (E) The polymerizable composition or liquid crystal composite for a light control element as described above, wherein the liquid crystal composition contains the compound (3-1), the compound (3-5), and the compound (3- 6) At least one of compound (3-7), compound (3-8), compound (3-12), compound (3-14), compound (3-19) and compound (3-34) is used as Ingredient C.

The present invention also includes the following items. (F) The liquid crystal composite as described above, wherein based on the liquid crystal composite, the ratio of the polymer is in the range of 5 mass% to 10 mass %, and the ratio of the liquid crystal composition is in the range of 95 mass% to 90 mass %.

The present invention also includes the following items. (G) The liquid crystal composite as described above, wherein based on the liquid crystal composite, the ratio of the polymer is in the range of 5% to 70% by mass, and the ratio of the liquid crystal composition is in the range of 95% to 30% by mass. (H) The liquid crystal composite as described above, wherein based on the liquid crystal composite, the ratio of the polymer is in the range of 20% by mass to 60% by mass, and the ratio of the liquid crystal composition is in the range of 80% by mass to 40% by mass. (I) The liquid crystal composite as described above, wherein based on the liquid crystal composite, the ratio of the polymer is in the range of 30% to 45% by mass, and the ratio of the liquid crystal composition is in the range of 70% to 55% by mass. In addition, the ratio of the polymer to the liquid crystal composition in the liquid crystal composite corresponds to the ratio of the polymer precursor 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 dimming 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 dimming element having the composite. The liquid crystal composite contains a nematic liquid crystal composition and a polymer.

The present invention will be described in the following order. First, the polymerizable composition will be described. Second, the liquid crystal composition will be described. Third, the main characteristics of the liquid crystal compound and the main effect of the compound on the liquid crystal composition or device will be described. Fourth, the combination or preferred ratio of the liquid crystal compounds will be described. Fifth, the preferred embodiment of the liquid crystal compound will be described. Sixth, preferred liquid crystal compounds will be described. Seventh, the preferred form of the polymer precursor and an example thereof will be described. Eighth, the synthesis method of the component compounds will be described. Ninth, the photopolymerization initiator 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 dimming element will be described.

First, the polymerizable composition will be described. The polymerizable composition of the present invention is a polymerizable composition for light control elements. Hereinafter, it may also be simply referred to as a polymerizable composition. The polymerizable composition is the precursor of the liquid crystal composite, and the liquid crystal composite is produced by the polymerization of the polymer precursor.

The polymerizable composition is a mixture of a polymer precursor, a liquid crystal composition, and a photopolymerization initiator. If the polymerizable composition is put into the device and polymerized, the polymer produced by the polymerization will undergo phase separation, and a liquid crystal composite will be provided. The amount of polymer in the liquid crystal composite corresponds to the amount of polymerizable precursor in the polymerizable composition. Furthermore, the quality of the photopolymerization initiator does not affect the quality of the polymer.

The device having a liquid crystal composite is classified into a polymer stable alignment type, a polymer network type, and a polymer dispersion type according to the polymerization of the polymer. When the ratio of the polymer is small, a polymer sustained alignment type element is produced. This is referred to as PSA element for short. In Example 1 of International Publication No. 2012-050178, it is described that "the monomer is added so as to be 0.5 wt% with respect to the liquid crystal material" (paragraph 0105). According to the above description, in a PSA element, a small amount of a polymerizable compound is added to a liquid crystal material (liquid crystal composition). 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 element is produced. In this type of element, the liquid crystal composition is dispersed in the polymer like liquid droplets. Each droplet is microencapsulated and is not continuous. The liquid crystal molecules are arranged along the inner wall of the capsule, so they are in a random state. Since the refractive index of the polymer is different from the refractive index of the liquid crystal molecules, the incident light is scattered. The component is 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, incident light passes through the element, and the element becomes transparent.

On the other hand, when the ratio of the polymer is moderate, a polymer network type element is produced. In this type of element, the polymer has a three-dimensional grid structure, and the liquid crystal composition is surrounded by the grid and is continuous. The liquid crystal molecules are in a random state, and the device is opaque. When a voltage is applied to the element, the liquid crystal molecules are aligned in the direction of the electric field, so the element becomes transparent. In order to efficiently cause 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 driving voltage is low. Therefore, from the viewpoint of low driving voltage, the ratio of the polymer is preferably small. When the droplet or grid is small, the response time is short. Therefore, from the viewpoint of short response time, the ratio of the polymer is preferably large.

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

When the ratio of the polymer precursor is in the range of 5 mass% to 70 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. Among these elements, unlike PSA elements, no polarizing plate is required. In the polymer network type element, an alignment film is used as necessary.

Based on the mass in the polymerizable composition, the ratio of the liquid crystal composition is preferably in the range of 30% by mass to 95% by mass, and the ratio of the polymer precursor is in the range of 5% by mass to 70% by mass.

Second, the liquid crystal composition will be described. The composition contains a plurality of liquid crystal compounds. The composition may also contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, polymerization initiators, polymerization inhibitors, polar compounds, and the like. From the viewpoint of a liquid crystal compound, the composition is classified into a composition A and a composition B. Composition A contains a compound selected from the group consisting of the compound represented by the formula (1), and optionally the compound represented by the formula (2) and the compound represented by the formula (3) (referred to as compound (1) and compound (2), respectively In addition to the liquid crystal compound in the compound (3)), other liquid crystal compounds, additives, etc. may also be contained. "Other liquid crystal compounds" are liquid crystal compounds different from compound (1), compound (2), and compound (3). The compound is mixed in the composition for the purpose of further adjusting the characteristics.

The composition B substantially contains only a liquid crystal compound selected from the compound (1), and optionally the compound (2) and the compound (3). "Substantially" means that although the composition B may contain additives, it does not contain other liquid crystal compounds. Compared with composition A, the number of components of composition B is small. From the viewpoint of cost reduction, composition B is superior to composition A. The composition A is superior to the composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.

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

Table 2. Characteristics of liquid crystal compounds Compound Compound (1) Compound (2) Compound (3) Upper temperature S～L S～L S～L Viscosity M～L S～M M～L Optical anisotropy M～L S～L M～L Dielectric constant anisotropy S～L 0 M～L ¹⁾ Specific resistance L L L 1) The value of dielectric constant anisotropy is negative, and the sign indicates the magnitude of the absolute value

The main effects of each liquid crystal compound on the characteristics of the liquid crystal composition are as follows. Compound (1) can be used as component A, and increases the dielectric anisotropy. Compound (2) can be used as component B, and the upper limit temperature is increased or the lower limit temperature is lowered.

The compound (3) can be used as the component C, and can increase the dielectric constant of the liquid crystal molecules in the minor axis direction. Fourth, the combination or preferred ratio of the liquid crystal compounds will be described. A preferred combination is component A+component B, component A+component C, or component A+component B+component C. A further preferred combination is component A+component B or component A+component B+component C. It is also possible to combine specific one or two compounds selected from component A with component B (or component C). The same applies to component B or component C.

Based on the quality of the liquid crystal composition, in order to increase the dielectric constant anisotropy, the preferable ratio of the component A is 5 mass% or more, and in order to lower the minimum temperature, the preferable ratio of the component A is 90 mass% or less. A further preferred ratio is in the range of 10% by mass to 85% by mass. A particularly preferred ratio is in the range of 20% by mass to 80% by mass.

Based on the mass of the liquid crystal composition, in order to increase the upper limit temperature or lower the lower limit temperature, the preferred ratio of component B is 5 mass% or more, and in order to increase the dielectric constant anisotropy, the preferred ratio of component B is 90 mass% or less. A further preferred ratio is in the range of 10% by mass to 85% by mass. A particularly preferred ratio is in the range of 20% by mass to 80% by mass.

Based on the mass of the liquid crystal composition, in order to increase the dielectric constant in the minor axis direction of the liquid crystal molecules, the preferred ratio of component C is 3% by mass or more, and in order to lower the minimum temperature, the preferred ratio of component C is 25% by mass or less. A further preferred ratio is in the range of 5% by mass to 20% by mass. A particularly preferred ratio is in the range of 5% by mass to 15% by mass.

Fifth, the preferred embodiment of the liquid crystal compound will be described. In the formula (1), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons. In order to improve the stability to light or heat, it is preferable that R ¹ is an alkyl group having 1 to 12 carbons. Preferred compounds are also the same as in (1) is an example of compound (Compound (1-1) to the compound (1-48) and the like), the definition of R ^1, suitable morphology.

In formula (2), R ² and R ³ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, or at least one hydrogen substituted by fluorine or chlorine Alkenyl having 2 to 12 carbons. In order to increase the upper limit temperature or lower the lower limit temperature, R ² or R ³ is preferably an alkenyl group having 2 to 12 carbons. In order to improve the stability to light or heat, preferably R ² or R ³ is 1 to 12 carbons. alkyl. In the compounds (compounds (2-1) to (2-23), etc.) which are preferred examples of the compound (2), the definitions, suitable forms, and the like of ^{R 2} and R ^{3 are also the same.}

In formula (3), R ⁴ and R ⁵ are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkene having 2 to 12 carbons.基oxy。 In order to improve the stability to light or heat, R ⁴ or R ⁵ is preferably an alkyl group having 1 to 12 carbons. In order to increase the dielectric constant in the minor axis direction of the liquid crystal molecules, R ⁴ or R ⁵ is preferably a carbon number. Alkoxy from 1 to 12. In the compounds (compounds (3-1) to (3-35), etc.) which are preferred examples of the compound (3), the definitions, suitable forms, and the like of ^{R 4} and R ^{5 are also the same.}

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. In order to reduce the viscosity, further preferred alkyl groups are methyl, ethyl, propyl, butyl or pentyl.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. In order to reduce the viscosity, further preferred alkoxy groups 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. In order to reduce the viscosity, further preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl or 3-pentenyl. The preferred configuration of -CH=CH- in these alkenyl groups depends on the position of the double bond. For reducing viscosity, etc., preferred among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl It is a trans configuration. The cis configuration is preferred among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. In order to reduce the viscosity, a further preferred alkenyloxy group is an allyloxy group or a 3-butenyloxy group.

Preferred examples of alkyl groups in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7 -Fluoroheptyl or 8-fluorooctyl. In order to increase the dielectric anisotropy, further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl.

Preferred examples of alkenyl groups in which at least one hydrogen is replaced by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4-pentenyl or 6,6-difluoro-5-hexenyl. In order to reduce the viscosity, further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

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 tetrahydropyridine Pyran-2,5-diyl. In order to increase the optical anisotropy, the preferred ring A is 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3-fluoro-1,4-phenylene. In order to increase the maximum temperature, the three-dimensional configuration related to 1,4-cyclohexylene is the trans configuration better than the cis configuration. Tetrahydropyran-2,5-diyl is

或

，優選為

。

or

, Preferably

.

Ring B and 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. In order to increase the upper limit temperature or to lower the lower limit temperature, the preferred ring B or ring C is 1,4-cyclohexylene, and in order to lower the lower limit temperature, the preferred ring B or ring C is 1,4-phenylene.

Ring D and ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen through fluorine or Chlorine-substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is substituted with fluorine or chlorine, chroman-2,6-diyl or at least A chroman-2,6-diyl group in which hydrogen is replaced by fluorine or chlorine. In order to lower the minimum temperature or increase the upper limit temperature, the preferred ring D or ring F is 1,4-cyclohexylene, and in order to decrease the minimum temperature, the preferred ring D or ring F is 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-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluoro- 2,7-diyl (FLF4), 4,6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2 ) Or 1,1,6,7-tetrafluoroindan-2,5-diyl (InF4).

In order to reduce the viscosity, the preferred ring E is 2,3-difluoro-1,4-phenylene. In order to increase the dielectric constant of the liquid crystal molecules in the minor axis direction, the preferred ring E is 4,6-difluorodiphenyl And thiophene-3,7-diyl.

Z ¹ is a single bond, an ethylene group, an ethylene group, an ethynylene group, a methyleneoxy group, a carbonyloxy group or a difluoromethyleneoxy group. In order to increase the upper limit temperature, Z ¹ is preferably a single bond, and in order to increase the dielectric anisotropy, Z ¹ is preferably a difluoromethyleneoxy group. Especially preferred Z ¹ is a single bond. Z ² is a single bond, an ethylene group, an ethylene group, an ethynylene group, a methyleneoxy group or a carbonyloxy group. In order to improve the stability to light or heat, Z ² is preferably a single bond. Z ³ and Z ⁴ are each independently a single bond, an ethylene group, an ethylene group, a methyleneoxy group or a carbonyloxy group. In order to lower the minimum temperature, Z ³ or Z ⁴ is preferably a single bond, and in order to increase the dielectric constant in the minor axis direction of the liquid crystal molecule, Z ³ or Z ⁴ is preferably a methyleneoxy group. Particularly preferred Z ³ or Z ⁴ is a single bond.

Divalent groups such as methyleneoxy are left-right asymmetrical. Among the methyleneoxy groups, -CH ₂ O- is better than -OCH ₂ -. Among carbonyloxy groups, -COO- is better than -OCO-. Among the difluoromethyleneoxy groups, -CF ₂ O- is better than -OCF ₂ -.

a is 1, 2, 3, or 4. In order to reduce the minimum temperature, a preferable value of a is 2, and in order to increase the dielectric anisotropy, a preferable value of a is 3. b is 1, 2 or 3. In order to lower the lower limit temperature, b is preferably 1, and in order to raise 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. In order to lower the lower limit temperature, the preferable c is 1, and in order to raise the upper limit temperature, the preferable c is 2 or 3. In order to increase the dielectric constant in the minor axis direction of the liquid crystal molecules, d is preferably 0, and in order to lower the minimum temperature, d is preferably 1.

X ¹ and X ² are hydrogen or fluorine. In order to increase the upper limit temperature, X ¹ or X ² is preferably hydrogen, and in order to increase the dielectric constant anisotropy, X ¹ or X ² is preferably fluorine. Y ¹ is fluorine, chlorine, cyano, an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, an alkoxy group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen Alkenyloxy having 2 to 12 carbons substituted with fluorine or chlorine. In order to reduce the viscosity, the preferred Y ¹ is fluorine, and in order to increase the dielectric constant anisotropy or the refractive index anisotropy, the preferred Y ¹ is a cyano group.

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

Sixth, preferred liquid crystal compounds are shown. Preferable compound (1) that can be used as component A is the compound represented by formula (1-1) to formula (1-48) described in item 2 (respectively referred to as compound (1-1) to compound (1-48) )).

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

In addition, it is preferable that at least two of component 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), Compound (1-9) and Compound (1-16), Compound (1-9) and Compound (1-24), Compound (1-9) and Compound (1-41), Compound (1-13) and compound (1-16), Compound (1-16) and Compound (1-24), Compound (1-16) and compound (1-41), Compound (1-16) and Compound (1-42), or Combination of compound (1-16) and compound (1-48).

Furthermore, multiple compounds (1-6), multiple compounds (1-9), multiple compounds (1-16), multiple compounds (1-29), and multiple compounds (1-41) may be combined. ^{By containing at least one compound in which Y 1} is fluorine in the compound (1) as the component A, the dielectric constant anisotropy or refractive index anisotropy of the liquid crystal composition tends to increase. ^{By containing at least one compound in which Y 1} is a cyano group in the compound (1) as the component A, the compatibility of the polymerizable compound and the liquid crystalline compound tends to be improved.

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

Preferably, at least two of component 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) The combination.

Furthermore, multiple compounds (2-9) and multiple 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 increase. In addition, there is a tendency that the compatibility of the fluorine-substituted terphenyl liquid crystal compound with other liquid crystal compounds is improved.

Preferable compound (3) that can be used as component C is the compound represented by formula (3-1) to formula (3-35) described in item 8 (respectively referred to as compound (3-1) to compound (3-35) )).

Among these compounds, at least one of component C is preferably compound (3-1), compound (3-3), compound (3-6), compound (3-8), compound (3-10), compound (3 -14) or compound (3-34). Preferably, at least two of component C are compound (3-1) and compound (3-8), compound (3-1) and compound (3-14), compound (3-3) and compound (3-8) , Compound (3-3) and compound (3-14), compound (3-3) and compound (3-34), compound (3-6) and compound (3-8), compound (3-6) and Compound (3-10) or a combination of compound (3-6) and compound (3-14).

Seventh, the preferred form of the polymer precursor and an example thereof will be described. Polymers are derived from polymer precursors through polymerization. The precursor of the polymer is a polymerizable compound. The polymer precursor for ensuring the adhesion between the plastic film with electrodes and the liquid crystal composite is preferably a monofunctional polymerizable compound (M-1) having no cyclic structure or a monofunctional polymer having a cyclic structure. A combination of any one of a sexual compound (M-2) and a polyfunctional urethane (meth)acrylate oligomer.

Each polymerizable compound and urethane (meth)acrylate oligomer may be independent or a mixture of a plurality of compounds. A preferable monofunctional polymerizable compound is a compound (compound (M-1)) represented by formula (M-1).

In the formula (M-1), M ¹⁰⁰ is hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is substituted with fluorine or chlorine, preferably hydrogen or methyl.

R ¹⁰⁰ and R ¹⁰¹ are each independently hydrogen, a linear or branched alkyl group having 1 to 12 carbons, a linear or branched hydroxyalkyl group having 1 to 12 carbons, these alkyl groups or hydroxy groups In the alkyl group, at least one -CH ₂ -can be substituted with -O-, -N(R ¹⁰² )-, -CO-, -COO- or -OCO-, and R ¹⁰² is hydrogen and a straight chain with 1 to 12 carbon atoms The alkyl group or branched chain alkyl group is preferably each independently hydrogen, a linear alkyl group having 1 to 10 carbons, or a branched alkyl group having 3 to 10 carbons, a linear hydroxyalkyl group having 1 to 10 carbons, or A branched hydroxyalkyl group having 3 to 10 carbon atoms. In these alkyl groups or hydroxyalkyl groups, at least one -CH ₂ -may be substituted with -O- or -N(R ¹⁰² )-, R ¹⁰² is hydrogen, and the carbon number is 1 To 10 straight chain alkyl groups.

The following examples can be given as a preferable compound (M-1). Is N,N-dimethylacrylamide, N,N-diethyl acrylamide, 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 (compound (M-2)) represented by formula (M-2).

In the formula (M-2), M ¹⁰¹ is hydrogen, fluorine, an alkyl group with 1 to 5 carbons or an alkyl group with 1 to 5 carbons in which at least one hydrogen is substituted by fluorine or chlorine, and Z ¹⁰⁰ is a single bond or carbon number The alkylene group of 1 to 10, in the alkylene group, at least one hydrogen may be substituted by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO-, -COO- or -OCO-, R ¹⁰³ is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, or a carbocyclic or heterocyclic A monovalent group with a carbon number of 5 to 35 is generated by removing one hydrogen in the aromatic compound. ^{At least one hydrogen contained in the R 103} can be substituted by an alkyl group with a carbon number of 1 to 12, and at least one -CH _2- It can be substituted by -O-, -CO-, -COO- or -OCO-.

It is preferably at least one compound selected from compounds represented by formula (M-2-1) to formula (M-2-10).

M ¹⁰¹ is hydrogen or methyl, n ¹⁰⁰ is 0, 1 or 2, and m ¹⁰⁰ is an integer of 2-6. The urethane (meth)acrylate oligomer having two or more (meth)acrylic acid groups used as the polyfunctional polymerizable compound is preferably a polyester-based urethane (meth)acrylate oligomer A polymer, a polyether-based urethane (meth)acrylate oligomer, more preferably a polyether-based 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 still more 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 effect of curing shrinkage increases and the adhesion tends to decrease. Conversely, 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 there is a polymer interface and liquid crystal The interaction of the sexual compound decreases and the driving voltage of the liquid crystal composition contained in the liquid crystal composite tends to decrease.

To further strengthen the adhesion, as the polymer precursor, a polymerizable compound (M-3) or compound (M-4) having a phosphoric acid site can be additionally used.

In formula (M-3) to formula (M-4), M ¹⁰² is hydrogen or methyl, and n ¹⁰¹ , n ¹⁰² and n ^{103 are} independently 1 to 4. Preferably, n ¹⁰¹ , n ¹⁰² and n ¹⁰³ are 2 independently.

Here, the function of the polymer precursor will be described. The monofunctional polymerizable compound (M-1) having a nitrogen atom and having an acyclic structure can control the glass transition temperature of the obtained polymer. The polymerizable compound (M-1) has a linear structure such as a linear alkyl group and 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, considering the strong interaction with the substrate interface or the electrode interface, or with the urethane (meth)acrylate described later, it is assumed that the contribution to the improvement of adhesion is large.

The monofunctional polymerizable compound (M-2) having a cyclic structure can also control the glass transition temperature of the obtained polymer. The polymerizable compound (M-2) tends to increase the glass transition temperature of the obtained polymer. It is considered that the polymer obtained from the polymerizable compound (M-2) tends to increase the elastic modulus compared with the polymer using the polymerizable compound (M-1). The adhesion was evaluated in a peeling test, and the peeling in the peeling test included cohesive peeling that occurred in the light control layer and interface peeling that occurred at the interface. It is considered that if the elastic modulus is increased, the cohesive peeling that occurs in the light control layer can be suppressed, and the adhesion to the support substrate tends to be improved.

In the case of a urethane (meth)acrylate oligomer containing a monomer unit having a linear structure in the polymer, if the chain length of the monomer unit becomes longer, the polymer interface and The interaction of the liquid crystal compound decreases and the driving voltage of the liquid crystal composition contained in the liquid crystal composite tends to decrease. Therefore, in the present invention, a predetermined molecular weight is adopted as described above. If an ether structure is contained in a monobody structure having a linear structure, the driving voltage of the liquid crystal composition contained in the obtained liquid crystal composite tends to be lower.

In the case of using the liquid crystal composite of the present application as a light control layer of a liquid crystal light control element, especially by combining a monofunctional polymerizable compound (M-1) having a non-cyclic structure having a nitrogen atom and having a cyclic structure The monofunctional polymerizable compound (M-2) and the urethane (meth)acrylate oligomer, the dimming layer and the electrode (for example, indium tin oxide (Indium Tin Oxide, ITO) The adhesiveness of the plastic film) interface tends to increase.

In addition, in order to increase the peel strength of the liquid crystal composite at the interface of the support substrate (for example, the interface with the plastic film with ITO electrode), a polymerizable compound containing a non-liquid crystalline phosphoric acid site with a polar group may also be used in combination. The compound is thought to induce hydrogen bonds with the hydroxyl groups present on the surface of the ITO electrode and the interaction becomes stronger.

Based on the total mass of the liquid crystal composition and the polymer precursor, The ratio of the compound (M-1) is in the range of 3% by mass to 25% by mass, preferably in the range of 5% by mass to 25% by mass, and more preferably in the range of 10% by mass to 25% by mass, The ratio of the compound (M-2) is 3% by mass to 30% by mass, preferably in the range of 10% by mass to 25% by mass, The ratio of the polyfunctional urethane (meth)acrylate oligomer is preferably in the range of 5% by mass to 25% by mass. Among them, the total ratio of polymer precursors does not exceed 70% by mass.

In order to improve the adhesion between the dimming layer and the interface of the electrode (for example, a plastic film with ITO (Indium Tin Oxide)), it is desirable to adopt the following mass ratio. 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, more preferably 2/1 to 1/2.

In addition, 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. Based on the total mass of the liquid crystal composition and the polymer precursor, the preferable addition amount of the polymerizable compound (M-3) or the compound (M-4) (the total amount when both are used) is from 0.001% by mass to 0.5% by mass, more preferably 0.01% by mass to 0.3% by mass.

In the present invention, the compound (M-1), compound (M-2), and urethane (meth)acrylate oligomers having the formula (M-5) and formula (M-5) may also be contained. -E) and/or a monofunctional polymerizable compound having a linear structure such as a linear alkyl group or a branched chain alkyl group represented by the formula (M-5-P) or an ether structure. In addition, it may contain a polyfunctional polymerizable compound ((formula (M-6)) having a linear structure such as a linear alkyl group or a branched alkyl group.

It can be used singly or multiple monofunctional polymerizable compounds. A plurality of polyfunctional polymerizable compounds can be used alone or in multiples. A monofunctional polymerizable compound and a polyfunctional polymerizable compound may be used in combination, or they may be used alone or in multiple types.

The main function of monofunctional polymerizable compounds with linear or ether structures such as linear or branched alkyl groups in the side chain is to improve compound (M-1), compound (M-2), carbamate (forma The solubility of the acrylate oligomer to the liquid crystal composition. Furthermore, by maintaining the uniformity of the polymerizable composition, the polymerized liquid crystal composite (for example, the light control layer of the liquid crystal light control element) can have uniform scattering characteristics. The polymerizable compound can control the glass transition temperature of the obtained polymer. The glass transition temperature of a polymer containing a linear structure such as a linear alkyl group or a branched alkyl group or an ether structure in the side chain tends to be lower. 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. Although the reason is not clear, it is thought that the reason is that if the chain length of the side chain of the polymer increases or has an ether structure, the interaction between the polymer surface and the liquid crystal compound decreases. In addition, when the chain length of the side chain of the polymer becomes longer or the side chain contains an ether structure, the driving voltage of the liquid crystal composition contained in the obtained liquid crystal composite tends to be lower. The reason for this is similarly unclear, but it is thought that the reason is that the interaction between the polymer surface and the liquid crystal compound is reduced.

In formula (M-5), M ⁵⁰¹ is hydrogen or methyl, and R ⁵⁰¹ is hydrogen or an alkyl group with 1 to 20 carbons. In the alkyl group, at least one hydrogen can be passed through an alkyl group with 1 to 12 carbons, It is substituted by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C-. In the formula (M-5-E) and the formula (M-5-P), M ⁵⁰¹ is hydrogen or methyl, R ⁵⁰² is an alkyl group having 1 to 6 carbons, and n is 1 to 30. The 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 formula (M-6), M ^{601 is} independently hydrogen or methyl, and R ⁶⁰¹ is an alkylene having 1 to 40 carbons. In the alkylene, at least one hydrogen may be passed through an alkylene having 1 to 20 carbons. Group, alkyl (meth)acrylate with 1 to 20 carbons, alkoxy (meth)acrylate with 1 to 20 carbons, alkyl ester (meth)acrylate with 1 to 20 carbons, fluorine Or substituted by chlorine, at least one -CH ₂ -in the alkylene group may be substituted by -O-, -CO-, -COO- or -OCO-.

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

In the example of the preferred compound represented by the formula (M-5-E), M ⁵⁰¹ is preferably hydrogen or methyl, more preferably hydrogen, and R ⁵⁰² is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group. , Ethyl or propyl, n is preferably 1-30, more preferably 2-25. Preferred specific examples include the following compounds.

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

此處，a及b分別表示這些文字的右側記載的基的個數。以下的式（M-6-17）、式（M-6-18）中也表示相同含義。

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

The main function of the polyfunctional polymerizable compound having a linear structure such as a linear alkyl group or a branched chain alkyl group is to increase the crosslink density of the obtained polymer. If the crosslinking density is increased, the reliability of moisture resistance, heat resistance, light resistance, and weather resistance will be 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 increase. If the crosslinking density increases and the glass transition temperature of the polymer increases, the interaction with the liquid crystal compound may also increase, and the driving voltage of the light-adjusting layer may increase. In order to perform low-voltage driving while maintaining reliability, it is desirable not to increase the crosslink density too high. From such a viewpoint, a polyfunctional polymerizable compound having a large molecular weight or a polyfunctional polymerizable compound containing a large number of ether bonds in which the glass transition temperature after polymerization tends to be low is preferable. Relative to the total amount of polymer precursors, a monofunctional polymerizable compound having a linear structure such as a linear alkyl group or a branched alkyl group, and a polyfunctional polymerization compound having a linear structure such as a linear alkyl group or a branched alkyl group The preferable addition amount of the sexual compound is 1% by mass to 50% by mass, more preferably 3% by mass to 30% by mass, and still more preferably 3% by mass to 20% by mass.

In the present invention, for the purpose of controlling scattering characteristics or improving heat resistance, a polymerizable compound having a liquid crystal structure (mesogen structure) may be further contained. The polymerizable compound having a liquid crystal structure is copolymerized with the polymer precursor 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) (respectively referred to as compound (7), compound (8), and compound (9)). The polymerizable compound having a liquid crystal structure may also be a mixture of compounds selected from compound (7), compound (8), or compound (9).

The mixture may contain a polymerizable compound different from compound (7), compound (8), or compound (9). In compound (7), compound (8) and compound (9), ring G, ring I, ring J, ring K, ring L and 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 pyridine-2,7-diyl In this case, at least one hydrogen may be fluorine, chlorine, cyano, hydroxy, methanoyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, alkyl with 1 to 5 carbons, carbon number Substitution is an alkoxy group having 1 to 5, an alkoxycarbonyl group having 2 to 5 carbons, or an alkanoyl group having 1 to 5 carbons. In compound (7), compound (8) and compound (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. A further preferred ring is 1,4-cyclohexylene or 1,4-phenylene.

Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ and Z ¹⁷ are single bonds, -O-, -COO-, -OCO- or -OCOO-. Z ⁹ , Z ¹¹ , Z ¹⁴ and Z ¹⁶ are single bonds, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-,- OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH ₃ )-, -C(CH ₃ )=N-, -N=N- or -C≡C-. Z ¹⁵ is a single bond, -O- or -COO-. Preferably Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ or Z ¹⁷ is a single bond or -O-. Preferably Z ⁹ , Z ¹¹ , Z ¹⁴ or Z ¹⁶ is a single bond, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CH ₂ CH ₂ -, -CH ₂ CH ₂ COO- Or -OCOCH ₂ CH ₂ -.

Y ² is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, linear alkyl having 1 to 20 carbons, linear alkenyl having 2 to 20 carbons, and 1 to 20 carbons A straight-chain alkoxy group or a straight-chain alkoxycarbonyl group having 2 to 20 carbons. Preferably Y ² is a cyano group, a linear alkyl group or a linear alkoxy group.

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. M ⁷ to M ¹² are hydrogen or methyl.

An example of the compound (7) is as follows.

式（7-1）至式（7-24）中，M⁷ 為氫或甲基，e為1至20的整數。

In formula (7-1) to formula (7-24), M ⁷ is hydrogen or methyl, and e is an integer of 1-20.

An example of the compound (8) is as follows.

式（8-1）至式（8-31）中，M⁸ 及M⁹ 為氫或甲基，g及i為1至20的整數。

In formula (8-1) to formula (8-31), M ⁸ and M ⁹ are hydrogen or methyl, and g and i are integers of 1-20.

An example of the compound (9) is as follows.

式（9-1）至式（9-10）中，M¹⁰ 、M¹¹ 及M¹² 為氫或甲基，j、l及n為1至20的整數。

In formulas (9-1) to (9-10), M ¹⁰ , M ¹¹ and M ¹² are hydrogen or methyl, and j, l and n are integers from 1 to 20.

Compound (7), compound (8) and compound (9) have at least one acryloxy group (-OCO-CH=CH ₂ ) or methacryloxy group (-OCO-(CH ₃ )C=CH ₂ ). Liquid crystal compounds have mesogens (a site that induces rigidity of liquid crystallinity), and these compounds also have mesogens. Therefore, these compounds and the liquid crystal compound are aligned in the same direction by the action of the alignment film. The alignment is also maintained after polymerization.

The liquid crystal composite obtained by polymerizing the polymerizable composition for light control elements 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 compound (7) to the compound (9) is 3% by mass to 50% by mass, and more preferably 5% by mass to 30% by mass relative to the total amount of the polymer precursor. Eighth, the synthesis method of the component compounds will be described. These compounds can be synthesized by known methods. Illustrate the synthesis method. The compound (1-9) and the compound (1-16) were synthesized by the method described in Japanese Patent Laid-Open No. 2-233626. The compound (2-1) was synthesized by the method described in Japanese Patent Application Laid-Open No. 59-176221. Compound (3-1) was synthesized by the method described in Japanese Patent Application Publication No. Hei 2-503441. Antioxidants are already commercially available. The compound (11-1) mentioned later can be obtained from Sigma-Aldrich Corporation. Compound (11-2) and the like were synthesized by the method described in the specification of US Patent No. 3660505. The polymerizable compound is commercially available or synthesized by a known method.

Compounds without a description of the synthesis method can be synthesized using the method described in the following book: "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Syntheses" (John Wiley & Sons, Inc.) Reactions" (John Wiley & Sons, Inc.), "Comprehensive Organic Synthesis" (Pergamon Press), "Lectures on New Experimental Chemistry" ( Maruzen) and so on. The composition is prepared from the compound obtained in the manner described above using a known method. For example, the component compounds are mixed and then heated to dissolve each other.

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

Regarding the preferable addition amount, the ratio of the photopolymerization initiator is 0.1% by mass to 5% by mass, more preferably 0.3% by mass to 3% by mass, based on the total mass of the liquid crystal composition and the polymer precursor. In addition, when the liquid crystal polymerizable compound is contained together with the liquid crystal composition and the polymer precursor, the total amount becomes the total amount of the liquid crystal composition, the polymer precursor, and the liquid crystal polymerizable compound.

Tenth, the additives that can be added to the polymerizable composition will be described. The additives are antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, polymerization initiators other than photopolymerization initiators, polymerization inhibitors, polar compounds, and the like. Additives may be added to the liquid crystal composition or polymerizable compound in advance.

Based on the total amount of the liquid crystal composition and the polymer precursor, the preferable addition amount is 0.1% by mass to 5% by mass, and more preferably 0.3% by mass to 3% by mass. In addition, when a polymerizable compound having a liquid crystal structure is contained, it becomes a ratio with respect to the total amount of the liquid crystal composition, the precursor of the polymer, and the polymerizable compound having a liquid crystal structure.

In addition, for the purpose of causing a helical structure of liquid crystal molecules to impart a torsion angle, an optically active compound may be added to the polymerizable composition. Examples of the compound are the compound (10-1-1) to the compound (10-7-1) represented by the following formula. The preferable ratio of the optically active compound with respect to the liquid crystal composition is 5 mass% or less. A further preferred ratio is in the range of 0.01% by mass to 2% by mass.

In order to prevent the decrease in specific resistance caused by heating in the atmosphere or to maintain a large voltage retention rate not only at room temperature but also at a temperature close to the upper limit temperature after using the element for a long time, the following Antioxidants such as the compound (11-1) to the compound (11-3) represented by the formula are added to the polymerizable composition.

A compound with low 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 using the device for a long time. In order to obtain the above effect, the preferred ratio of the antioxidant relative to the total amount of the liquid crystal composition is 50 ppm by mass or more. In order not to lower the upper limit temperature or increase the lower limit temperature, the preferred ratio of the antioxidant is 600 ppm by mass or less. . A further preferable ratio is in the range of 100 ppm by mass to 300 ppm by mass.

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 preferable. Preferable examples of the light stabilizer are the compound (12-1) to the compound (12-16) represented by the following formula, and the like. In order to obtain the above-mentioned effect, the preferred ratio of these absorbents or stabilizers is 50 mass ppm or more relative to the total amount of the liquid crystal composition. In order not to lower the upper limit temperature or increase the lower limit temperature, these absorbents or stabilizers The preferred ratio is 10000 ppm by mass or less. A further preferable ratio is in the range of 100 ppm by mass to 10,000 ppm by mass.

The matting agent is a compound that receives light energy absorbed by the liquid crystal compound and converts it into thermal energy to prevent the decomposition of the liquid crystal compound. Preferable examples of the matting agent are compound (13-1) to compound (13-7) and the like. In order to obtain the effect, the preferable ratio of these matting agents is 50 ppm by mass or more. In order not to increase the minimum temperature, the preferable ratio of these matting agents is 20,000 ppm by mass or less with respect to the total amount of the liquid crystal composition. A further preferable ratio is in the range of 100 ppm by mass to 10,000 ppm by mass.

In order to be suitable for elements in a guest host (GH) mode, a dichroic dye (dichroic dye) as a dye is added to the composition. Liquid crystal dimming elements are sometimes used for room partitions. In this case, a dye is added to the polymerizable composition for the purpose of absorbing specific light. A variety of pigments can be added. Liquid crystal dimming elements are sometimes used to block sunlight. In this case, a black (or blackened color) dichroic dye is added to the liquid crystal composition. Black is prepared by mixing cyan, magenta, and yellow dichroic pigments. In Example 42 of JP 2006-193742 A, a black dichroic dye is described. The pigment is prepared by mixing three azo compounds with anthraquinones.

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

The dichroic dye has at least some of the characteristics described below. a) The molecules of the pigment are linear. b) A skeleton unique to dichroic dyes such as a benzothiadiazole ring or a diketopyrrolopyrrole ring exists in the center of the molecule. c) The benzene ring or thiophene ring that constitutes the molecule together with the unique skeleton is located on the same plane. d) The side chain is alkyl or alkoxy. e) It has a conjugated double bond in the center.

Preferred dichroic pigments 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 dyes having a benzothiadiazole ring.

R及R'表示可具有取代基的碳數1～30的烴基等，也可在結構內還具有偶氮基。

R and R'represent a C1-C30 hydrocarbon group etc. which may have a substituent, and may also have an azo group in a structure.

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

The preferred ratio of the dichroic dye is in the range of 0.01% by mass to 25% by mass based on the weight of the liquid crystal composition. A further preferred ratio is in the range of 0.02% by mass to 20% by mass. A particularly preferred ratio is in the range of 0.03% by mass to 15% by mass.

In order to prevent foaming, defoamers such as dimethyl silicone oil and methyl phenyl silicone oil may be added to the polymerizable composition. In order to obtain the effect, the preferred ratio of the antifoaming agent is 1 mass ppm or more with respect to the total amount of the polymerizable composition, and in order to prevent display failure, the preferred ratio of the antifoaming agent is 1000 mass ppm or less. A further preferable ratio is in the range of 1 ppm by mass to 500 ppm by mass.

It is preferable to irradiate ultraviolet rays during polymerization of the polymerizable compound. Examples of ultraviolet irradiation lamps are metal halide lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, ultraviolet-light emitting diode (UV-LED) lamps 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 range of the photopolymerization initiator. Avoid the absorption wavelength region of the liquid crystal composition. The preferred wavelength is 330 nm or more. Furthermore, the preferable wavelength is 350 nm or more, for example, 365 nm. The reaction can be carried out around room temperature, or can be carried out under heating.

Generally, when storing a polymerizable compound, a polymerization inhibitor may be added in order 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 polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tertiary butylcatechol, 4-methoxyphenol, phenothiol, and the like.

The polar compound is a polar organic compound different from the compound (M-1), the compound (M-2), the compound (M-3), or the compound (M-4). It may also have a polymerizable group. Here, compounds having ionic bonds are not included. Atoms such as oxygen, sulfur, and nitrogen are negatively charged and tend to have partial negative charges. Carbon and hydrogen are neutral or have a tendency to have a partial positive charge. Polarity is caused by the uneven distribution of partial charges among the atoms of different species in the compound. For example, the polar compound has at least one partial structure such as -OH, -COOH, -SH, -NH ₂ , >NH, >N-, or an isocyanurate group or a sulfo group. As a preferred compound, the following compound (14) or hydroxyalkyl (meth)acrylate can be exemplified. Specific examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and 3 -Hydroxypropyl, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxy acrylate Amyl ester, 2-hydroxypentyl methacrylate.

Based on the total mass of the liquid crystal composition and the polymer precursor, the preferred ratio of the compound (14) is in the range of 1% by mass to 10% by mass, and more preferably in the range of 1% by mass to 7% by mass. Based on the total mass of the liquid crystal composition and the polymer precursor, the preferred ratio of the hydroxyalkyl (meth)acrylate is in the range of 1% by mass to 20% by mass, more preferably in the range of 3% by mass to 15% by mass . It is believed that by using hydroxyalkyl (meth)acrylate in combination with the compound (M-5-E) and/or the compound (M-5-P), the glass transition temperature of the polymer is lowered, so it is expected that the temperature will be lower It can also be driven in a different environment. The combined preferred hydroxyalkyl (meth)acrylate is 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, acrylic acid 4 -Hydroxybutyl or 4-hydroxybutyl methacrylate, more preferably 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate or 4-hydroxybutyl acrylate. When the hydroxyalkyl (meth)acrylate and the compound (M-5-E) and/or the compound (M-5-P) are used in combination, based on the total mass of the liquid crystal composition and the polymer precursor, ( 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.

The polar group has a non-covalent bonding interaction with the surface of a glass substrate, a metal oxide film, and the like. The compound is adsorbed on the surface of the substrate through the action of the polar group and controls the alignment of the liquid crystal molecules. The polar compound not only controls the liquid crystal compound, but also sometimes controls the polymerizable compound. Such effects are 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 the liquid crystal dimming layer of the liquid crystal dimming element, a polymerizable composition can be used and the liquid crystal dimming element can be prepared, for example, in the following manner. First, the polymerizable composition is sandwiched between a pair of substrates. At this time, it is preferable to drop or apply the polymerizable composition 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 the period from the start of the dropping or coating to the polymerization of the polymerizable composition. When dripping or coating is performed, as a method of sandwiching the polymer-dispersed liquid crystal composition with two substrates, it can be carried out by a method of sandwiching two substrates with a laminator or the like. It is sandwiched between two substrates, and then the polymerizable compound is polymerized by light. At this time, as described above, the polymerization is preferably performed by ultraviolet irradiation. Through the polymerization, the polymer phase separates from the polymerizable composition. Thereby, a dimming layer is formed between the substrates, and the dimming layer has the following layers: a layer containing a liquid crystal composition having a dimming function; and a layer containing a polymer. The light-adjusting layer is classified into a polymer dispersion type, a polymer network type, and a mixture of both types. 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 use of the liquid crystal composite and the liquid crystal dimming element will be described. An example of a preferable use of the liquid crystal composite obtained as described above is a liquid crystal dimming element. The liquid crystal dimming element has a dimming layer including a liquid crystal composite and a pair of substrates, and the dimming layer is sandwiched by the pair of substrates. The substrate has electrodes, and the electrodes are generally arranged toward the side (inner side) of the light-adjusting layer. The substrate contained in the liquid crystal dimming element is preferably a transparent substrate, and it is preferable that a pair of transparent substrates are contained in the liquid crystal dimming element so as to sandwich the dimming layer. In addition, the electrode included in the substrate is preferably a transparent electrode.

An example of the transparent substrate contained in the liquid crystal dimming element is a plastic plate (typically a transparent plastic plate) represented by a glass plate, a quartz plate, and an acrylic plate, which is made of a material that is difficult to deform. board. Examples of preferred transparent substrates are glass plates and plastic plates (typically transparent plastic plates).

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

The substrate has electrodes, typically transparent electrodes, on it. It is also possible to have an alignment film or the like on the transparent electrode. Examples of transparent electrodes are indium tin oxide (tin-doped indium oxide (ITO)) or conductive polymers.

Regarding the alignment layer that 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 heat curing at a temperature of 180°C or higher, and rubbing treatment with cotton cloth or rayon cloth as necessary. .

The pair of substrates are typically opposed to each other so that the transparent electrode layer is inside (the light control layer side). In order to make the thickness between the substrates uniform, spacers can also be placed. Examples of spacers are glass particles, plastic particles, alumina particles, and photo spacers. The spacer is contained in the polymerizable composition of the present invention, and it can be used as a raw material of the liquid crystal dimming element. The preferred thickness of the light-adjusting layer is 2 μm to 50 μm, and more preferably 5 μm to 20 μm. The spacers may be spread on the substrate in advance, or may be mixed into the polymerizable composition in advance, and coated on the substrate at the same time as the polymerizable composition is applied. When bonding a pair of substrates together, a general-purpose sealant can be used. An example of the sealing agent is an epoxy-based thermosetting composition.

The method of coating the polymerizable composition on the film substrate may adopt either a discontinuous batch method or a continuous roll to roll method. For example, after the polymerizable composition is applied between the film substrate and the film substrate, it is polymerized by UV irradiation to form a light-adjusting film. The coating method may include a micro-gravure method or a slot die method. By choosing an appropriate coating method, a light-adjusting film can be manufactured. In addition, substrates can also be produced by printing such as flexographic printing, gravure printing, UV offset printing, and screen printing. At this time, a light-adjusting film with textures such as borders, stripes, fabrics, gradients, and dots can also be produced by masking or other methods. The viscosity (25°C) of the polymerizable composition varies depending on the coating method, and the optimal viscosity is 10 mPa·s to 1000 mPa·s. When a film substrate is used, it is preferably 50 mPa·s to 500 mPa·s, and more preferably 100 mPa·s to 300 mPa·s. If the viscosity is too low, it will cause sagging, and if the viscosity is too high, it will be difficult to control the film thickness.

In the element, if necessary, a light absorption layer, a diffuse reflection plate, etc. may be arranged on the back of the element. Functions such as specular reflection, diffuse reflection, retroreflective reflection, and total image reflection can also be added.

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

According to the present invention, a liquid crystal dimming element with high durability against external light and low driving voltage can be obtained. The liquid crystal dimming element will be described below with reference to the drawings. Figures 1 and 2 show an example of a liquid crystal dimming 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 crystal compound exists in an unaligned form. When light enters the light-adjusting layer, strong scattering of the incident light occurs at the interface due to the difference in refractive index between the polymer, which is a transparent substance, and the liquid crystal composition. Therefore, the transmission of light is hindered. When a voltage is applied between the substrates as shown in FIG. 1, the liquid crystal compound is aligned. At this time, the difference in refractive index between the polymer, which is a transparent substance, and the liquid crystal composition is reduced, the scattering of incident light is reduced, and the light passes through the light control layer.

In the reverse mode, the electrode interface is equipped with an alignment film, and the liquid crystal compound is aligned when no voltage is applied. (State when voltage is applied in the normal mode) At this time, the difference in refractive index between the polymer as a transparent substance and the liquid crystal composition is reduced, the light incident on the light control layer is scattered less, and the light passes through the light control layer. In the reverse mode, when a voltage is applied between the substrates, the alignment of the liquid crystal is disrupted, resulting in a difference in refractive index with the polymer, which scatters incident light, thereby obstructing the transmission of light.

The element has a function as a dimming film or a dimming glass. When the element is in the form of a film, it can be attached to an existing window or sandwiched between a pair of glass plates to make laminated glass. The elements are used to partition windows arranged on the outer wall or the conference room and the corridor. That is, there are applications such as electronic blinds, dimming windows, and smart windows. Furthermore, the function as an optical switch can be used for liquid crystal shutters and the like.

Sometimes changes over time are caused by long-term use of components. Sometimes the haze ratio changes from the initial stage. The change in the haze rate is preferably small. When the haze change rate is small, a good state of transparency/opacity can be maintained. The haze change rate before and after the weather resistance test performed under the conditions of illuminance (180 W/m ² ), irradiation time (100 hours), and tank temperature (35° C.) 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 haze change rate is an important factor for the long life of the liquid crystal dimming element. When the weather resistance of the element is tested, the haze change rate before and after it is preferably small. In order to achieve a small haze change rate, it is important to select the type of liquid crystal compound, combine it with a specific polymerizable compound, and study the ratio of each component compound. In order to obtain better results, it is useful to study the type or amount of additives, polymerization conditions, and the like.

[Example] The present invention is further described in detail through examples. The present invention is not limited by these examples. In the examples, the composition (M1), the composition (M2), and the like are described. In the examples, the mixture of the composition (M1) and the composition (M2) is not described. However, it is deemed that the mixture is also disclosed. It is deemed that a mixture of at least two components selected from the examples is also disclosed. The synthesized compounds are identified by methods such as nuclear magnetic resonance (NMR) analysis. The characteristics of the compound, composition, and device are measured by the following methods.

Measurement method: Use the following method to measure the characteristics. Most of these methods are the methods described in the JEITA standard (JEITA·ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (JEITA) or modified. method. In the twisted nematic (TN) element used for the measurement, the Thin Film Transistor (TFT) is not installed.

(1) The upper limit temperature of the nematic phase (NI; °C): Place the sample on the heating plate of the melting point measuring device including the polarizing microscope, and heat it at a rate of 1 °C/min. The temperature at which a part of the sample changes from a nematic phase to an isotropic liquid is measured. The upper limit temperature of the nematic phase is sometimes referred to simply as the "upper limit temperature". (2) Lower limit temperature of nematic phase (TC; ℃): put the sample with nematic phase into a glass bottle and freeze at 0℃, -10℃, -20℃, -30℃ and -40℃ After 10 days of storage in the container, the liquid crystal phase was observed. For example, when the sample maintains a nematic phase at -20°C and changes to a crystal or a smectic phase at -30°C, TC is described as ≦-20°C. The lower limit temperature of the nematic phase is sometimes referred to simply as the "lower limit temperature". (3-1) Viscosity of the composition (bulk viscosity; η; measured at 20°C; mPa·s): The E-type rotary viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement. (3-2) Viscosity of the polymerizable composition (bulk viscosity; η; measured at 25°C; mPa·s): The E-type rotary viscometer (VISCOMETER) manufactured by Toki Sangyo Co., Ltd. was used for measurement. TV-25 type). (4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s): According to M. Imai et al. "Molecular Crystals and Liquid Crystals" Vol. 259 No. The measurement is performed by the method described on page 37 (1995). The sample was placed in a TN device with a torsion angle of 0° and a distance between two glass substrates (cell gap) of 5 μm. In the range of 16 V to 19.5 V, a voltage is applied to the element stepwise in units of 0.5 V. After the voltage was not applied for 0.2 seconds, it was repeatedly applied with only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by the application are measured. Based on these measured values and the calculation formula (10) described on page 40 of the paper by M. Imai et al., the value of the rotational viscosity is obtained. The value of dielectric anisotropy required for the calculation is obtained by the method described below using an element whose rotational viscosity has been measured. (5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25°C): Using light with a wavelength of 589 nm, it is measured with an Abbe refractometer equipped with a polarizing plate on the eyepiece. After rubbing the surface of the main shaft in one direction, drop the sample on the main shaft. The refractive index n∥ is measured when the direction of polarized light is parallel to the direction of rubbing. The refractive index n⊥ is measured when the direction of polarized light is perpendicular to the direction of rubbing. The value of optical anisotropy is calculated according to the formula of Δn=n∥-n⊥. (6) Dielectric constant anisotropy (Δε; measured at 25°C): A sample is placed in a TN element with a gap (cell gap) of 9 μm between two glass substrates and a twist angle of 80 degrees. A sine wave (10 V, 1 kHz) was applied to the device, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured after 2 seconds. A sine wave (0.5 V, 1 kHz) was applied to the element, and the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured after 2 seconds. The value of dielectric anisotropy is calculated by the formula Δε=ε∥-ε⊥.

Method for measuring the physical properties of the liquid crystal light control element: The physical properties are measured by the following method. (1) Determination of the haze (%) of the unit Set the unit (liquid crystal dimming element) in the haze meter NDH5000 manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD so that the light of the light source is perpendicular to the unit surface, and measure at room temperature Haze (%).

(2) Change rate of haze (%) The units obtained in each of the Examples and Comparative Examples were put into a Xenon weather meter under the conditions described later and irradiated with ultraviolet A (ultraviolet A). For the units, the haze (%) was measured at room temperature. ). From the haze (%) of the cell before UVA irradiation and the haze (%) after UVA irradiation, the rate of change in haze was calculated as shown below. Haze rate of change = (((Haze before UVA irradiation (%))-(Haze after UVA irradiation (%)))/(Haze before UVA irradiation (%)))*100

(3) Color difference change rate (%) (3-1) Confirmation of the color difference of the unit Use JASCO V-650 spectrophotometer manufactured by JASCO, irradiate the wavelength from 380 nm to 780 nm, and measure the transmittance of the cell at each wavelength. Then, using the color calculation program software (JASCO V-600 for windows (JASCO V-600 for windows)) that conforms to the calculation formula described in the Japanese Industrial Standard (JIS) Z8729-2004 Analyze and calculate b* based on the L*a*b* color system. In addition, the color difference value used to calculate the color difference change rate% of the cell described later is a value when an electric field of 60 V is applied to the cell at room temperature.

(3-2) Calculation method of unit color difference change rate (%) The cells obtained in the respective Examples and Comparative Examples were put into a xenon weather meter under the conditions described later and irradiated with UVA, and the color difference of the cells (room temperature, 60 V electric field application) was measured for the cells. The rate of change of color difference is calculated as shown below. Change rate of chromatic aberration = (((color difference before UVA irradiation)-(color difference after UVA irradiation))/(color difference before UVA irradiation))*100

(3-3) Weather resistance test of components: Measure the haze (%) before and after the test, and calculate the haze change rate. The test was conducted in accordance with Japanese Industrial Standards (JIS) K5600-7-7, promotion of weather resistance and promotion of light resistance (xenon lamp method). The super xenon weather meter (super xenon weather meter) SX75 model manufactured by Suga Testing Machine (Stock) was used for the measurement. The measurement conditions are illuminance (UVA; 180 W/m ² ), irradiation time (100 hours), blackboard temperature (63°C±2°C), tank temperature (35°C), and tank relative humidity (40%RH). UVA refers to ultraviolet A (ultraviolet A).

(4) Confirmation of the drive Unless otherwise stated, a case where a voltage is applied from a state where no voltage is applied at room temperature (25° C.) and the haze (%) becomes 10% or less at 100 V or less is evaluated as being driveable.

(5) Evaluation of adhesion For the test of adhesion evaluation, VESO5D (STOROGRAPH) manufactured by Toyo Seiki Seisakusho Co., Ltd. was used. On a plastic flat plate with a width of 25.0 mm and a length of 200 mm, the nicetack NWBB-N30 manufactured by Nichiban Co., Ltd. is attached to the entire width. A dimmer film made with a width of 25 mm and a length of 350 mm was attached to it as a test piece. The test piece was mounted on a testing machine, and the average peel force when one side of the test piece was peeled in a 180° direction in an environment of 25°C at a tensile speed of 100 mm/min was determined. For each test piece, the average peel force was calculated from the force-grip movement curve on the peel length of at least 100 mm except for the first 25 mm. The test is continued until the bonding length peels off at least 125 mm, the number of test pieces is set to 3 or more, and the average value is calculated and evaluated. Here, if the peeling force is 0.3 N/cm (0.1 N/inch in inches) or more, the adhesion is evaluated as good.

Examples of the composition are shown below. The liquid crystal compound is represented by a symbol based on the definition in Table 3 below. In Table 3, the steric configuration related to 1,4-cyclohexylene is trans. The number in parentheses after the symbolized compound indicates the chemical formula to which the compound belongs. The symbol (-) refers to other liquid crystal compounds. Finally, the characteristic values of the composition are summarized.

The following compositions were used in the examples.

The polymerizable compound is appropriately selected and used from the following compounds. The following compounds can be mentioned as the monofunctional monomer (M-1). N,N-dimethylacrylamide, N,N-diethylacrylamide, N-(butoxymethyl)acrylamide, N-(2-hydroxyethyl)acrylamide, N- [3-(Dimethylamino)propyl]acrylamide.

The following compounds can be mentioned as the monofunctional monomer (M-2) having a cyclic structure.

其中，本實施例中，使用了（M-2-2-1）、（M-2-7-1）及（M-2-10-1）。

Among them, in this embodiment, (M-2-2-1), (M-2-7-1), and (M-2-10-1) are used.

As a multifunctional urethane (meth)acrylate oligomer, Using a polyether-based urethane acrylate oligomer with a weight average molecular weight of approximately 11,000, UN6202 (manufactured by Negami Industrial Co., Ltd.), and a polyether-based urethane acrylate oligomer with a weight average molecular weight of 27,000 UN6207 (manufactured by Nejo Industrial Co., Ltd.).

As a polymerizable compound (M-3) having a phosphoric acid site, in the formula (M-3), M ¹⁰² is a methyl group and n ¹⁰¹ is 2 Light Ester P-1M (Kyoeisha Chemical Co., Ltd.) Company manufacturing). As the hydroxyalkyl (meth)acrylate as the polar compound, 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate is used.

As a monofunctional polymerizable compound (formula (M-5-E)) having a linear structure such as a linear alkyl group or a branched chain alkyl group, the compound (M-5-E-1) and the compound (M-5 -E-2), compound (M-5-E-3), compound (M-5-E-4). In this example, as the compound (M-5-E-1), Biscoat #190, CBA, EEEA (manufactured by Osaka Organic Chemical Industry) was used, and as the compound (M-5-E-4), NK ester AM-130G (manufactured by Shin Nakamura Chemical Industry).

[Example 1] (1) Production of liquid crystal dimming components The composition (M4) has positive dielectric constant anisotropy. 60% by mass of the composition (M4), 10% by mass of N,N-diethylacrylamide, 20% by mass urethane acrylate oligomer UN6202, and 10% by mass of polymerizable compound (M-2-7-1) is mixed, Prepare polymerizable composition. Based on the total mass of the mixture of the liquid crystal composition and the polymerizable compound, Omnirad 651 (photopolymerization initiator; registered trademark; IGM resin (IGM Resins)) was added at a ratio of 0.4% by mass to prepare a blend Polymerizable composition for optical devices. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). A 15 μm spacer was placed in the polymerizable composition for light control elements, and it was applied to a PET film with ITO (film thickness 125 μm), and then bonded to another film using a laminator.

Second, use a UV-LED exposure device (manufactured by AKS Co., Ltd., LED exposure device AMU-35-DU/LED), irradiate 3 J/cm ² at room temperature (25°C) with a wavelength of 365 nm and an illuminance of 15 Ultraviolet rays of mW/cm ² produce a device with a liquid crystal composite. The resulting element is opaque. A voltage of 60 V was applied to the element and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode.

(2) Evaluation of adhesion The peeling force of the element was measured under the conditions described in the measurement (5). As a result, the peeling force was 0.6 N/cm.

(3) Evaluation of haze change rate after weather resistance test The obtained element was set in the haze meter so that the element was perpendicular to the incident light. A voltage in the range of 0 V to 60 V was applied to the element, and the haze ratio was measured. Next, the haze rate after the weather resistance test carried out under the conditions described in the measurement (3-3) was measured, and the haze change rate was calculated. As a result, it was about 5%.

[Example 2] 60% by mass of the composition (M4), 10% by mass of N,N-diethylacrylamide, 20% by mass urethane acrylate oligomer UN6202, and 10% by mass of polymerizable compound (M-2-2-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.3 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 4%.

[Example 3] 60% by mass of the composition (M4), 15% by mass of N,N-diethylacrylamide, 15% by mass urethane acrylate oligomer UN6202, and 10% by mass of polymerizable compound (M-2-2-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.8 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 5%.

[Example 4] 55% by mass of the composition (M4), 22.5 mass% of N,N-diethyl acrylamide, 11.25% by mass of urethane acrylate oligomer UN6202, and 11.25% by mass of polymerizable compound (M-2-2-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 2.3 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 5%.

[Example 5] The composition (M5) has positive dielectric constant anisotropy. 60% by mass of the composition (M5), 20% by mass of N,N-diethylacrylamide, 10% by mass urethane acrylate oligomer UN6202, and 10% by mass of polymerizable compound (M-2-7-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.3 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 5%.

[Example 6] 60% by mass of the composition (M5), 10% by mass of N,N-diethylacrylamide, 10% by mass urethane acrylate oligomer UN6202, and 20% by mass of polymerizable compound (M-2-7-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 2.3 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 4%.

[Example 7] 60% by mass of the composition (M5), 15% by mass of N,N-diethylacrylamide, 15% by mass urethane acrylate oligomer UN6202, and 10% by mass of polymerizable compound (M-2-7-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.8 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 5%.

[Example 8] 60% by mass of the composition (M5), 10% by mass of N,N-diethylacrylamide, 10% by mass urethane acrylate oligomer UN6202, and 20% by mass of polymerizable compound (M-2-2-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.5 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 5%.

[Example 9] 60% by mass of the composition (M5), 20% by mass of N,N-diethylacrylamide, 10% by mass urethane acrylate oligomer UN6202, and 10% by mass of polymerizable compound (M-2-2-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 2.5 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 4%.

[Example 10] 60% by mass of the composition (M4), 10% by mass of N,N-diethylacrylamide, 19.8% by mass urethane acrylate oligomer UN6202 10% by mass of polymerizable compound (M-2-7-1), and 0.2% by mass of Light Ester (Light Ester) P-1M mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 11.4 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 5%.

[Example 11] 60% by mass of the composition (M4), 10% by mass of N,N-diethylacrylamide, 19.8% by mass urethane acrylate oligomer UN6202 10% by mass of polymerizable compound (M-2-2-1), and 0.2% by mass of Light Ester (Light Ester) P-1M mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 10.2 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 4%.

[Example 12] 60% by mass of the composition (M1), 15% by mass of N,N-diethylacrylamide, 15% by mass urethane acrylate oligomer UN6202, and 10% by mass of polymerizable compound (M-2-7-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.9 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 2%.

[Example 13] 60% by mass of the composition (M2), 15% by mass of N,N-diethylacrylamide, 15% by mass urethane acrylate oligomer UN6202, and 10% by mass of polymerizable compound (M-2-7-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.7 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 3%.

[Example 14] 60% by mass of the composition (M3), 15% by mass of N,N-diethylacrylamide, 15% by mass urethane acrylate oligomer UN6202, and 10% by mass of polymerizable compound (M-2-7-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.8 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 2%.

[Example 15] The composition (M10) has positive dielectric constant anisotropy. 60% by mass of the composition (M10), 5% by mass of N,N-diethylacrylamide, 10% by mass urethane acrylate oligomer UN6202 15% by mass of polymerizable compound (M-2-2-1), 5% by mass of 4-hydroxybutyl acrylate, and 5 mass% of the compound (M-5-E-4) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. In addition, the temperature during driving was set to 110°C or -40°C, a voltage of 60 V was applied to the element, and it was confirmed that it became transparent even when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.5 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 5%.

[Example 16] 60% by mass of the composition (M10), 5% by mass of N,N-diethylacrylamide, 10% by mass urethane acrylate oligomer UN6202 15% by mass of polymerizable compound (M-2-2-1), 5% by mass of 2-hydroxyethyl acrylate, and 5 mass% of the compound (M-5-E-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. In addition, the temperature during driving was set to 110°C or -30°C, a voltage of 60 V was applied to the element, and it was confirmed that it became transparent even when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.9 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 4%.

[Example 17] 60% by mass of the composition (M10), 5% by mass of N,N-diethylacrylamide, 10% by mass urethane acrylate oligomer UN6202 7 mass% polymerizable compound (M-2-2-1), 9% by mass of 2-hydroxyethyl acrylate, and 9% by mass of the compound (M-5-E-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. In addition, the temperature during driving was set to 110°C or -40°C, a voltage of 60 V was applied to the element, and it was confirmed that it became transparent even when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.2 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 4%.

[Example 18] 60% by mass of the composition (M11), 5% by mass of N,N-diethylacrylamide, 10% by mass urethane acrylate oligomer UN6207, 10% by mass of polymerizable compound (M-2-2-1), 5 mass% polymerizable compound (M-2-10-1), 2% by mass of 4-hydroxybutyl acrylate, and 8% by mass of the compound (M-5-E-1) is mixed, A polymerizable composition was prepared, and in the same manner as in Example 1, a photopolymerization initiator was added. The polymerizable composition is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. In addition, the temperature during driving was set to 110°C or -30°C, a voltage of 60 V was applied to the element, and it was confirmed that it became transparent even when irradiated with light. According to the result, it can be known that the element is in the normal mode. The peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 1.0 N/cm. The haze change rate after the weather resistance test was calculated by the same method as in Example 1. As a result, it was about 3%. [Comparative Example 1] 60% by mass of the composition (M4), 20% by mass urethane acrylate oligomer UN6202, and 20% by mass of polymerizable compound (M-2-7-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. On the other hand, the peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 0.1 N/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 polymerizable compound (M-2-7-1) is mixed, A polymerizable composition was prepared, a photopolymerization initiator was added in the same manner as in Example 1, and a polymerizable composition for a light control element was prepared. The polymerizable composition for a light control element is in an isotropic phase state at room temperature (25°C). Except for using the polymerizable composition for a light control element, an element having a liquid crystal composite was produced by the same method as in Example 1. The resulting element is opaque. A voltage of 60 V was applied to the element, and it became transparent when irradiated with light. According to the result, it can be known that the element is in the normal mode. On the other hand, the peeling force of the element was measured by the same method as in Example 1. As a result, the peeling force was 0.1 N/cm or less.

From the above results, it can be seen that the elements of Examples 1 to 18 have a normal mode, have good adhesion, and the haze change rate after the weather resistance test is also 10% or less with little change over time. Therefore, we concluded that a liquid crystal composite formed by combining a specific nematic composition and a specific polymer can be suitably used in a liquid crystal dimming element.

[Industrial availability] The liquid crystal light control element containing the liquid crystal composite obtained by polymerizing the polymerizable composition for light control elements of the present invention can be used for light control windows, smart windows, and the like.

1: Substrate with electrode layer 2: Liquid crystal compound 3: Transparent substance

FIG. 1 is a schematic diagram of a liquid crystal light control element showing a state in which light passes through the light control layer (the electrode layer is not shown). When a voltage is applied between the upper and lower substrates, the liquid crystal compound is aligned, and the difference in refractive index between the polymer, which is a transparent substance, and the liquid crystal composition decreases, and the scattering of incident light decreases. 2 is a schematic view of a liquid crystal dimming element (the electrode layer is not shown) in a state that when no voltage is applied between the upper and lower substrates, the liquid crystal compound is present in an unaligned manner, and when light is incident on When the light-adjusting layer is used, strong scattering of incident light occurs at the interface due to the difference in refractive index between the polymer, which is a transparent material, and the liquid crystal composition.

1: Substrate with electrode layer

2: Liquid crystal compound

3: Transparent substance

Claims (27)

A polymerizable composition for a light control element, comprising a liquid crystal composition, a polymer precursor, and a photopolymerization initiator, the liquid crystal composition comprising a liquid crystal compound represented by formula (1) as component A, and the polymerization The precursors of the compounds each contain at least one monofunctional polymerizable compound selected from the compounds represented by the formula (M-1), and at least one monomer selected from the compounds represented by the formula (M-2) having a cyclic structure. A functional polymerizable compound, and at least one selected from urethane (meth)acrylate oligomers having two or more (meth)acrylic groups as a multifunctional polymerizable compound;

In formula (1), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons or an alkenyl group having 2 to 12 carbons; 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-di Fluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl; Z ¹ is a single Bond, ethylene, ethylene, ethynylene, methyleneoxy, carbonyloxy or difluoromethyleneoxy; X ¹ and X ² are each independently hydrogen or fluorine; Y ¹ is fluorine, Chlorine, cyano, alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, alkoxy group having 1 to 12 in carbon numbers in which at least one hydrogen is replaced by fluorine or chlorine, or at least one hydrogen is replaced by fluorine or chlorine Alkenyloxy with 2 to 12 carbons; a is 1, 2, 3 or 4;

In the formula (M-1), M ¹⁰⁰ is hydrogen, fluorine, an alkyl group with 1 to 5 carbons or an alkyl group with 1 to 5 carbons in which at least one hydrogen is substituted by fluorine or chlorine; R ¹⁰⁰ and R ¹⁰¹ are each independently Is hydrogen or an alkyl group or a hydroxyalkyl group having 1 to 12 carbon atoms. Among these alkyl group or hydroxyalkyl group, at least one -CH ₂ -can be controlled by -O-, -N(R ¹⁰² )-, -CO-,- Substituted by COO- or -OCO-, R ¹⁰² is hydrogen and an alkyl group having 1 to 12 carbon atoms;

In the formula (M-2), M ¹⁰¹ is hydrogen, fluorine, an alkyl group with 1 to 5 carbons, or an alkyl group with 1 to 5 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ¹⁰⁰ is a single bond or carbon number An alkylene group of 1 to 10, in which at least one hydrogen may be substituted by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO-, -COO- or -OCO-; R ¹⁰³ is a carbocyclic saturated aliphatic compound, a heterocyclic saturated aliphatic compound, a carbocyclic unsaturated aliphatic compound, a heterocyclic unsaturated aliphatic compound, or a carbocyclic or heterocyclic A monovalent group with a carbon number of 5 to 35, which can be substituted by an alkyl group with a carbon number of 1 to 12, is generated by removing one hydrogen from the aromatic compound. At least one of the monovalent groups -CH ₂ -can be -O -, -CO-, -COO- or -OCO- substitution. The polymerizable composition for a light control element according to claim 1, wherein the liquid crystal compound represented by formula (1) is selected from the group consisting of compounds represented by formula (1-1) to formula (1-48) At least one compound in the constituent group;

In formulas (1-1) to (1-48), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons, X ¹ and X ² each independently is hydrogen or fluorine; Y ¹ is fluorine, chlorine, cyano, an alkyl group having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, and a carbon number of 1 to 12 in which at least one hydrogen is replaced by fluorine or chlorine. An alkoxy group of 12 or an alkenyloxy group having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. The polymerizable composition for a dimming element according to claim 1 or 2, wherein the ratio of component A is in the range of 5 mass% to 90 mass% based on the mass of the liquid crystal composition. The polymerizable composition for a dimming element according to claim 1 or 2, wherein the liquid crystal composition further contains a liquid crystal compound represented by formula (2) as component B;

In formula (2), R ³ is a group bonded to a carbon atom of ring C, R ² and R ³ are each independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and 2 to 12 alkenyl or carbon 2 to 12 alkenyl 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; Z ² is a single bond, Ethylene, ethylene, ethynylene, methyleneoxy or carbonyloxy; b is 1, 2, or 3. 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 formula (2-1) to formula (2-23) As ingredient B;

In formulas (2-1) to (2-23), R ² and R ³ are alkyl groups having 1 to 12 carbons, alkoxy groups having 1 to 12 carbons, alkenyl groups having 2 to 12 carbons, or at least An alkenyl group having 2 to 12 carbons in which hydrogen is replaced by fluorine or chlorine. The polymerizable composition for a light control element according to claim 4, wherein the ratio of the component B is in the range of 5 mass% to 90 mass% based on the mass of the liquid crystal composition. The polymerizable composition for a dimming element according to claim 1 or 2, wherein the liquid crystal composition contains a liquid crystal compound represented by formula (3) as component C;

In formula (3), R ⁴ and R ⁵ are each independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons. The alkenyloxy group; ring D and ring F are each independently 1,4-cyclohexenyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4- Phenyl, 1,4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chromane -2,6-diyl or chroman-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-Difluorochroman-2,6-diyl, 3,4,5,6-tetrafluoro-2,7-diyl, 4,6-difluorodibenzofuran-3,7- Diyl, 4,6-difluorodibenzothiophene-3,7-diyl or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ³ and Z ⁴ are each independently Single bond, ethylene, ethylene, methyleneoxy or carbonyloxy; c is 0, 1, 2 or 3, d is 0 or 1, and the sum of c and d is 3 or less. The polymerizable composition for a dimming element according to claim 7, wherein component C is at least one selected from the group consisting of liquid crystal compounds represented by formula (3-1) to formula (3-35) Compound

In formulas (3-1) to (3-35), R ⁴ and R ⁵ are each independently hydrogen, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and 2 to 12 carbons. Alkenyl or alkenyloxy having 2 to 12 carbons. The polymerizable composition for a light control element according to claim 7, wherein the ratio of the component C is in the range of 3% by mass to 25% by mass based on the mass of the liquid crystal composition. The polymerizable composition for a light control element according to claim 1, wherein in the compound represented by the formula (M-1), M ¹⁰⁰ is hydrogen or methyl; R ¹⁰⁰ and R ¹⁰¹ are each independently hydrogen, A linear alkyl group having 1 to 10 carbons or a branched alkyl group having 3 to 10 carbons or a linear hydroxyalkyl group having 1 to 10 carbons or a branched hydroxyalkyl group having 3 to 10 carbons; these alkyl groups or In the hydroxyalkyl group, at least one -CH ₂ -may be substituted with -O- or -N(R ¹⁰² )-, and R ¹⁰² is hydrogen or a linear alkyl group having 1 to 10 carbons; the formula (M-2) The compound represented is at least one compound selected from the group consisting of compounds represented by formula (M-2-1) to formula (M-2-10), the urethane (meth)acrylic acid The ester oligomer is at least one selected from the group consisting of polyester-based urethane (meth)acrylate oligomers and polyether-based urethane (meth)acrylate oligomers, And its weight average molecular weight is in the range of 2,000 to 30,000;

In the formula, M ¹⁰¹ is hydrogen or methyl; n ¹⁰⁰ is 0, 1 or 2, and m ¹⁰⁰ is an integer of 2-6. The polymerizable composition for a dimming element according to claim 1 or claim 2, further containing a phosphoric acid selected from the group consisting of compounds represented by formula (M-3) and formula (M-4) At least one polymerizable compound in the site serves as the precursor of the polymer;

In formula (M-3) to formula (M-4), M ¹⁰² is hydrogen or methyl; n ¹⁰¹ , n ¹⁰² and n ^{103 are} independently 1 to 4. The polymerizable composition for a dimming element according to claim 1 or claim 2, further containing a group selected from the group consisting of compounds represented by formula (M-5-E) and formula (M-5-P) At least one polymerizable compound in and at least one polymerizable compound selected from hydroxyalkyl (meth)acrylate as the precursor of the polymer;

In formula (M-5-E) and formula (M-5-P), M ⁵⁰¹ is hydrogen or methyl, R ⁵⁰² is an alkyl group having 1 to 6 carbons, and n is 1 to 30; The hydrogen in the ethylene glycol structure of -E) and the propylene glycol structure of formula (M-5-P) can be substituted by an alkyl group having 1 to 3 carbons; the alkyl group in the hydroxyalkyl (meth)acrylate is A straight-chain or branched alkylene group with a carbon number of 2 to 10 or a branched chain with a carbon number of 3 to 10). The polymerizable composition for a dimming element according to claim 1 or claim 2, further containing at least one selected from the group consisting of compounds represented by formula (7), formula (8) and formula (9) A polymerizable compound as the precursor of the polymer;

In formula (7), formula (8) and formula (9), ring G, ring I, ring J, ring K, ring L and ring M are each independently 1,4-cyclohexyl, 1,4-cyclohexyl Phenyl, 1,4-cyclohexenylene, pyridine-2,5-diyl, 1,3-dioxane-2,5-diyl, naphthalene-2,6-diyl or pyri-2, 7-diyl group, where at least one hydrogen contained in these groups can be fluorine, chlorine, cyano, hydroxyl, methanoyl, trifluoroacetyl, difluoromethyl, trifluoromethyl, carbon number Substitution with 1 to 5 alkyl group, carbon number 1 to 5 alkoxy group, carbon number 2 to 5 alkoxycarbonyl group or carbon number 1 to 5 alkanoyl group; Z ⁸ , Z ¹⁰ , Z ¹² , Z ¹³ And Z ¹⁷ are each independently a single bond, -O-, -COO-, -OCO- or -OCOO-; Z ⁹ , Z ¹¹ , Z ¹⁴ and Z ¹⁶ are each independently a single bond, -OCH ₂ -,- CH ₂ O-, -COO-, -OCO-, -COS-, -SCO-, -OCOO-, -CONH-, -NHCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH _2- , -CF ₂ CF ₂ -, -CH=CHCOO-, -OCOCH=CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH ₂ -, -CH=CH-, -N=CH-, -CH= N-, -N=C(CH ₃ )-, -C(CH ₃ )=N-, -N=N- or -C≡C-; Z ¹⁵ is a single bond, -O- or -COO-; Y ² is hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, linear alkyl with 1 to 20 carbons, linear alkenyl with 2 to 20 carbons, and 1 to 20 carbons Linear alkoxy or linear alkoxycarbonyl having 2 to 20 carbons; f and h are each independently an integer from 1 to 4; k and m are each independently an integer from 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 from 0 to 20; M ⁷ to M ¹² are each independently hydrogen or methyl. The polymerizable composition for a light control element according to claim 1 or 2, wherein the ratio of the liquid crystal composition is in the range of 30% by mass to 95% by mass based on the total mass of the liquid crystal composition and the polymer precursor , The ratio of the polymer precursor is in the range of 5 mass% to 70 mass%. The polymerizable composition for a dimming element according to claim 1 or 2, wherein based on the total mass of the liquid crystal composition and the polymer precursor, The ratio of the compound (M-1) is in the range of 3% by mass to 25% by mass, The ratio of the compound (M-2) is in the range of 3% by mass 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 polymer precursor does not exceed 70% by mass, Based on the total mass of the liquid crystal composition and the polymer precursor, the ratio of the photopolymerization initiator is in the range of 0.1% by mass to 5% by mass. The polymerizable composition for a light control element according to claim 11, wherein based on the total mass of the liquid crystal composition and the polymer precursor, The ratio of the compound (M-3) and the compound (M-4) is in the range of 0.001% by mass to 0.5% by mass. The polymerizable composition for a light control element according to claim 12, wherein based on the total mass of the liquid crystal composition and the polymer precursor, The total ratio of the compound (M-5-E) and/or the compound (M-5-P) and the hydroxyalkyl (meth)acrylate is in the range of 2% by mass to 30% by mass. A liquid crystal dimming element, wherein the dimming layer is sandwiched by a pair of transparent substrates, the transparent substrate has transparent electrodes, and the dimming layer is used for the dimming element according to any one of claim 1 to claim 17. A liquid crystal composite obtained by polymerizing a polymerizable composition. The liquid crystal dimming element according to claim 18, wherein the transparent substrate includes a glass plate, a plastic plate or a plastic film. The liquid crystal dimming element according to claim 18 or claim 19, wherein ^{the fog before and after a weather resistance test conducted under the conditions of an illuminance of 180 W/m 2} , an irradiation time of 100 hours, and a tank temperature of 35°C The degree change rate is less than 20%. A dimming window using the liquid crystal dimming element described in any one of Claim 18 to Claim 20. A smart window using the liquid crystal dimming element described in any one of claim 18 to 20. A liquid crystal composite obtained by polymerizing the polymerizable composition for a dimming element according to any one of claims 1 to 17. A use of a liquid crystal composite, which is the liquid crystal composite according to claim 23, which is used in a liquid crystal dimming element. A use of a liquid crystal composite, which is the liquid crystal composite according to claim 23, which is used in a liquid crystal dimming element whose transparent substrate includes a plastic plate or a plastic film. A use of a liquid crystal composite, which is the liquid crystal composite according to claim 23, which is used in a dimming window. A use of a liquid crystal composite, which is the liquid crystal composite according to claim 23, which is used in smart windows.

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