TW201412703A - Novel compound, polymerizable liquid crystal compound, monomer/liquid crystal mixed material and polymer/liquid crystal composite - Google Patents

Abstract

The present invention provides a monomer/liquid crystal mixed material suitable for the industrial production through making a temperature range exhibiting blue phase before photo-polymerization broader without using a specific liquid crystal molecule having low molecular weight. Also, the present invention provides a polymer/liquid crystal composite from which a liquid crystal display element with excellent contrast property can be obtained. The present invention is characterized in a novel compound having bend-type molecular structure, which is represented by the general formula (1).

Description

Novel compounds, polymerizable liquid crystal compounds, monomer/liquid crystal hybrid materials, and high Molecular/liquid crystal composite

The present invention relates to a novel compound, and a liquid crystal display material using the novel compound, and more particularly to a liquid crystal display material having a polymer-stabilized blue phase.

A liquid crystal display device including a flat panel liquid crystal display has the characteristics of light weight and low power consumption, and therefore has been rapidly popularized in recent years. Further, the size and high image quality of the liquid crystal display device are also an object pursued by the industry. However, the conventional liquid crystal display device has a slow response to the electric field, the animation display quality is poor, and there is a problem of high-speed animation followability. Further, since the alignment film is imparted with an alignment property, it is necessary to perform an alignment treatment. Therefore, there is a problem of low productivity due to the alignment process.

On the other hand, the liquid crystal display device of the blue phase mode is regarded as the liquid crystal display device of the next generation. The liquid crystal display device of the blue phase mode uses a liquid crystal display device called a blue phase liquid crystal phase.

The so-called blue phase (hereinafter referred to as "BP") refers to the biliary One of the liquid crystal phases found in the narrow temperature range in which the sterol phase and the isotropic phase differ by a few ° C (generally 1 to 3 ° C). Blue has better high-speed responsiveness than conventional liquid crystal phases, and has high productivity because it does not require alignment treatment.

However, due to the narrow temperature range of the blue phase, precise temperature management must be performed. In this way, there will be problems that are difficult to use.

In order to solve the above problems, the industry actively tried to broaden the study of the blue phase temperature range. For example, the blue phase temperature range (temperature range) is greatly broadened by forming a network polymer composed of a monomer having a specific structure in a low molecular liquid crystal having a blue phase (see, for example, Patent Document 1).

Specifically, in a low molecular liquid crystal in which a blue phase can be found, a mixture of a polymerizable liquid crystal compound, a non-liquid crystalline monomer, a chiral molecule, and a photopolymerization initiator is light at a blue phase temperature. polymerization.

However, although the method described in Patent Document 1 can broaden the blue phase temperature after photopolymerization, it cannot broaden the temperature range before photopolymerization. Therefore, when mass production of a liquid crystal display of a large-size screen is carried out by the method of Patent Document 1, it is necessary to control the temperature before photopolymerization in a narrow temperature range of about 1 ° C or so and uniformly treat a wide area. Such a narrow temperature range will hinder mass production.

On the other hand, the industry has also tried to broaden the blue phase temperature before photopolymerization. For example, the industry has proposed a method of broadening the temperature of the blue phase by designing special liquid crystal molecules called λ type, U type, and curved type (see, for example, Non-Patent Document 1).

However, the manufacture of special liquid crystal molecules is complicated, and there is a problem of high cost in mass production.

[Practical Technical Literature] [Patent Document]

Patent Document 1: Japanese Patent No. 3779937

Non-Patent Document 1: A. Yoshizawa, M. Sato, J. Rokunohe, "A blue phase observed for a novel chiral compound possessing molecular biaxiality" J. Matter. Chem., 15, pp. 3285~3290 (2005).

Therefore, the present invention proposes a solution to the above problems, and an object thereof is to provide a monomer/liquid crystal hybrid material which can broaden the temperature range of the blue phase before photopolymerization without using a special low molecular liquid crystal. Further, another object of the present invention is to provide a polymer/liquid crystal composite material which can produce a liquid crystal display device of comparative use.

The inventors of the present invention conducted research and investigation based on the above-mentioned problems, and as a result, have found that a compound having a novel curved molecular structure can broaden the temperature range before photopolymerization of a blue phase by adding a liquid crystal composition, and thus the present invention has been proposed. In addition, it was also found that the obtained polymer-stabilized blue phase has high light transmittance and high contrast. That is, the present invention is as follows.

The compound of the present invention is a compound represented by the following chemical formula (1).

(In the formula, A ₁ and A ₂ are independent of each other, are a polymerizable group, S ₁ and S ₂ are a methylene group, and m and n are independent of each other, and are an integer of Tables 1 to 20, and B is a single bond or an oxygen atom. D is a 1,4-phenylene group having a carboxyl group at the position of the first or fourth substituent (wherein one or more hydrogen atoms may be substituted with F, Cl, Br, an alkyl group having 1 to 8 carbon atoms) , a linear fluoroalkyl group having a carbon number of 1 to 3, a linear fluoroalkoxy group having a carbon number of 1 to 3, a cyano group, a Q-based 1,2-phenylene or 1,3-phenylene (In addition, one or more hydrogen atoms may be replaced by F, Cl, Br, an alkyl group having 1 to 8 carbon atoms, a linear fluoroalkyl group having 1 to 3 carbon atoms, and a carbon number of 1 to 3; Linear fluoroalkoxy, cyano)).

Further, the monomer/liquid crystal hybrid material of the present invention includes a compound represented by the chemical formula (1).

Further, the monomer/liquid crystal hybrid material of the present invention preferably comprises a compound represented by the above formula (1) and a polymerizable liquid crystal compound other than the compound represented by the formula (1).

The monomer/liquid crystal hybrid material preferably further includes a low molecular liquid crystal compound, a non-liquid crystal monomer, a chiral molecule, and a photopolymerization initiator.

The polymer/liquid crystal composite material of the present invention is a photopolymer of the above monomer/liquid crystal hybrid material.

A liquid crystal display device according to the present invention is characterized in that: at least one side is a transparent pair of substrates, an electrode formed on at least one side of the pair of substrates, and a liquid crystal layer sandwiched between the pair of substrates; a polarizing plate on one side of a pair of substrates, and an electric field applied to the liquid crystal layer by the electrodes A liquid crystal display device of a field application device, comprising: the liquid crystal layer comprising the polymer/liquid crystal composite material.

The novel compounds of the present invention are compounds having novel curved molecular structures. This compound is used by being added to a liquid crystal material, and the blue phase temperature range before polymerization of the liquid crystal material can be broadened. As a result, even a liquid crystal display device of a blue phase mode of a large-sized screen was obtained to obtain a polymer/liquid crystal composite material which can be mass-produced.

Further, the polymer/liquid crystal composite material obtained by polymerizing the novel compound of the present invention together with a usual polymerizable liquid crystal compound has a broad blue phase temperature range, high responsiveness, and excellent contrast. As a result, a high quality liquid crystal display device is obtained. In addition, alignment processing is not required.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic view of an optical system for measuring the intensity of light transmission to an applied electric field in the examples and comparative examples.

Fig. 2 is a graph showing the relationship between the applied electric field and the light transmission intensity when the polymer/liquid crystal composite materials of Examples 6 and 9 and Comparative Example 1 of the present invention were used.

(chemical compound represented by the general formula (1))

The compound represented by the chemical formula (1) is a compound in which 1,2-phenylene or 1,3-phenylene is used at Q, and has a 1, 2 or 1st, 3 substituent position of the phenylene group. At the same time, the structure combined with other molecules. Therefore, it has a crimped molecular structure (curved molecular structure). The curved molecular structure is considered to have Broaden the function of the blue phase temperature range. Further, the compound of the formula (1) has a polymerizable group at both ends as long as it can be polymerized with another polymerizable compound. The compound of the formula (1) may be a liquid crystalline compound or a non-liquid crystalline compound.

The compound of the present invention is specifically a compound represented by the following chemical formula (1).

(In the formula, A ₁ and A ₂ are independent of each other, are a polymerizable group, S ₁ and S ₂ are a methylene group, and m and n are independent of each other, and are an integer of Tables 1 to 20, and B is a single bond or an oxygen atom. D is a 1,4-phenylene group having a carboxyl group at the position of the first or fourth substituent (wherein one or more hydrogen atoms may be substituted with an anion of F, Cl, Br, and a carbon number of 1-8) a base, a linear fluoroalkyl group having a carbon number of 1 to 3, a linear fluoroalkoxy group having a carbon number of 1 to 3, or a group consisting of a cyano group, and a Q system 1,2- Benzene or 1,3-phenylene (in which one or more hydrogen atoms may be replaced by a linear chain of F, Cl, Br, an alkyl group having 1 to 8 carbon atoms, and a carbon number of 1 to 3) A fluoroalkyl group, a linear fluoroalkoxy group having 1 to 3 carbon atoms, or a group consisting of a cyano group).

In the above formula, the alkyl group having a carbon number of 1 to 8 may specifically be, for example, a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group or a 2-methylpropyl group. , 2-butyl, 1,1-dimethylethyl, 1-pentyl, 3-methylbutyl, 2,2-dimethicone 1,1,1-dimethylpropyl, 1-hexyl, 4-methylpentyl, 1-heptyl, 1-methylhexyl, 1,1-dimethylpentyl, 2,2-dimethylpentyl, 2 -methylhexyl, 2-ethylpentyl, 2-ethyl-2-methylbutyl, 4,4-dimethylpentyl, 1-octyl, 1-methylheptyl, 1,1-dimethylhexyl, 2 2-2-Ethyl, 2-methylheptyl, 2-ethylhexyl, 2-ethyl-2-methylheptyl, 5,5-dimethylhexyl, and the like.

In the above formula (1), the linear fluoroalkyl group having 1 to 3 carbon atoms may be, for example, one or more hydrogens of a methyl group, an ethyl group and a 1-propyl group, which are replaced by fluorine. Functional group.

In the above formula, the linear fluoroalkoxy group having a carbon number of 1 to 3 may be, for example, a functional group obtained by replacing one or more hydrogens of a methoxy group, an ethoxy group, and a propyl group with fluorine. base.

In the formula (1), the polymerizable group represented by A ₁ and A ₂ may be, for example, CH ₂ =CX-COO-, CH ₂ =CXCOS-, CH ₂ =CX-, CH ₂ =CH-O-, HS-(CH ₂ ) _I -COO-, or a functional group represented by the following chemical formula, or a combination thereof.

In the above chemical formula, X is a hydrogen atom, a chlorine atom, fluorine, a trifluoromethyl group, an alkyl group or the like. I Tables 1 to 10, preferably 1 to 7. The alkyl group is, for example, an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and specifically, for example, a methyl group. Ethyl, 1-propyl and the like.

In the above chemical formula, m and n are independent of each other, preferably from 1 to 12, more preferably from 1 to 6, more preferably from 1 to 4.

In the above chemical formula, at least one hydrogen atom in Q is preferably replaced by From F, Cl, Br, an alkyl group having 1 to 8 carbon atoms, a linear fluoroalkyl group having 1 to 3 carbon atoms, a linear fluoroalkoxy group having 1 to 3 carbon atoms, and a cyano group Any of the constituent ethnic groups. Further, in particular, when Q is 1,3-phenylene, at least one or more hydrogen atoms are preferably substituted with a linear chain of Cl, Br, an alkyl group having 1 to 8 carbon atoms, and a carbon number of 1 to 3. Any one of a group consisting of a fluoroalkyl group, a linear fluoroalkoxy group having 1 to 3 carbon atoms, and a cyano group. Further, Q is more preferably substituted by Cl, Br, or an alkyl group having 1 to 3 carbon atoms.

In another embodiment of the present invention, the chemical formula (1) is The compound is preferably a compound represented by the following chemical formula (1a).

In the formula, A ₃ and A ₄ are independent of each other and may, for example, be CH ₂ =CX-COO-, CH ₂ =CXCOS-, CH ₂ =CX-, CH ₂ =CH-O-, HS-(CH ₂ ) _I -COO-, or a functional group represented by the following chemical formula, or a combination thereof.

In the above chemical formula, X is a hydrogen atom, a chlorine atom, a fluorine atom, a trifluoromethyl group or an alkyl group. I Tables 1 to 10, preferably 1 to 7. p and q are independent of each other and are integers from 1 to 4, and Q ₁ is a 1,2-phenylene or 1,3-phenylene having at least one substituent Y on the aromatic ring, and Y is Cl, Br, and carbon number. It is any one of a group consisting of an alkyl group having 1 to 8 carbon atoms, a linear fluoroalkyl group having 1 to 3 carbon atoms, a linear fluoroalkoxy group having 1 to 3 carbon atoms, and a cyano group.

The alkyl group represented by the formula (1a), the alkyl group having 1 to 8 carbon atoms, the linear fluoroalkyl group having 1 to 3 carbon atoms, and the linear fluoroalkoxy group having 1 to 3 carbon atoms. It is the same as that described in the formula (1).

Specific examples of the compound of the formula (1) can be, for example, the following 1,3-bis-[4-(3-propenyloxypropyloxy)benzylideneoxy]-5-methylbenzene ( 2) 1,2-di-[4-(3-propenyloxypropoxyoxy)benzylideneoxy]-4-methylbenzene (3) and the like. The following compounds are novel compounds.

(Method for producing a compound represented by the chemical formula (1))

The compound represented by the chemical formula (1) can be produced, for example, in the following manner. First, after the intermediate 1 is synthesized and then the intermediate 2 is formed, the intermediate 2 is reacted to obtain a compound represented by the chemical formula (1).

[Synthesis of Intermediate 1]

First, a 4-hydroxybenzoic acid ester such as methyl 4-hydroxybenzoate is reacted with a halogen alcohol such as chloropropanol to synthesize the intermediate 1.

[7]

In the chemical formula, R and D are bonded to a carboxyl group to form an ester. Further, Hr is a halogen such as chlorine, bromine or iodine.

[Synthesis of Intermediate 2]

Intermediate 2 is synthesized by reacting Intermediate 1 with an unsaturated carboxylic acid ester such as methyl acrylate or the like. The polymerizable group introduced at both ends of the compound of the formula (1) of the present invention can be changed by selecting a compound which reacts with the intermediate 1.

In the chemical formula, R is bonded to the carboxyl group of A _{1 to} form an ester, for example, a transesterification reaction is carried out between the hydroxyl group of the intermediate 1 and the hydroxyl group of the intermediate 1.

(chemical compound represented by the general formula (1))

The above intermediate 2 is reacted with 1,2-phenylene or 1,3-phenylene which may have a substituent to obtain a compound represented by the formula (1). In this case, when the intermediate 2 is used in combination with a compound having a different polymerizable group, an asymmetric polymerizable group can be introduced into 1,2-phenylene or 1,3-phenylene.

(monomer/liquid crystal mixed material)

The monomer/liquid crystal hybrid material of the present invention comprises a compound represented by the above formula (1) as a monomer, and has no polymerizable group, and exhibits a nematic phase and a chirality. A mixed material of a nematic or blue phase liquid crystal composition. The monomer/liquid crystal hybrid material of the present invention preferably further comprises a polymerizable liquid crystal compound other than the compound represented by the above formula (1). The compound represented by the above formula (1) exhibits an effect of broadening the blue phase temperature range in the state of the monomer/liquid crystal mixed material before polymerization. In addition, when a compound represented by the formula (1) is used in combination with a polymerizable liquid crystal compound other than the compound represented by the formula (1), not only the blue phase temperature range before polymerization but also the post-polymerization can be obtained. The blue phase has a better polymer stabilization effect.

Polymerizable liquid crystal compound other than the compound represented by the formula (1) The material is not particularly limited, and a conventional polymerizable liquid crystal compound can be used. In the present specification, the term "polymerizable liquid crystalline compound" means a liquid crystalline compound having a polymerizable functional group. Further, the polymerizable liquid crystal compound is preferably a photopolymerizable type. The polymerizable liquid crystalline compound may, for example, be a compound represented by the following chemical formula.

The amount of the compound represented by the formula (1) is relative to the formula (1) The polymerizable liquid crystal compound other than the compound shown is preferably 2 to 8% by mass, and more preferably 4 to 6% by mass. When the amount of the compound represented by the formula (1) is less than 2% by mass, the blue phase temperature range may not be broadened. When the amount of the compound represented by the formula (1) is more than 8% by mass, the effect of stabilizing the polymer is lowered.

The monomer/liquid crystal hybrid material of the present invention further includes low molecular liquid crystallinity A compound, a non-liquid crystalline monomer, a chiral molecule, a photopolymerization initiator, and the like.

(liquid crystal composition)

The liquid crystal composition constituting the monomer/liquid crystal hybrid material and the polymer/liquid crystal composite material of the present invention is a combination of a low molecular liquid crystal compound and a chiral molecule, and has no polymerizable functional group in its structure. In the present invention, the composition of the low molecular liquid crystalline compound and the chiral molecule is broadly referred to as a chiral nematic liquid crystal, and the liquid crystal phase represented by the liquid crystal composition is a chiral nematic phase.

The liquid crystal composition of the present invention exhibits at least chirality at room temperature The nematic phase, or the blue phase (BP), preferably the composition system, exhibits a liquid crystal composition of BP. Here, room temperature means 10 to 45 °C.

In the present invention, the liquid crystal composition is hand-in-hand for the purpose of displaying BP The spiral pitch in the liquid crystal is preferably 500 nm or less. The discovery of BP was confirmed by a small-plate observation of the characteristics by a polarizing microscope or by measuring the peak of the corresponding wavelength of occurrence by a reflection spectrum.

a low molecular liquid crystalline compound constituting a liquid crystal composition, for example The nematic liquid crystal compound, the smectic liquid crystal compound, the dish liquid crystal compound, and the like are preferably a nematic liquid crystal compound. One type of the low molecular liquid crystal compound can be used. However, in order to optimize various characteristics, it is preferred to use two or more kinds of low molecular liquid crystal compounds. When two or more kinds of low molecular liquid crystalline compounds are used, it is preferred to exhibit a nematic liquid crystal phase after mixing. The mixing ratio of the two or more kinds of low molecular liquid crystal compounds is appropriately selected depending on the type of the low molecular liquid crystalline compound to be used.

Specific examples of the low molecular liquid crystalline compound may be, for example, a biphenyl system. A liquid crystal compound, a terphenyl liquid crystal compound, a diphenylacetylene liquid crystal compound, or the like.

The chiral molecule may be a liquid crystalline compound or may be non-liquid crystalline. Compound. The asymmetric structure having a chiral molecule may be any asymmetric structure of asymmetric carbon atoms, axis asymmetry, or surface asymmetry, and is preferably a compound having axial asymmetry from the viewpoint of helical induction. Among them, preferred are, for example, isosorbide inducers, binaphthol inducers, and atropisomers.

The amount of chiral molecules can be based on low molecular liquid crystal compounds The combination with the chiral molecule is suitably determined in accordance with the desired helical pitch, and is preferably 20% by mass or less, more preferably 1% to 10% by mass based on the liquid crystal material. When the amount of the chiral molecule is more than 20% by mass, when it is used as a polymer/liquid crystal composite material, it may cause adverse effects on the material properties due to precipitation, phase separation, etc., and therefore it is preferable not to exceed it. On the other hand, the lower limit of the amount of the chiral molecule added is preferably an amount at which the desired helical pitch can be obtained.

In the monomer/liquid crystal hybrid material of the present invention, it will be described later. In the polymer/liquid crystal composite material of the invention, in order to improve the durability, contrast, and the like, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and hexyl acrylate may be appropriately added. A non-liquid crystalline monomer having an asymmetric structure composed of an acrylate such as dodecyl acrylate or octadecyl acrylate or a non-liquid crystalline monofunctional monomer such as an alkyl acrylate. The amount of the non-liquid crystal monomer to be added is not particularly limited as long as it exhibits the above-described function, and it is preferable to add 5% by mass or less, more preferably 2 to 5% by mass, to the composite material.

(polymer/liquid crystal composite material)

The polymer/liquid crystal composite material of the present invention can be obtained by performing polymerization of the above monomer/liquid crystal hybrid material. It is, for example, a liquid crystal composition having no polymerizable group In the optically isotropic state to be described later, a polymerizable liquid crystal compound other than the compound represented by the formula (1) and the compound represented by the formula (1) is dispersed and polymerized by heat or light. . The polymer/liquid crystal composite material thus obtained forms a copolymer as a network polymer in the liquid crystal composition, and the network polymer can improve the arrangement order structure when the liquid crystal compound is polymerized in the liquid crystal composition, that is, The thermodynamic stability of the blue phase is increased to achieve a wide range of temperatures that can be utilized to broaden the arrangement.

a compound represented by the above formula (1) and the above formula (1) The more the monomer distribution ratio of the polymerizable liquid crystal compound other than the compound shown, the higher the durability as a polymer/liquid crystal composite material, but in order to simultaneously increase the driving voltage, the range of durability is not lost. It is preferable to use a low monomer distribution ratio, which is set to be 1 to 40% by mass relative to the total amount of the polymer/liquid crystal composite material produced, and when the polymer/liquid crystal composite material is used as a display device, it is feasible. The total amount of the polymerizable liquid crystal compound other than the compound represented by the above formula (1) and the compound represented by the above formula (1) is further set to 5 to 15% by mass of the polymer/liquid crystal composite material. proportion. Therefore, the distribution ratio of the liquid crystal composition is preferably set to 99 to 60% by mass, and more preferably 95 to 85% by mass based on the total amount of the obtained polymer/liquid crystal composite material. Further, in the present invention, the content of the liquid crystal composition refers to a distribution ratio of a low molecular liquid crystal when only a low molecular liquid crystal is used, and a low molecular liquid crystal and a chiral molecule when a low molecular liquid crystal and a chiral molecule are used together. Total amount.

When polymerizing, the compound represented by the above formula (1), and Other photopolymerization initiators and thermal polymerization initiators can be used for the reactivity of the polymerizable liquid crystal compound other than the compound represented by the formula (1). Photopolymerization initiator The thermal polymerization initiator is not particularly limited, and a conventional compound can be used.

The photopolymerization initiator may be, for example, an acetophenone, a benzophenone or a benzophenone. Insular, biphenyl quinone, Michler's ketone, benzoin alkyl ether, biphenyl fluorenone or thioxanthone. Further, the thermal polymerization initiator may be, for example, a peroxide, an azo compound or the like.

The addition amount of the polymerization initiator can be determined according to the above formula (1) The reactivity of the compound and the polymerizable liquid crystal compound other than the compound represented by the formula (1) is appropriately selected. If the addition is excessive, an undesired side reaction may occur, so the amount of addition is preferably relative to The total amount of the polymerizable liquid crystal compound other than the compound represented by the above formula (1) and the compound represented by the formula (1) and the polymerization initiator is 5% by mass or less.

The polymerization temperature can be set to the compound represented by the above formula (1), The mixture of the polymerizable liquid crystal compounds other than the compound represented by the formula (1) has an optical isotropic temperature which is displayed at the start of the polymerization, and is preferably set to exhibit a temperature of BP. This temperature can be appropriately selected depending on the type and combination of the mixtures.

The polymer/liquid crystal composite material of the invention can be obtained by optical etc. The sexual state, that is, the polymerization under BP or in an isotropic state, may also be referred to as a polymer stabilized blue phase. Here, the optical isotropic state means that the arrangement order structure in the polymer/liquid crystal composite material is below the optical order, and does not have a macroscopic anisotropy. In the liquid crystalline compound, the state in which the optical isotropic property is thus displayed may be, for example, BP or the like.

a compound represented by the above formula (1) and a compound represented by the formula (1) a mixture of a polymerizable liquid crystal compound other than the compound and a liquid crystal composition The object exhibits an optical isotropic property at a polymerization temperature, and may, for example, exhibit a BP method as described above, perform a small plate-like observation by a polarizing microscope, or measure a peak of a corresponding wavelength thereof by a reflection spectrum, or the like. The method was confirmed; however, when the isocratic phase was displayed, it was confirmed by observing the anisotropy by a polarizing microscope.

The mixture confirmed by the above method is in an optical isotropic state At a temperature, the compound represented by the formula (1) and the polymerizable liquid crystal compound other than the compound represented by the formula (1) in the mixture are polymerized by light or heat to produce a composite of the present invention. material.

In the present invention, the composite material of the present invention broadens the temperature during polymerization Degree range. For example, when a polymerizable liquid crystalline compound other than the compound represented by the general formula (1) is used, the general composite material exhibits a BP temperature range of about 3.5 °C. This temperature range can be broadened by about 1 to 2 ° C by using the compound of the formula (1) of the present invention. As a result, even if it is a large-sized screen, it is possible to obtain a homogeneous BP phase without rigorous temperature control, and to mass-produce a polymer/liquid crystal composite material. Further, since a special polymerizable liquid crystal compound is not used, the manufacturing cost can be reduced.

The polymer/liquid crystal composite material of the invention can be applied according to photoelectric Optical components such as optical modulation components and optical switches. The optimum utilization type of these optical modulation elements is a suitable type for various uses, and is not particularly limited.

For example, the basic components of the optical modulation component and the optical switch can be For example, an element formed by sandwiching the composite material of the present invention with an electrode substrate or an element formed by sandwiching a substrate having a comb-shaped electrode and a substrate having no electrode And the like, preferably a liquid crystal display device of the present invention.

The liquid crystal display device of the present invention comprises: at least one side is transparent a pair of substrates, an electrode formed on at least one of the pair of substrates, a liquid crystal layer sandwiched between the pair of substrates, a polarizing plate formed on one of the outer sides of the pair of substrates, and a liquid crystal layer by the electrode An electric field applying device for applying an electric field to the layer, the liquid crystal layer comprising the composite material of the present invention. At this time, in order to align the liquid crystal molecules on the substrate in the horizontal or vertical direction, an alignment film composed of polyamine or the like can be used.

When the polymer/liquid crystal composite material of the invention is applied to liquid crystal display In the case of an optical element such as a device, the light transmittance is higher as compared with the case of using only a general polymerizable liquid crystalline compound, and a preferable contrast is also exhibited. Further, it can exhibit the same response speed as in the case where the compound represented by the formula (1) is not used and only the polymerizable liquid crystal compound of the present invention is used. Therefore, the polymer/liquid crystal composite material of the present invention can be effectively applied to an optical element such as a liquid crystal display device.

[Examples]

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples.

(Example 1) Synthesis of 1,3-bis-[4-(3-propenyloxypropyloxy)benzylideneoxy]-5-methylbenzene (KM3AA006)

(Synthesis of Intermediate 1)

Prepare 150 g of methyl 4-hydroxybenzoate (1 mol), 158 g of potassium carbonate, 7.6 g of triethylammonium chloride, and two ethylene in a reaction vessel prepared with a stirring device, a countercurrent condenser, a dropping funnel, and a thermometer. Glycol dimethyl ether 600g at room temperature After stirring, it was heated to 120 °C.

For the heated solution, it took 1 hour to drip 3-chloro with a dropping funnel. Propyl alcohol (104 g, 1.1 mol) was subjected to a reaction for 6 hours. After the temperature of the solution after the reaction was lowered to 100 ° C, 400 g of a 20% aqueous sodium hydroxide solution was added thereto, followed by stirring for 3 hours. After the reaction solution was cooled to room temperature, it was adjusted to pH 3 with a 10% aqueous hydrochloric acid solution, and 440 g of tetrahydrofuran and 270 g of water were added thereto, followed by stirring for 1 hour. After stirring, the aqueous phase was separated and the organic phase was concentrated under reduced pressure at 55 °C. The white slurry obtained after concentration was filtered, washed with toluene and then hexane, and dried under reduced pressure to obtain 128 g of Intermediate 1.

(Synthesis of Intermediate 2)

In a reaction vessel prepared with a stirring device, a countercurrent condensing tube, a distillation column, a fractionating tube, and a thermometer, 98 g (500 m mol) of intermediate 1, 1290 g of methyl acrylate, 75 g of hexane, and 14 g of 70% methanesulfonic acid were prepared. 1.2 g of butylhydroxytoluene was stirred at 70 to 80 ° C after stirring. From the top of the distillation column, the methanol formed by the reaction is separated by a fractionation tube, and the reaction proceeds until no methanol is formed. After the reaction solution was cooled to room temperature, it was transferred to a separatory funnel and washed with 200 mL of water until the pH of the liquid phase reached 3. The organic phase was concentrated under normal pressure at 65 to 75 ° C after adding 100 g of toluene to prepare a slurry. This slurry was filtered, washed with toluene and then hexane, and dried under reduced pressure to obtain 94 g of Intermediate 2.

[12]

Synthesis of 1,3-bis-[4-(3-propenyloxypropyloxy)benzylideneoxy]-5-methylbenzene (KM3AA006)

Prepare 50g (20m mol) of intermediate 2, dimethylaminopyridine 2g, 1-ethyl-3-(3-dimethylaminopropyl) in a reaction vessel prepared with a stirring device, a counterflow condenser, and a thermometer. After 51 g of carbon diamine hydrochloride and 225 g of dichloromethane were stirred and cooled in ice water, 10 g of 5-toluene resorcinol was slowly added in small amounts. Thereafter, the reaction was carried out for 6 hours at room temperature. The reaction solution was washed twice with 130 g of a 10% aqueous hydrochloric acid solution. Then, the organic phase was concentrated under reduced pressure, and the obtained residue was recrystallized from acetone/methanol mixed solvent to obtain 82 g of the final product KM3AA006.

Physical property value

¹ H-NMR (measuring solvent: heavy dimethyl hydrazine): 2.09~2.13 (m, 4H), 2.36 (s, 3H), 4.13 (d, 4H), 4.28 (d, 4H), 5.93 (d, 2H), 6.18 (dd, 2H), 6.33 (d, 2H), 7.03 (s, 3H), 7.11 (d, 4H), 8.05 (d, 4H)

(Example 2) Synthesis of 1,2-bis-[4-(3-propenyloxypropyloxy)benzylideneoxy]-4-methylbenzene (KM3AA007)

The same operation was carried out except that 5-toluene resorcinol of Example 1 was replaced with 4-methylphenylphosphonate to obtain 84.8 g of the final product KM3AA007.

Physical property value

¹ H-NMR (measuring solvent: heavy dimethyl sulfoxide): 2.02~2.09 (m, 4H), 2.36 (s, 3H), 4.09~4.12 (m, 4H), 4.22~4.25 (m, 4H), 5.91 (d, 2H), 6.17 (dd, 2H), 6.32 (d, 2H), 6.96 to 6.99 (m, 4H), 7.18 (dd, 1H), 7.25 (d, 1H), 7.31 (d, 1H) , 7.86~7.90 (m, 4H)

(Example 3)

The fluorine-based mixed liquid crystal JC-1041XX (manufactured by JNC Co., Ltd.) which is a liquid crystal composition is 46.25 mass%, 4-cyano-4'-pentylbiphenyl (5CB) 46.25 mass%, and 2,5 of a chiral molecule. - bis-[4'-(hexyloxy)-phenyl-4-carbon oxime]-1,4:3,6-dianhydride-D-sorbitol (ISO-(6OBA) ₂ ) 7.5 mass%, The entire system was uniformly mixed at an isocratic temperature to prepare a liquid crystal composition.

Next, 92% by mass of the liquid crystal composition, lauryl acrylate 3.84% by mass of the ester, 3.84% by mass of KM3AA006 obtained in Example 1, and 0.32% by mass of 2,2'-dimethoxyphenylacetophenone (DMPAP) as a photopolymerization initiator were uniformly mixed to prepare Photopolymerizable monomer/liquid crystal hybrid material.

(Example 4)

The same operation was carried out except that the KM3AA006 3.84 mass% of Example 3 was changed to a mixture of RM-257 1.92 mass% and KM3AA006 1.92 mass%.

(Example 5)

The same operation was carried out except that the KM3AA006 3.84% by mass of Example 3 was changed to a mixture of RM-257 2.69 mass% and KM3AA006 1.15 mass%.

(Example 6)

The same operation was carried out except that the KM3AA006 3.84% by mass of Example 3 was changed to a mixture of RM-257 3.46 mass% and KM3AA006 0.38 mass%.

(Example 7)

The same operation was carried out except that 3.84% by mass of the dodecyl acrylate of Example 3 was changed to 2.30% by mass, and the mass of KM3AA006 3.84 was changed to 5.38% by mass.

(Comparative Example 1)

The same operation as in Example 3 was carried out except that 3.84 mass% of KM3AA006 of Example 3 was changed to RM-257 of 3.84 mass%.

(Example 8)

In addition to changing the KM3AA006 3.84% by mass of Example 3, The same operation as in Example 3 was carried out except that KM3AA007 was 3.84% by mass.

(Example 9)

The same operation as in Example 3 was carried out except that the KM3AA006 of Example 3 was 3.84 mass%, and the mixture was changed to a mixture of RM-257 3.46 mass% and KM3AA007 0.38 mass%.

<Evaluation of temperature range of blue phase liquid crystal before photopolymerization>

The photopolymerizable monomer/liquid crystal hybrid material obtained in Examples 3 to 9 and Comparative Example 1 was filled in an evaluation liquid crystal cell composed of one of the glass substrates (substrate pitch: 10 μm) which was not subjected to the alignment treatment, and was used. The polarizing microscope placed perpendicular to the analyzer and the analyzer was used to confirm the temperature range of the blue phase at a heating rate of 0.5 ° C / minute.

The results are shown in Table 1.

As can be seen from Table 1, when the monomer/liquid crystal hybrid material of the present invention is used, the temperature range in which the blue phase is found is broadened.

<Preparation of photopolymerized macromolecular stabilized blue phase liquid crystal and evaluation of photoelectric characteristics>

The photopolymerizable monomer/liquid crystal hybrid material obtained in Examples 3 to 9 and Comparative Example 1 was filled in a evaluation liquid crystal cell (substrate pitch) composed of a comb-shaped electrode substrate which was not subjected to alignment treatment and a glass substrate. 10 μm) was irradiated with ultraviolet rays (ultraviolet intensity 1.5 mWcm ^-2 , 365 nm) for 20 minutes while maintaining the temperature at which the blue phase was observed.

The obtained polymer-stabilized blue phase liquid crystal sample (polymer/liquid crystal composite material) was placed in the optical system shown in Fig. 1 . A rectangular wave alternating electric field (frequency of 1 kHz) was applied to the sample to measure the intensity of light transmission to the applied electric field. The results are shown in Table 2 and Figure 2.

Figure 2 is a high score using Examples 6 and 9 of the present invention and Comparative Example 1. In the case of a sub/liquid crystal composite, the relationship between the applied electric field and the light transmission intensity is shown. In the figure, the horizontal axis represents the applied voltage (V), the vertical axis represents the light transmittance (%), ● represents Example 6, Δ represents Example 9, and ■ represents Comparative Example 1.

It can be seen from Table 2 and Figure 2 that the polymer/liquid crystal composite of the present invention The material has a higher light transmission intensity against an applied voltage than the polymer/liquid crystal composite material of the comparative example. Therefore, when using the polymer/liquid crystal composite material of the present invention In time, optical components with high light transmission intensity and high contrast can be provided.

Claims (6)

A compound represented by the following chemical formula (1): In the formula, A ₁ and A ₂ are independent of each other, and are a polymerizable group. S ₁ and S ₂ are a meenyl group, and m and n are independent of each other, and are an integer of Tables 1 to 20, and B is a single bond or an oxygen atom. D is a 1,4-phenylene group having a carboxyl group at the position of the first or fourth substituent (wherein one or more hydrogen atoms may be substituted with F, Cl, Br, an alkyl group having 1 to 8 carbon atoms, a linear fluoroalkyl group having 1 to 3 carbon atoms, a linear fluoroalkoxy group having 1 to 3 carbon atoms, a cyano group, a Q-based 1,2-phenylene or 1,3-phenylene ( Among them, one or more hydrogen atoms may be replaced by F, Cl, Br, an alkyl group having 1 to 8 carbon atoms, a linear fluoroalkyl group having 1 to 3 carbon atoms, and a straight carbon number of 1 to 3. Chain fluoroalkoxy, cyano). A monomer/liquid crystal hybrid material comprising a compound represented by the following chemical formula (1): In the formula, A ₁ and A ₂ are independent of each other, and are a polymerizable group. S ₁ and S ₂ are a meenyl group, and m and n are independent of each other, and are an integer of Tables 1 to 20, and B is a single bond or an oxygen atom. D is a 1,4-phenylene group having a carboxyl group at the position of the first or fourth substituent (wherein one or more hydrogen atoms may be substituted with F, Cl, Br, an alkyl group having 1 to 8 carbon atoms, a linear fluoroalkyl group having 1 to 3 carbon atoms, a linear fluoroalkoxy group having 1 to 3 carbon atoms, a cyano group, a Q-based 1,2-phenylene or 1,3-phenylene ( Among them, one or more hydrogen atoms may be replaced by F, Cl, Br, an alkyl group having 1 to 8 carbon atoms, a linear fluoroalkyl group having 1 to 3 carbon atoms, and a straight carbon number of 1 to 3. Chain fluoroalkoxy, cyano). The monomer/liquid crystal hybrid material as described in claim 2 includes a polymerizable liquid crystal compound other than the compound represented by the following chemical formula (1). The monomer/liquid crystal hybrid material as described in claim 2 or 3, further comprising a low molecular liquid crystalline compound, a non-liquid crystalline monomer, a chiral molecule, and a photopolymerization initiator. A polymer/liquid crystal composite material, such as a photopolymer of a monomer/liquid crystal hybrid material as described in claim 2 of the patent application. A liquid crystal display device comprising: at least one side of a transparent pair of substrates; an electrode formed on at least one of the pair of substrates; a liquid crystal layer sandwiched between the pair of substrates; and one of the pair of substrates A liquid crystal display device of the polarizing plate on the outer side and an electric field applying device for applying an electric field to the liquid crystal layer by the electrode, wherein the liquid crystal layer comprises the polymer/liquid crystal composite material according to claim 5 of the patent application.