KR20120060160A - liquid crystal display device - Google Patents

Abstract

The present invention prevents various problems due to the formation of the alignment film by performing the alignment control of the liquid crystal molecules without forming the alignment film, and reduces the weight by using an inexpensive flexible substrate generally known in the art. A liquid crystal display device capable of thinning and cost down, comprising: a liquid crystal display device having a pair of substrates on which no alignment film is formed and a liquid crystal layer sandwiched between the pair of substrates, wherein at least one of the pair of substrates One is a flexible substrate, and the liquid crystal layer is characterized by including a liquid crystal component and a dendrimer and / or a dendron compatible with the liquid crystal component.

Description

Liquid crystal display device

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid crystal display device, and more particularly, to a liquid crystal display device used for a display panel of a watch, a display of a cellular phone, a display of a computer or a television, and the like.

Since liquid crystal displays have characteristics such as low driving voltage, low power consumption, and light weight, they are used for display panels of watches, displays of mobile phones, computers, and televisions.

Currently, the liquid crystal display adopts a driving method such as twisted nematic (TN) mode, vertical alignment (VA) mode, in-plane switching (IPS) mode, etc. (For example, temperature range, viscosity, etc. of a liquid crystal phase) differ. Therefore, in order to satisfy desired characteristics, a mixed liquid crystal containing not only a single liquid crystal component but also two or more liquid crystal components is used as the liquid crystal material.

In the liquid crystal display device of the above drive method, a means for controlling the alignment of liquid crystal molecules is required, and a means for forming an alignment film is used. For example, in the liquid crystal display device of TN or IPS mode, the orientation film which performed the rubbing process is carrying out orientation control of the liquid crystal molecule with respect to a board | substrate in parallel. On the other hand, in the VA mode liquid crystal display device in which rubbing processing is unnecessary, the alignment film controls the liquid crystal molecules in the direction perpendicular to the substrate.

4 is a cross-sectional view of such a conventional liquid crystal display device. As shown in FIG. 4, a conventional liquid crystal display device has a pair of substrates (first substrate 1 and second substrate 2), a liquid crystal layer 3, a spacer 4, and a sealing material ( 5) and the alignment film 8, the alignment control of the liquid crystal molecules in the liquid crystal layer 3 is performed by the alignment film 8 formed between the pair of substrates and the liquid crystal layer 3.

Generally, an oriented film is a film which controls the arrangement | positioning state of a liquid crystal molecule, and is formed with the composition based on polyimide. When the liquid crystal molecules are oriented in the vertical direction with respect to the substrate, hydrophobic structures such as alkyl groups and fluorine-containing groups are introduced into the alignment film (see Non-Patent Document 1, for example).

However, if the introduction amount of the hydrophobic structure is increased, the vertical alignment ability of the alignment film is improved, while the printability of the alignment film is lowered, resulting in printing unevenness (mura) of the alignment film, and it becomes difficult to form a uniform alignment film. There is. That is, when orientation control is performed by the alignment film, it is important to consider the balance between the printability of the alignment film and the alignment ability of the alignment film.

In addition, recently, a liquid crystal display device using a flexible substrate has attracted attention because of its thinner, lighter and more robust than a conventional liquid crystal display device using a glass substrate. As a liquid crystal display device using a flexible substrate, however, a TN mode (for example, see Non-Patent Document 2), a cholesteric liquid crystal, or the like is known. However, it is still in the beginning stage and has not been put into practical use.

[Non-Patent Document 1] Display Materials Division LCD Materials Division, "Vertical Alignment Film for LCD", JSR Technical Review, JSR Corporation, March 2007, No. 114

[Non-Patent Document 2] Hirai Tsuyoshi and two others, "Development of High Reliability Alignment Agent for Low Temperature Plasticity Active Matrix LCD," JSR Technical Review, JSR Corporation, March 2008, March 2008, No. 115.

In the case of performing alignment control of liquid crystal molecules by the alignment film, there are generally various problems due to the formation of the alignment film. For example, when forming an alignment film, there exists a problem of the yield of printed products of manufacture reduced by dust and a pinhole, or the investment cost required for the formation process of an alignment film increases with the enlargement of a board | substrate.

Moreover, compared with the conventional glass substrate, the flexible substrate has bad printability of an orientation film, and it is difficult to obtain orientation stability. Furthermore, in the case of manufacturing a liquid crystal display device, a high temperature baking process of 150 ° C. or more, for example, when forming an alignment film, hardens a high temperature baking process (eg, 20 minutes or more at 150 to 200 ° C.) or a thermosetting seal material. The use of generally known inexpensive flexible substrates with low heat resistance is limited because high temperature firing processes (eg, at least 3 hours at 160 ° C. to 250 ° C.) are required.

Among these, in the case of hardening the seal material, the high temperature firing process can be avoided by employing a UV hardenable seal material and adopting ODF (Liquid Drop Injection), but still avoiding the high temperature firing process when forming the alignment film. Can't.

Therefore, it is necessary to select and use a flexible substrate having excellent heat resistance and excellent temperature shrinkage, and it is not possible to use a cheap flexible substrate generally known in the art, which leads to an increase in the manufacturing cost of the liquid crystal display device. There is.

SUMMARY OF THE INVENTION The present invention solves the above problems and prevents various problems caused by the formation of the alignment film by performing the alignment control of the liquid crystal molecules without forming the alignment film, and is generally known in the art. It is an object of the present invention to provide a liquid crystal display device that can be reduced in weight, thickness, and cost by using a flexible substrate.

The present inventors have studied to solve the above problems, and as a result, by mixing a dendrimer and / or dendron compatible with the liquid crystal component as a liquid crystal component, there is no need to form an alignment film, and also in the technical field It has been found that orientation control can be easily performed even using a generally known inexpensive flexible substrate, and the present invention has been completed.

That is, the present invention is a liquid crystal display device having a pair of substrates on which no alignment film is formed and a liquid crystal layer sandwiched between the pair of substrates, at least one of the pair of substrates being a flexible substrate, The liquid crystal layer is a liquid crystal display device comprising a liquid crystal component and a dendrimer and / or dendron compatible with the liquid crystal component.

According to the present invention, by controlling the alignment of the liquid crystal molecules without forming the alignment film, various problems caused by the formation of the alignment film are prevented, and by using an inexpensive flexible substrate generally known in the art, A liquid crystal display device that can be thinned and cost down can be provided.

1 is a cross-sectional view showing a liquid crystal display device according to the present invention.
2 is a cross-sectional view of a liquid crystal display according to another exemplary embodiment of the present invention.
3 is a cross-sectional view of a liquid crystal display device manufactured according to an embodiment.
4 is a cross-sectional view showing a liquid crystal display device according to the prior art.

The liquid crystal display device of the present invention has a pair of substrates on which no alignment film is formed, and a liquid crystal layer sandwiched between the pair of substrates.

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of the liquid crystal display device which concerns on this invention is described using drawing.

As shown in FIG. 1, the liquid crystal display according to the present invention includes a pair of substrates (the first substrate 1 and the second substrate 2), the liquid crystal layer 3, the spacer 4, The sealing material 5 is provided. One side of the pair of substrates is used as the display side substrate and the other side as the liquid crystal drive side substrate.

At least one of the 1st board | substrate 1 and the 2nd board | substrate 2 is a flexible substrate. Here, in this specification, a "flexible substrate" means the board | substrate which has flexibility and can be greatly deformed. As a flexible board | substrate, the cheap thing known in the said technical field can be used. It is preferable that the glass transition temperature of a flexible substrate is 200 degrees C or less from a practical point of view.

As an example of a flexible substrate, the board | substrate, metal, etc. which consist of a resin substrate, resin, glass fiber, etc. are mentioned. Examples of the resin include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polypropylene, polyphenylene sulfide, polyimide, polyvinyl chloride and synthetic resins such as chloride, polyethersulphone, polyamide imide, polyamide, and aromatic polyamide.

By using such a flexible substrate, the liquid crystal display device can be significantly reduced in weight, thickness, and cost down compared with the case of using a conventional glass substrate.

Specifically, one side of the first substrate 1 and the second substrate 2 may be a glass substrate, and the first substrate 1 and the second substrate 2 on the other side may be a flexible substrate. In addition, you may make both the 1st board | substrate 1 and the 2nd board | substrate 2 a flexible substrate. If both the first substrate 1 and the second substrate 2 are flexible substrates, it is possible to provide flexibility to the liquid crystal display device in addition to weight reduction, thinning, and cost down of the liquid crystal display device.

Although not shown, in the liquid crystal display device of the present invention, electrodes such as planar electrodes, common electrodes, and pixel electrodes can be formed on the first substrate 1 and the second substrate 2, as necessary. Therefore, a color filter and the overcoat for protecting a color filter can be formed. As the electrode, the color filter and the overcoat, those known in the art can be used.

In addition, as shown in FIG. 2, in the liquid crystal display device of the present invention, the surface of the first substrate 1 and the second substrate 2 is opposite to the surface in contact with the liquid crystal layer 3 in the same manner as the conventional liquid crystal display device. The polarizing plate 6 is provided in the surface. However, in the liquid crystal display of the present invention, the polarizing plates may be used as the first substrate 1 and the second substrate 2 without the polarizing plates 6 being individually provided.

By setting it as such a structure, since a polarizing plate has not only the original function but a function as a board | substrate, it becomes unnecessary to use the glass substrate itself. As a result, it is possible to further reduce the weight, thickness and cost of the conventional liquid crystal display device.

Here, a "polarizing plate" means the element which converts natural light and various polarization into arbitrary polarization about this specification. As a polarizing plate, a well-known thing can be used in the said technical field. For example, what is comprised by the protective film for protecting a polarizer and a polarizer may be used as a polarizing plate.

As a polarizer, uniaxial stretching by adsorbing dichroic substances, such as iodine and a dichroic dye, to hydrophilic polymer films, such as a polyvinyl alcohol-type film, a partially formalized polyvinyl alcohol-type film, and an ethylene-vinyl acetate copolymerization system partially-generated film And polyene-based oriented films such as dehydration treatment of polyvinyl alcohol and dehydrochlorination treatment of polyvinyl chloride.

Moreover, as a protective film, polycarbonate resin, polyvinyl alcohol resin, cellulose resin, polyester resin, polyarylate resin, polyimide resin, cyclic polyolefin resin, poly And sulfonic resins, polyether sulfone resins, polyolefin resins, polystyrene resins, polyvinyl alcohol resins, and optically isotropic films formed from such mixtures.

The liquid crystal layer 3 is composed of a liquid crystal composition including a liquid crystal component and a dendrimer and / or a dendron compatible with the liquid crystal component. Here, in this specification, a "dendrimer" is a twig polymer which has a structure which branched regularly from the center, and means what is comprised from the central part called a core and the side chain part called a dendron.

In addition, in this specification, although a "dendron" is a branched polymer which has a structure which branched regularly from the center similarly to a dendrima, it means that it spreads in one direction from the center (pocal point).

By containing the dendrimer and / or the dendron in the liquid crystal layer 3, the dendrimer and / or the dendron are present at the interface of the first substrate 1 and the second substrate 2 in the liquid crystal layer 3 to have the same effect as the alignment film. The liquid crystal molecules in the liquid crystal layer 3 can be aligned perpendicularly to the substrate. Therefore, in the liquid crystal display device of the present invention, it is not necessary to form an alignment film for orientation control of liquid crystal molecules.

The dendrimer and / or the dendron are not particularly limited as long as they are compatible with the liquid crystal component. If it is a dendrimer and / or a dendron which is incompatible with a liquid crystal component, it will precipitate without melt | dissolving in a liquid crystal composition, and characteristics, such as contrast of a liquid crystal display device, will fall.

Here, when "dendrimer and / or a dendron compatible with a liquid crystal component" is mix | blended with a dendrimer and / or a dendron to a liquid crystal component, this is made to equilibrate by raising the phase transition of the liquid crystal component to the temperature more than the temperature in an oven, and making it is isotropic. Even when the dendrimer and / or dendron is dissolved (i.e., the mixture of the liquid crystal component and the dendrimer and / or dendron is transparent) and returned to room temperature (e.g., 25 DEG C), precipitation of the dendrimer and / or dendron is confirmed. It means not.

As the dendrimer compatible with the liquid crystal component, one having at least one selected from the group consisting of an alkyl group, an alkoxy group and fluorine at the terminal is preferable. The reason is that the dendrimer having such a structure is excellent in compatibility with not only a single component Cyano type liquid crystal but also a mixed liquid crystal containing two or more types of liquid crystal components.

In particular, fluorine-based mixed liquid crystals generally used in liquid crystal display devices are designed to be difficult to dissolve impurities from the viewpoint of securing the reliability of the liquid crystal display device, so that additives are difficult to dissolve, and dendrimers having such groups at their ends are fluorine-based mixed liquid crystals. Good compatibility is shown also about a liquid crystal.

The dendrimer which has at least 1 terminal selected from the group which consists of an alkyl group, an alkoxy group, and fluorine can be represented by following General formula (1), for example.

In Formula 1, R ¹ is represented by Formula 2.

In Formula 2, A ¹ has the following Formula 3.

(Y in formulas 1 to 3 is an alkyl group or alkoxy group having 1 to 12 carbon atoms, or fluorine), X is a direct bond, a -COO- group or a -N = N- group, A ² is a formula (4).

And n is an integer of 3-12.

The dendrimer having such a structure can be obtained by reacting a polyfunctional amine compound giving a core portion and an acrylic acid ester derivative given a side chain portion in an organic solvent.

Examples of the polyfunctional amine compound include polypropylene tetramine dendrimer (Generation 1.0), polypropylene octopamine dendrimer (Generation 2.0), and DAB- manufactured by Aldrich. Commercial items, such as Am-4 and DAB-Am-8, can also be used.

Moreover, this polyfunctional amine compound can also synthesize | combine ethylenediamine and acrylonitrile as a raw material.

What is necessary is just to select suitably according to the dendrimer synthesize | combined as an acrylic ester derivative, For example, when synthesize | combining the dendrimer represented by said Formula (1), the compound represented by following formula (5) can be used as a raw material.

In Formula 5, X, A ¹ , A ² and n are the same as defined above.

The reaction ratio of the polyfunctional amine compound and the acrylic acid ester derivative is 1.0 to 3.0 mol, preferably 1.1 to 1.5 mol of the acrylic acid ester derivative with respect to 1 mol of the polyfunctional amine compound.

As an organic solvent, a conventionally well-known thing can be used. For example, Halogenated hydrocarbon solvents, such as 1, 2-dichloroethane and chloroform; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Cyclic ether ether solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon solvents such as toluene and xylene; N-Methyl-2-pyrrolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, etc. Aprotic polar solvents may be mentioned. Such an organic solvent can be used individually or in mixture of 2 or more types.

In addition, what is necessary is just to adjust the quantity of an organic solvent suitably according to the quantity of a polyfunctional amine compound, an acrylic acid ester derivative, etc.

As reaction temperature, it is -50-150 degreeC, Preferably it is 25-80 degreeC. If reaction temperature is less than -50 degreeC, reaction speed will fall remarkably. Moreover, when reaction temperature exceeds 150 degreeC, stability of a polyfunctional amine compound and an acrylic acid ester derivative will fall.

As reaction time, it is 2 to 200 hours, Preferably it is 48 to 100 hours. If the reaction time is less than 2 hours, the reaction does not proceed sufficiently. If the reaction time exceeds 200 hours, it takes too long to be practical.

After completion of the reaction, the target dendrimer can be obtained by removing the solvent. Moreover, you may refine | purify by adding and heating a poor solvent, such as methanol, ethanol, isopropyl alcohol, hexane, and toluene, and removing a surface layer liquid.

As the dendron compatible with the liquid crystal component, it is preferable to have at least one selected from the group consisting of an alkyl group, an alkoxy group and fluorine at a non focal point terminal. Moreover, it is preferable that a dendron has an amino group at a polcal point. It is because the dendron which has such a structure is excellent in compatibility with not only a single component cyano type liquid crystal but a mixed liquid crystal containing 2 or more types of liquid crystal components.

In particular, fluorine-based mixed liquid crystals generally used in liquid crystal display devices are difficult to dissolve because impurities are designed to be difficult to dissolve from the viewpoint of securing the reliability of the liquid crystal display device. Good compatibility is also shown for.

Moreover, it is preferable that the dendron used for this invention has a mesogenic group. The reason for this is that the dendron hardly inhibits the characteristics of the liquid crystal component and is excellent in liquid crystal alignment control. Here, a mesogenic group means the organic group which has a rigid structure required in order to express liquid crystallinity.

As such a mesogenic group, for example, sodium benzoate phenyl, biphenyl, biyan, cyanobiphenyl, terphenyl, cyanotaphenyl, phenylbenzoate, Azobenzene, diazobenzene, anilinebenzylidene, azomethine, azomethine, azoxybenzene, stilbene, phenylcyclohexyl, biphenylcyclohexyl ), Phenoxyphenyl, benzalaniline, benzylbenzoate, benzylbenzoate, phenylpyrimidine, phenyldioxane, benzoaniani, benzoylaniline, tran, and derivatives thereof. Can be.

Although the generation of the dendron used for this invention is not specifically limited, Generally, the 1st-6th generation is used. Here, in the present invention, one number of branches is referred to as first generation.

Preferred dendrons for use in the present invention have the following formula (6).

In Formula 6, R is hydrogen, an alicyclic group, an aromatic group, or a HO- (CH ₂ ) _m -group (wherein m is an integer of 2 to 6). Here, although it does not specifically limit as alicyclic group, For example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclophthalyl group, a cyclooctyl group, adamantyl (adamantyl) Group, norbornyl group, isobornyl group, campanyl group, campanyl group, dicyclopentyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclodecanyl group, andro And stanyl groups.

Moreover, as an aromatic group, a phenyl group, a naphthyl group, a biphenyl group, a triphenyl group, a binaphthyl group, anthracenyl group, a fluorenyl group, etc. are mentioned, for example.

In addition, in formula (6), A ¹ has the following formula (7).

(Wherein Y in formula (7) is an alkyl group or alkoxy group having 1 to 12 carbon atoms or fluorine), and A ² has the following formula (8).

X is a direct bond, a -COO- group, or -N = N- group, n is an integer of 3-12.

The dendron used for this invention can be synthesize | combined using the well-known method described in the various literature. Generally, what is necessary is just to react the compound which has the amino group which gives a focal point, and the compound which couple | bonds with this compound and gives the branch part of a dendron. For example, what is necessary is just to make the compound which has the acrylic acid ester derivative which gives the branch part of a dendron, the terminal amino group which reacts with this acrylic acid ester derivative, and the amino group which gives a focal point react in an organic solvent.

As a compound which has an amino group which gives a focal point, what is necessary is just to select suitably according to the dendron to synthesize | combine. In addition, when adjusting the generation (order of branching) of a dendron, after making the compound which has the amino group which gives a focal point into a branched structure by making it react with acrylonitrile etc., it uses nitrile using a reducing agent, such as lithium aluminum hydride, and the like. May be converted into an amine.

For example, when synthesize | combining the dendron which has said formula (6), the compound which has the following general formula can be used.

RN-((CH ₂ ) ₃ -NH ₂ ) ₂

Wherein R is as defined above.

The compound described above can be synthesized by reacting R-NH ₂ with acrylonitrile (CH ₂ = CHCN), and then converting the nitrile to an amine using a reducing agent such as lithium aluminum hydride.

As an acrylic ester derivative which gives the branch part of a dendron, what is necessary is just to select suitably according to the dendron synthesize | combined. For example, when synthesize | combining the dendron which has said formula (6), the acrylic acid ester derivative which has the following formula (9) can be used as a raw material.

In Formula 9, A ¹ , A ² , X, and n are the same as defined above.

The reaction ratio of a compound having an amino group imparting a focal point (for example, a compound of the general formula) and an acrylic acid ester derivative (for example, a compound of Formula 9) needs to be appropriately adjusted according to the type of raw material to be used. In general, however, 1 to 10 moles of an acrylic ester derivative may be used per 1 mole of the compound having an amino group imparting a focal point.

As an organic solvent used for the said reaction, a well-known thing can be used in the said technical field. Examples of the organic solvent include halogenated hydrocarbon solvents such as 1,2-dichloroethane and chloroform; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Cyclic ether ether solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon solvents such as toluene and xylene; N-Methyl-2-pyrrolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, etc. Aprotic polar solvents may be mentioned. Such an organic solvent can be used individually or in mixture of 2 or more types.

In addition, what is necessary is just to adjust suitably the quantity of the organic solvent according to the kind, quantity, etc. of the raw material to be used, and are not specifically limited.

As reaction temperature, it is -50-150 degreeC, Preferably it is 25-80 degreeC. If reaction temperature is less than -50 degreeC, reaction speed will fall remarkably. Moreover, when reaction temperature exceeds 150 degreeC, stability of a polyfunctional amine compound and an acrylic acid ester derivative will fall.

As reaction time, it is 2 to 200 hours, Preferably it is 48 to 100 hours. If the reaction time is less than 2 hours, the reaction does not proceed sufficiently. If the reaction time exceeds 200 hours, it takes too long to be practical.

After completion of the reaction, the target dendrimer can be obtained by removing the solvent. Moreover, you may refine | purify by adding and heating a poor solvent, such as methanol, ethanol, isopropyl alcohol, hexane, and toluene, and removing a surface layer liquid.

The content of the dendrimer and / or dendron in the liquid crystal composition (liquid crystal layer 3) is such that the dendrima and / or dendron are present at the interface between the first substrate 1 and the second substrate 2 and the liquid crystal layer 3. It is not limited as long as it is made. Actually, the compounding amount of the dendrimer and / or the dendron in the liquid crystal composition (liquid crystal layer 3) depends on the area of the first substrate 1 and the second substrate 2 sandwiching the liquid crystal layer 3, and therefore, it can be defined. Although it is not number, it is generally 0.01-50 mass%.

When the content of the dendrimer and / or the dendron is less than 0.01% by mass, the long-term reliability of the orientation control of the liquid crystal molecules decreases because the dendrimer and / or the dendron present at the interface is too small. On the other hand, when the compounding quantity of a dendrimer and / or a dendron exceeds 50 mass%, the quantity of a liquid crystal component will become small, and desired performance as a liquid crystal display device, such as delay of a response time and an increase of a drive voltage, cannot be obtained.

Although it does not specifically limit as a liquid crystal component, It is preferable that it is a mixed liquid crystal containing 2 or more types of liquid crystal components. Although this mixed liquid crystal is prepared by mixing several liquid crystal components so as to satisfy desired physical properties (for example, refractive anisotropy, dielectric anisotropy, viscosity, phase potential temperature, etc.) according to the intended use, it is difficult to define arbitrarily. And mixed liquid crystal mixed with a fluorine mixed liquid crystal, cyano based liquid crystal, and the like.

Among these, it is preferable to use the fluorine-type mixed liquid crystal generally used for a liquid crystal display device. Here, "fluorine-based mixed liquid crystal" means a mixed liquid crystal containing at least one fluorine-based liquid crystal, and "cyano-based mixed liquid crystal" means a mixed liquid crystal containing at least one cyano-based liquid crystal. The mixed liquid crystal is generally known and commercially available.

As a method of mix | blending a dendrimer and / or a dendron to a liquid crystal component, it can carry out using a well-known method. For example, after adding a dendrimer or a dendron to a liquid crystal component, you may mix using a well-known mixing means.

The spacer 4 is formed to maintain a gap between the first substrate 1 and the second substrate 2. In addition, the sealing material 5 is formed in order to sandwich the liquid crystal layer 3 between the first substrate 1 and the second substrate 2. As the spacer 4 and the seal member 5, those known in the art can be used.

As a driving method of the liquid crystal display device of this invention, various modes can be set. Among them, the VA mode which is superior to the TN mode in terms of viewing angle, response speed and contrast is used.

The liquid crystal display device of the present invention having the above configuration can be carried out in accordance with a conventional method for manufacturing a liquid crystal display device. For example, the liquid crystal display device of the present invention can be manufactured by the following method.

First, a spacer 4 is formed on the first substrate 1. Here, as the formation method of the spacer 4, well-known methods, such as the port lithography method, can be used. Next, after cleaning and drying the 1st board | substrate 1 in which the spacer 4 was formed, the seal | sticker material 5 is apply | coated, the 2nd board | substrate 2 is matched, hardened by UV irradiation, etc., and adhere | attached.

Here, an injection hole for injecting the liquid crystal composition is formed in a part of the seal member 5. Next, after inject | pouring a liquid crystal composition between the 1st board | substrate 1 and the 2nd board | substrate 2 by a vacuum injection method, an injection hole is sealed.

On the other hand, in the above description, the liquid crystal composition is injected into the vacuum injection method using the capillary phenomenon, but an ODF (liquid drop injection method) may be used.

Since the liquid crystal display device of the present invention thus obtained can be produced without performing the alignment film forming process or the rubbing treatment, various problems caused by the alignment film forming process and the rubbing treatment (by dust or pinholes when forming the alignment film). It becomes possible to prevent the problem that the ratio of the manufactured product of a printing falls, or the cost required for the formation process of an oriented film increases with the enlargement of a board | substrate, etc.).

In addition, in the liquid crystal display of the present invention, since a high temperature firing process is not required at the time of manufacture, it is possible to use a generally known and inexpensive flexible substrate in the technical field, thereby reducing the weight, thickness and cost of the liquid crystal display. This becomes possible.

Hereinafter, although description of this invention was demonstrated by the Example, these are not specific to this invention.

Synthesis of Dendrimer A

In the above formula (1), a dendrimer represented by the following formula (10) in which R ¹ is synthesized as follows.

Synthesis of 6- [4- (4-hexylphenylziazyl) phenoxy] hexanol

In a 200 ml three-necked flask, 4- (4-hexylphenylziazenyl) phenol (5.0 g, 17.7 mmol), 6-bromohexanol (4.9 g, 18 mmol), potassium carbonate ( 2.45 g, 17.7 mmol) and ethanol (20 mL) were added to dissolve and heated to reflux for 48 hours. After the completion of heating reflux, the residue obtained by removing ethanol under reduced pressure was dissolved in diethyl ether, and the solution was washed three times with water.

Next, anhydrous sodium sulfate was added to this solution to remove water, and diethyl ether was distilled off under reduced pressure, and the obtained residue was recrystallized from n-hexane to yield 3.9 g of orange needle crystals (58% yield). ) In this acicular crystal, characteristic absorption of 3289 cm ^-1 (OH), 2919 cm ^-1 (CH), 1473 cm ^-1 (N = N), and 1253 cm ^-1 (PhO-) was observed by IR.

Synthesis of 6- [4- (4-hexylphenylziazyl) phenoxy] hexanol

In a 100 mL three-necked flask [4- (4-hexylphenylziazyl) phenoxy] hexanol (3.5 g, 9.2 mmol), triethylamine (0.92 g, 9.2 mmol), and THF (30 mL) ) Was added to dissolve and cooled to 0 ° C. with ice. Acryloyl chloride (1.2g, 14mmol) was added to this solution using the syringe, and it stirred at room temperature for 24 hours. The resulting white solid was partitioned, the liquid was concentrated under reduced pressure, and the obtained residue was purified by column chromatography (fixed phase: silica gel, mobile phase: chloroform) to yield a yellow solid in a yield of 3.4 g (85% yield).

This yellow solid has a characteristic absorption of 2935 cm ^-1 (CH), 1716 cm ^-1 (C = O), 1473 cm ^-1 (N = N) and 1261 cm ^-1 (PhO-) by IR. It became. The elemental analytical value of this yellow solid was consistent with the value calculated as C ₂₇ H ₃₆ N ₂ O ₃ within a range of 0.5% (calculated value -C: 74.28%, H: 8.31%, N: 6.42%, Found: C: 74.48%, H: 8.61%, N: 6.35%.

Synthesis of Dendrimer A

In a 100 ml Naus flask, DAB-Am-8 (0.39 g, 0.51 mmol), 6- [4- (4-hexylphenylziazyl) phenoxy] hexyl acrylate (4.9 g, 11 mmol) and THF (Aldrich) 20 ml) was added and heated at 50 ° C. for 72 hours. Next, the solution was concentrated under reduced pressure, and the residue was dissolved in a small amount of THF, added to 400 ml of hexane, and the surface layer solution was removed by decantation to recover a precipitate. By repeating this operation twice, it refine | purified and obtained the paste-like orange solid in yield 3.9g (98% yield).

In this orange solid, characteristic absorption of 2931 cm ^-1 (CH), 1735 cm ^-1 (C = O), 1457 cm ^-1 (N = N) and 1253 cm ^-1 (PhO-) was observed by IR. It became. In addition, the elemental analysis value of this orange solid was consistent with the value calculated as C ₄₇₂ H ₆₇₂ N ₄₆ O ₄₈ within a range of 0.5% (calculated value-C: 73.07%, H: 8.73%, N: 8.30%, found value). ~ C: 72.86%, H: 8.49%, N: 8.40%). Moreover, DSC measurement of this solid was carried out. The temperature rising process was observed at T13, 33 ° C, and 83 ° C at -13 ° C, and the exothermic peak at 81 ° C and 28 ° C at -13 ° C, and -29 ° C. Tg was observed at ° C.

Synthesis of Dendrimer B

In the general formula (1), a dendrimer represented by the following general formula (11) in which R ¹ was synthesized as follows.

Synthesis of 6- [4- (trans-4-pentyl cyclohexyl) phenoxy] hexanol

In a 200 ml Naus flask, 4- (trans-4-pentyl cyclohexyl) phenoxy phenol (10 g, 41 mmol), 6-bromohexanol (8.8 g, 49 mmol), potassium carbonate (11 g, 80 mmol) and 2-bro; Tannon (50 ml) was added and dissolved, and the mixture was heated to reflux for 60 hours. After the completion of heating reflux, the residue obtained by removing 2-butanone under reduced pressure was dissolved in ethyl acetate and the solution was washed three times with water.

Then, anhydrous sodium sulfate was added to this solution to remove water, and the residue obtained by removing ethyl acetate under reduced pressure was recrystallized with n-hexane to obtain white crystals having a yield of 6.2 g (yield 94%).

As for this white crystal, characteristic absorption of 3340 cm ^-1 (OH), 2922 cm ^-1 (CH), and 1245 cm ^-1 (PhO-) was observed by IR.

Synthesis of 6- [4- (trans-4-pentyl cyclohexyl) phenoxy] hexyl acrylate

6- [4- (trans-4-pentylcyclohexyl) phenoxy] hexanol (6.0 g, 17 mmol), triethylamine (2.2 g, 22 mmol) and THF (50 mL) were added to a 200 mL three neck flask. It melt | dissolved and cooled to 0 degreeC with ice.

Acrylonyl chloride (1.9 g, 21 mmol) was slowly added to this solution using a syringe, and it stirred at room temperature for 12 hours. The resulting white solid was separated, the liquid was concentrated under reduced pressure, and the obtained residue was dissolved in ethyl acetate and washed three times with 100 mL of water.

Next, anhydrous magnesium sulfate was added to the organic phase to remove water, and then concentrated under reduced pressure. The residue was then purified by column chromatography (fixed phase: silica gel, mobile phase: hexane / chloroform (volume ratio 50: 1)) to give a colorless transparent liquid in a yield of 6.4 g (yield). 93%). The absorption of 2920 cm ^-1 (CH), 1716 cm ^-1 (C = O), and 1245 cm ^-1 (PhO-) of this liquid was observed by IR.

Synthesis of Dendrimer B

In a 20 ml Naus flask, DAB-Am-8 (0.16 g, 0.21 mmol), 6- [4- (trans-4-pentyl cyclohexyl) phenoxy] hexyl acrylate (4.0 g, 10 mmol) and THF manufactured by Aldrich (5 ml) was added and it heated at 50 degreeC for 72 hours. Next, the solution was concentrated under reduced pressure, and the residue was dissolved in a small amount of chloroform, added to 100 mL of methanol, and the surface layer solution was removed by decantation to recover a precipitate. By repeating this operation twice, the product was purified to give a paste-like pale yellow solid in a yield of 0.45 g (30% yield).

As for this pale yellow solid, the characteristic absorption of 2921 cm ^-1 (CH), 1736 cm ^-1 (C = O), and 1247 cm ^-1 (PhO-) was observed by IR. In addition, the elemental analytical value of this pale yellow solid was consistent with the value calculated as C ₄₅₆ H ₇₃₆ N ₁₄ O ₄₈ within the range of 0.5% (calculated value-C: 76.25%, H: 10.33%, N: 2.73%, found value ~). C: 76.09%, H: 10.52%, N: 2.80%).

Moreover, the molecular weight of this pale yellow solid by MALDI-TOF-MS was measured, but actual value m / Z = 7181 with respect to theoretical value m / Z = 7183 (M + H). 2 (M + H). Furthermore, DSC measurements of this pale yellow solid were carried out, with an endothermic peak observed at Tg, 14 ° C. and 73 ° C. at −24 ° C. for the temperature rise process, and an exothermic peak at 69 ° C. and 15 ° C., −26 for the temperature decrease process. Tg was observed at ° C.

Synthesis of Dendrimer C

In the formula (1), a dendrimer represented by the following formula (12) in which R ¹ is synthesized as follows.

Synthesis of 3- [4- (trans-4-pentyl cyclohexyl) phenoxy] propanol

300 ml of Nas Flask 4- (trans-4-pentyl cyclohexyl) phenol (15 g, 61 mmol), 3-bromo-1-propanol (10 g, 73 mmol), potassium carbonate (17 g, 122 mmol) and 2-broken Tannon (80 mL) was added to dissolve and heated to reflux for 60 hours. After the completion of heating reflux, the residue obtained by removing 2-butanone under reduced pressure was dissolved in 300 mL of ethyl acetate, and the solution was washed three times with 100 mL of water.

Then, anhydrous sodium sulfate was added to this solution to remove water, and the residue obtained by removing ethyl acetate under reduced pressure was recrystallized with hexane to obtain white crystals with a yield of 12.2 g (66% yield). This white crystal is 7.2 to 7.0 ppm (d, 2H, ArH), 6.9 to 6.8 ppm (d, 2H, ArH), 4.1 ppm (t, 2H,) by 1 H-NMR (CDCl ₃ , 400 MHz). Δ of OCH ₂ ), 3.85 ppm (q, 2H, PhCH ₂ ), 2.4 ppm (m, 1H, ArCH), 1.9 to 1.2 ppm (m, 20H, CH ₂ ), 0.85 ppm (t, 3H, CH ₃ ) This was observed. In addition, by IR, characteristic absorption of 3340 cm ^-1 (OH), 2922 cm ^-1 (CH), and 1245 cm ^-1 (PhO-) was observed.

Synthesis of 3- [4- (trans-4-pentyl cyclohexyl) phenoxy] propyl acrylate

Into a 300 ml Naus flask, 3- [4- (trans-4-pentyl cyclohexyl) phenoxy] propanol (10 g, 33 mmol), triethylamine (3.4 g, 33 mmol) and THF (100 ml) were dissolved. It cooled to 0 degreeC with ice.

Acrylonyl chloride (4.4 g, 49 mmol) was added to this solution using the syringe, and it stirred at room temperature for 24 hours. The residue obtained by depressurizingly removing the solvent was dissolved in 300 mL of ethyl acetate, and the solution was washed three times with 100 mL of water. Next, anhydrous magnesium sulfate was added to this solution to remove water, and then concentrated under reduced pressure.

The residue was purified by column chromatography (fixed phase: silica gel, mobile phase: chloroform) to give a white solid in a yield of 8.6 g (73% yield). This white solid is 7.2 to 7.0 ppm (d, 2H, ArH), 6.9 to 6.8 ppm (d, 2H, ArH), and 6.4 to 5.8 ppm (m, 3H) by 1 H-NMR (CDCl ₃ , 400 MHz). , OCHCH ₂ ), 4.3 ppm (t, 2H, OCH ₂ ), 4.0 ppm (q, 2H, PhCH ₂ ), 2.4 ppm (m, 1H, ArCH), 1.9 to 1.2 ppm (m, 20H, CH ₂ ), Δ of 0.85 ppm (t, 3H, CH ₃ ) was observed. Moreover, by IR, characteristic absorption of 2920 cm ^-1 (CH), 1715 cm ^-1 (C = O), and 1245 cm ^-1 (PhO-) was observed.

Synthesis of Dendrimer C

In a 200 mL nio flask, DAB-Am-8 (0.48 g, 0.57 mmol), 3- [4- (trans-4-pentyl cyclohexyl) phenoxy] propyl acrylate (6.5 g, 18 mmol) and THF (manufactured by Aldrich) 10 ml) was added, and the mixture was stirred at 50 ° C for 7 days in a nitrogen atmosphere. Next, the solution was concentrated under reduced pressure, and the residue was dissolved in a small amount of chloroform, added to methanol, and the surface layer solution was removed by decantation to recover a precipitate. By repeating this operation 3 times, the product was purified to yield 2.1 g (yield 57%) of light yellow solid.

This pale yellow solid is 7.2 to 6.7 ppm (m, 64H, ArH), 4.2 ppm (t, 32H, OCH ₂ ), 3.95 ppm (t, 32H, PhOCH ₂ ) by 1 H-NMR (CDCl ₃ , 400 MHz). ), 2.74 ppm (t, 32H, N-CH ₂ ), 2.6 to 2.2 ppm (t, 100H, N-CH ₂ , CH ₂ C = O, ArCH), 1.9 to 0.9 ppm (m, 332H, CH ₂ ), 0.85 δ of ppm (t, 48H, CH ₃ ) was observed. Moreover, by IR, characteristic absorption of 2923 cm <^-1> (CH), 1735 cm <^-1> (C = O), and 1243 cm <^-1> (PhO-) was observed.

Moreover, the molecular weight of this pale yellow solid by MALDI-TOF-MS was measured, but the theoretical value m / Z = 6531. For 82 (M + Na), found m / Z = 6531. 69 (M + Na). Moreover, the elemental analytical value of this pale yellow solid was in agreement with the value calculated as C ₄₀₈ H ₆₄₀ N ₁₄ O ₄₈ within a range of 0.5% (calculated value-C: 75.28%, H: 9.91%, N: 3.01%, found value ~). C: 75.26%, H: 10.10%, N: 2.85%).

Moreover, DSC measurement of this pale yellow solid was carried out, and the endothermic peak was observed at 17 degreeC and 78 degreeC about the temperature rise process, and the exothermic peak was observed at 74 degreeC and 15 degreeC about the temperature-fall process.

Synthesis of Dendrimer D

In the formula (1), a dendrimer represented by the following formula (13) in which R ¹ is synthesized as follows.

Synthesis of 12- [4- (trans-4-pentyl cyclohexyl) phenoxy] dedecanonor

In 300 ml Nas flask, 4- (trans-4-pentyl cyclohexyl) phenol (15 g, 61 mmol), 12-bromo-1-ddecanol (19 g, 73 mmol), potassium carbonate (17 g, 122 mmol) and 2- Butanone (100 mL) was added to dissolve and heated to reflux for 60 hours. After the completion of heating reflux, the residue obtained by removing 2-butanone under reduced pressure was dissolved in 300 mL of ethyl acetate, and the solution was washed three times with 100 mL of water.

Next, anhydrous sodium sulfate was added to this solution to remove water, and the residue obtained by removing ethyl acetate under reduced pressure was recrystallized with hexane to obtain white crystals with a yield of 21.5 g (82% yield). This white crystal is 7.2 to 7.0 ppm (d, 2H, ArH), 6.9 to 6.8 ppm (d, 2H, ArH), 3.9 ppm (t, 2H, OCH ₂ ) by 1 H-NMR (CDCl ₃ , 400 MHz). ), 3.6 ppm (q, 2H, PhCH ₂ ), 2.4 ppm (m, 1H, ArCH), 1.9 to 1.2 ppm (m, 38H, CH ₂ ), 0.86 ppm (t, 3H, CH ₃ ) It became. In addition, by IR, characteristic absorption of 3340 cm ^-1 (OH), 2922 cm ^-1 (CH), and 1245 cm ^-1 (PhO-) was observed.

Synthesis of 12- [4- (trans-4-pentyl cyclohexyl) phenoxy] dodecyl acrylate

12- [4- (trans-4-pentyl cyclohexyl) phenoxy] decanol (15 g, 35 mmol), triethylamine (3.5 g, 35 mmol) and THF (150 mL) were dissolved in a 300 mL Naus flask. And it cooled at 0 degreeC with ice. Acrylonyl chloride (4.7 g, 52 mmol) was added to this solution using the syringe, and it stirred at room temperature for 24 hours.

The residue obtained by depressurizingly removing the solvent was dissolved in 400 mL of ethyl acetate, and the solution was washed three times with 200 mL of water. Next, anhydrous magnesium sulfate was added to this solution to remove water, and then concentrated under reduced pressure. The residue was purified by column chromatography (fixed phase: silica gel, mobile phase: chloroform) to obtain a white solid in a yield of 9.2 g (yield 55%).

This white solid is 7.2 to 7.0 ppm (d, 2H, ArH), 6.9 to 6.8 ppm (d, 2H, ArH), and 6.4 to 5.8 ppm (m, 3H, by 1 H-NMR (CDCl ₃ , 400 MHz). OCHCH ₂ ), 4.3 ppm (t, 2H, OCH ₂ ), 4.0 ppm (q, 2H, PhCH ₂ ), 2.4 ppm (m, 1H, ArCH), 1.9-1.2 ppm (m, 38H, CH ₂ ), 0.85 δ of ppm (t, 3H, CH ₃ ) was observed. Moreover, by IR, characteristic absorption of 2923 cm <^-1> (CH), 1717 cm <^-1> (C = O), and 1244 cm <^-1> (PhO-) was observed.

Synthesis of Dendrimer D

In a 200 ml niro flask, DAB-Am-8 (0.26 g, 0.34 mmol), 12- [4- (trans-4-pentyl cyclohexyl) phenoxy] dodecyl acrylate (8.0 g, 17 mmol) manufactured by Aldrich Corporation, and THF (15 mL) was added thereto, and the mixture was stirred at 50 ° C. for 7 days in a nitrogen atmosphere. Next, the solution was concentrated under reduced pressure, and the residue was dissolved in a small amount of chloroform, added to methanol, and the surface layer solution was removed by decantation to recover a precipitate. This operation was repeated three times to obtain a pale yellow solid in a yield of 1.1 g (38% yield).

This pale yellow solid is 7.2 to 6.7 ppm (m, 64H, ArH), 4.05 ppm (t, 32H, OCH ₂ ), 3.9 ppm (t, 32H, PhOCH ₂ ) by ¹ H-NMR (CDCl ₃ , 400 MHz). ), 2.75 ppm (t, 32H, N-CH ₂ ), 2.6 to 2.2 ppm (t, 100H, N-CH ₂ , CH ₂ C = O, ArCH), 1.9 to 0.9 ppm (m, 640H, CH ₂ ) , Δ of 0.85 ppm (t, 48H, CH ₃ ) was observed. Moreover, the characteristic absorption of 2921 cm <^-1> (CH), 1733 cm <^-1> (C = O), and 1245 cm <^-1> (PhO-) was observed by IR.

Moreover, the molecular weight of this pale yellow solid by MALDI-TOF-MS was measured, but the theoretical value m / Z = 8552. For 08 (M + Na), found m / Z = 8552. 12 (M + Na). Moreover, the elemental analytical value of this pale yellow solid was consistent with the value calculated as C ₅₅₂ H ₉₂₈ N ₁₄ O ₄₈ within the range of 0.5% (calculated value-C: 77.73%, H: 10.97%, N: 2.30%, found value ~). C: 77.48%, H: 11.02%, N: 2.29%). Moreover, DSC measurement of this pale yellow solid was carried out, and the endothermic peak was observed at 74 degreeC and 82 degreeC about the temperature rise process, and the exothermic peak was observed at 79 degreeC and 72 degreeC about the temperature-fall process.

Synthesis of Dendrimer E

In the general formula (1), a dendrimer represented by the following formula (14) in which R ¹ is synthesized as follows.

DAB-Am-8 (0.28 g, 0.31 mmol) manufactured by Aldrich Co., Ltd., 4-methoxy phenyl-6-hexyloxycyacrylbenzoate (6.0 g, 15 mmol) and THF (10) manufactured by Koyo Chemical Co., Ltd. Ml) was added and stirred at 50 ° C for 7 days in a nitrogen atmosphere. Next, the solution was concentrated under reduced pressure, and then the residue was dissolved in a small amount of chloroform, added to hexane, and the surface layer solution was removed by decantation to recover a precipitate. This operation was repeated three times to purify to obtain 1.7 g (76% yield) of a pale yellow solid in the form of a paste.

This pale yellow solid is 8.2 to 8.1 ppm (d, 32H, ArH), 7.1 ppm (d, 32H, ArH), 6.9 ppm (t, 64H, ArCH) by ¹ H-NMR (CDCl ₃ , 400 MHz), 4.1 ppm (t, 32H, OCH ₂ ), 4.0 ppm (t, 32H, PhOCH ₂ ), 3.8 ppm (s, 48H, OCH ₃ ), 2.74 ppm (t, 32H, N-CH ₂ ), 2.6-2.2 ppm δ of (t, 84H, N-CH ₂ , CH ₂ C═O) and 1.9 to 0.9 ppm (m, 284H, CH ₂ ) were observed. In addition, by IR, 2944 cm ^-1 (CH), 1732 cm ^-1 (C = O), 1250 cm ^-1 (COC), 1198 cm ^-1 and 1169 cm ^-1 (C (C = O) OC) The characteristic absorption of was observed. Moreover, the molecular weight of this pale yellow solid by MALDI-TOF-MS was measured, and the theoretical value m / Z = 7170. For 57 (M + Na), found m / Z = 7172. 48 (M + Na).

Synthesis of Dendrimer F

In the formula (1), a dendrimer represented by formula (15) below in which R ¹ was synthesized as follows.

DAB-Am-8 (0.33 g, 0.43 mmol) manufactured by Aldrich Co., Ltd., 6- (4- (4-fluorophenyl) phenylroxyoxy) hexyl acrylate (7.0 g, 20 mmol) manufactured by Aldrich Co., Ltd. ) And THF (10 ml) were added, and the mixture was stirred at 50 ° C for 7 days in a nitrogen atmosphere. Next, the solution was concentrated under reduced pressure, and the residue was dissolved in a small amount of chloroform, added to methanol, and the surface layer solution was removed by decantation to recover a precipitate. This operation was repeated three times to obtain a pale yellow solid in a yield of 1.9 g (72% yield).

This pale yellow solid is 7.5 to 7.2 ppm (m, 64H, ArH), 7.1 ppm (t, 32H, ArH), 6.9 ppm (d, 32H, ArCH) by ¹ H-NMR (CDCl ₃ , 400 MHz), 4.1 ppm (t, 32H, OCH ₂ ), 3.9 ppm (t, 32H, PhOCH ₂ ), 2.74 ppm (t, 32H, N-CH ₂ ), 2.6-2.2 ppm (t, 84H, N-CH ₂ , CH2C = O), and δ of 1.9 to 0.9 ppm (m, 284H, CH ₂ ) were observed. In addition, by IR, 2940 cm ^-1 (CH), 1732 cm ^-1 (C = O), 1235 cm ^-1 (COC), 1182 cm ^-1 (CF), 1160 cm ^-1 (C (C = O) ) Characteristic absorption of OC) was observed. Moreover, DSC measurement of this pale yellow solid was carried out, and an endothermic peak was observed at 56.90 ° C for the temperature rise process, and an exothermic peak was observed at 49.51 ° C for the temperature decrease process.

Synthesis of Dendrimer G

In the formula (1), a dendrimer represented by R ¹ is represented by the following formula (16) was synthesized as follows.

DAB-Am-8 (0.25 g, 0.32 mmol) manufactured by Aldrich Co., Ltd., 6- (4- (3,4,5-trifluorophenyl) phenylroxy) hexyl acrylate (manufactured by Koyo Chemical Co., Ltd.) 6.0 g, 15 mmol) and THF (10 mL) were added, and the mixture was stirred at 50 ° C for 7 days in a nitrogen atmosphere. Next, the solution was concentrated under reduced pressure, and then the residue was dissolved in a small amount of chloroform, added to hexane, and the surface layer solution was removed by decantation to recover a precipitate. This operation was repeated three times to obtain a pale yellow solid in a yield of 1.3 g (yield 59%).

This pale yellow solid is 7.5 to 7.2 ppm (d, 32H, ArH), 7.1 ppm (t, 32H, ArH), 6.9 ppm (d, 32H, ArCH) by ¹ H-NMR (CDCl ₃ , 400 MHz), 4.1 ppm (t, 32H, OCH ₂ ), 3.9 ppm (t, 32H, PhOCH ₂ ), 2.74 ppm (t, 32H, N-CH ₂ ), 2.6-2.2 ppm (t, 84H, N-CH ₂ , CH ₂ C = O) and 1.9 to 0.9 ppm (m, 284H, CH ₂ ) were observed. Furthermore, by IR, 2943 cm ^-1 (CH), 1732 cm ^-1 (C = O), 1243 cm ^-1 (COC), 1182 cm ^-1 (CF), 1118 cm ^-1 (C (C = O) ) Characteristic absorption of OC) was observed. Furthermore, DSC measurement of this pale yellow solid was carried out, but no peak was observed in any of the temperature rise process and the temperature decrease process.

<Synthesis of dendron>

The dendron represented by following formula (17) was synthesize | combined as follows.

Synthesis of 2- [N, N-Biz (2-cyanoethyl) amino] ethanol

Water (60 ml), 2-amino ethanol (10 g, 0.17 mmol) and acrylonitrile (22 g, 0.42 mol) were added to a 200 ml naus flask and stirred at 80 ° C. for 1 hour, followed by acrylonitrile and Water was removed. Next, the residue was dissolved in chloroform, anhydrous magnesium sulfate was added to this solution to remove water, and chloroform was removed under reduced pressure to yield a colorless transparent liquid in a yield of 27 g (yield 97%). IR of this liquid was measured, and characteristic absorption of 3492 cm ^-1 (OH) and 2248 cm ^-1 (CN) was observed.

Synthesis of 2- [N, N-Nees (3-aminopropyl) amino] ethanol

Lithium aluminum hydride (6.9 g, 0.18 mol) and THF (160 mL) were put into a 300 mL three neck flask, and the mixture was stirred at room temperature for 30 minutes. Next, concentrated sulfuric acid (3.6 mL, 0.068 mol) was added to this solution at -5 ° C, and stirred for 1 hour. Next, THF solution (30 mL) of 2- [N, N-nez (2-cyanoethyl) amino] ethanol (5.0 g, 0.03 mol) was added to the solution, and the mixture was further stirred at room temperature for 8 hours.

Next, water (9.7 mL) was added to this mixed solution on ice using a syringe. After separating the produced solid by filtration, the solid was extracted with Soxhlet for 24 hours with methanol. Next, after extracting the extract and the liquid separated by filtration, anhydrous magnesium sulfate was added to the solution to remove water. Subsequently, the solvent was removed under reduced pressure to yield a yellow liquid having a yield of 2.9 g (yield 54%). IR of this liquid was measured and a characteristic absorption of 3285 cm ^-1 (OH) was observed.

Synthesis of Dendron

2- [N, N-needs (3-aminopropyl) amino] ethanol (0.18 g, 1.0 mmol), 6- [4- (trans-4-pentyl cyclohexyl) phenoxy] hexyl acrylate in a 50 mL Naus flask (2.1g, 5.1mmol) and THF (1.0mL) were added, and it stirred for 3 days in nitrogen atmosphere. Next, after THF was removed under reduced pressure, the residue was dissolved in chloroform and the solution was washed three times with water.

Next, anhydrous magnesium sulfate was added to this solution to remove water, and then chloroform was removed under reduced pressure. Next, after the residue was dissolved in a small amount of chloroform, the solution was added to 100 mL of methanol to recover the precipitate by removing the surface layer solution by decantation. By repeating this operation 6 times, it refine | purified and obtained the yield of a pale yellow solid in 0.85 g of yield (49% of yield).

1H-NMR (CDCl ₃ , 400 MHz) of this pale yellow solid was measured, 7.12 to 6.69 ppm (m, ArH, 16H), 4.07 ppm (t, COOCH ₂ , 8H), 3.91 ppm (t, PhOCH ₂ , 2H) , 3.53ppm (t, HOCH ₂ , 2H) characteristic absorption was observed. Moreover, the molecular weight of this pale yellow solid by MALDI-TOF-MS was measured, but the theoretical value m / Z = 1777. Found m / Z = 1778 for 37 (M + H). 27 (M + H). Moreover, DSC measurement of this pale yellow solid was carried out, and the endothermic peak was observed at 14 degreeC and 63 degreeC about the temperature rise process, and the exothermic peak was observed at 19 degreeC and 58 degreeC about the temperature-fall process.

The liquid crystal composition was prepared by mixing each dendrimer or dendron and the fluorine-based mixed liquid crystal ZLI-4792 (P type, Merck Co., Ltd.) prepared above. Here, content of each dendrimer or dendron in a liquid crystal composition was 0.1 mass%.

Next, the liquid crystal display device shown in FIG. 3 was manufactured using the liquid crystal composition obtained above.

First, the glass substrate 7 and the polarizing plate 6 of 100 mm x 100 mm x 0.7 mm which were equipped with the ITO pixel electrode and the common electrode (10 micrometers of electrode distance, electrode area 1cm <2>) were prepared. Next, on the glass substrate 7, a spacer 4 having a height of 3 μm was formed by photolithography.

Subsequently, after apply | coating UV curable resin using the dispenser around the glass substrate 7 except the part used as a liquid crystal injection hole part, the glass substrate 7 and the polarizing plate 6 which formed the spacer 4 were bonded together, It adhere | attached by irradiating UV from the glass substrate 7 side with the polarizing plate 6 side down. Next, the liquid crystal composition obtained above was vacuum-injected from the liquid crystal injection hole, and the liquid crystal injection hole was sealed with said UV curable resin. Then, the other polarizing plate 6 was arrange | positioned on the back surface of the glass substrate 7 so that it might become a cross nicol state.

Next, in order to evaluate the vertical alignment property of each liquid crystal display device produced above, it evaluated using the luminance meter. Specifically, the liquid crystal display device was placed on the backlight, and a luminance meter was disposed on the opposite side where the liquid crystal display device was sandwiched. The luminance was measured at five places (center, top, bottom, left and right). In this evaluation, in general, if the vertical alignment is uniform, the same value is obtained at any measurement site and the luminance value is small. If the vertical alignment is insufficient, the luminance value is increased due to light leakage.

As a result of the measurement, the liquid crystal display device produced above confirmed that the luminance value was clearly smaller than the case where the vertical alignment was insufficient at any measurement place, and the vertical alignment was uniform.

As can be seen from the above results, according to the present invention, by controlling the alignment of liquid crystal molecules without forming the alignment film, a problem caused by the formation of the alignment film is prevented and inexpensive flexible generally known in the art. By using a substrate, it is possible to provide a liquid crystal display device that can be reduced in weight, thickness, and cost.

1: first substrate 2: second substrate
3: liquid crystal layer 4: spacer
5: sealing material 6: polarizing plate
7: glass substrate 8: alignment film

Claims (12)

A liquid crystal display device having a pair of substrates on which no alignment film is formed and a liquid crystal layer sandwiched between the pair of substrates,
At least one of the pair of substrates is a flexible substrate, and wherein the liquid crystal layer comprises a liquid crystal component and a dendrimer and / or a dendron compatible with the liquid crystal component. The liquid crystal display device according to claim 1, wherein the glass transition temperature of the flexible substrate is 200 ° C or less. The liquid crystal display device according to claim 1, wherein the driving method is VA mode. The liquid crystal display device according to claim 1, wherein a polarizing plate is used as said flexible substrate. The liquid crystal display device according to claim 1, wherein the dendrimer has at least one selected from the group consisting of alkyl group, alkoxy group and fluorine at the terminal. According to claim 1, wherein the dendrimer has the formula
[Formula 1]

(In Formula 1, R ¹ has the structure of Formula 2,
(2)

And A ¹ is represented by Formula 3
(3)

(In Formulas 2 and 3, Y is an alkyl group or alkoxy group having 1 to 12 carbon atoms, or fluorine), X is a direct bond, -COO- group or -N = N- group, A ² is
[Chemical Formula 4]

And n is an integer of 3 to 12). The liquid crystal display device according to claim 1, wherein the dendron has at least one selected from the group consisting of an alkyl group, an alkoxy group and a fluorine at a non-focal point terminal. The liquid crystal display device according to claim 1, wherein the dendron has an amino group at a focal point. The liquid crystal display device according to claim 1, wherein the dendron has a mesogen group. According to claim 1, wherein the dendron is represented by the following formula (5);
[Chemical Formula 5]

(In the formula 5 R is hydrogen, an alicyclic group, an aromatic group, or HO- (CH ₂₎ m- group (where, m is an integer a) of 2 ~ 6; A ¹ of the formula 6;
[Formula 6]

(Wherein Y is an alkyl group or an alkoxy group having 1 to 12 carbon atoms or a fluorine group), and A ² is represented by Formula 7;
[Formula 7]

And X is a direct bond, a -COO- group or a -N = N- group, n is an integer of 3 to 12). The liquid crystal display device according to claim 1, wherein the liquid crystal component is a mixed liquid crystal containing two or more liquid crystal components. The liquid crystal display device according to claim 1, wherein the liquid crystal component is a fluorine-based mixed liquid crystal.

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