KR20140031176A - Polymeric liquid crystal compound, polymeric liquid crystal composition, and oriented film - Google Patents

Abstract

(식 중, X¹, X², X³ 및 X⁴는 서로 독립하여 수소 원자 또는 불소 원자를 나타내고, R은 수소 원자, 할로겐 원자, 시아노기, 알킬기, 알콕시기, 또는 알콕시카르보닐기를 나타내고, G는 -C(=O)O- 또는 -OC(=O)- 기를 나타내고, n은 4∼10의 정수를 나타낸다.)The polymerizable liquid crystal compound represented by following formula [1], the polymeric liquid crystal composition containing this, the polymer obtained from it, a film, and an oriented film, and the optical member provided with the said oriented film are provided.

(Wherein X ¹ , X ² , X ³ and X ⁴ independently represent a hydrogen atom or a fluorine atom, R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group, and G Represents a -C (= O) O- or -OC (= O)-group, and n represents an integer of 4 to 10.

Description

POLYMERIC LIQUID CRYSTAL COMPOUND, POLYMERIC LIQUID CRYSTAL COMPOSITION, AND ORIENTED FILM

The present invention relates to a polymerizable liquid crystal compound having polymerizability and liquid crystallinity, a composition containing the same, a polymer obtained by using these, and an alignment film, for example, a material having optical properties such as a display device or a recording material, In particular, it is related with the polymeric liquid crystal compound which can be used suitably for optical compensation films, such as a polarizing plate and retardation plates for liquid crystal displays, the composition containing this, and the polymer and orientation film obtained using these.

The demand for the polymer film whose molecular orientation structure was controlled as optical compensation films, such as a polarizing plate and a retardation plate, is increasing from the request of the improvement of display quality of a liquid crystal display device, light weight, etc. In order to meet this demand, development of a film using optical anisotropy of a polymerizable liquid crystal compound has been carried out.

The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure portion (a structural portion having a spacer portion and a mesogen portion), and an acrylic group is widely used as the polymerizable group.

Such a polymerizable liquid crystal compound generally becomes a polymer (film) by a method of polymerizing by irradiation with radiation such as ultraviolet rays.

For example, the method of obtaining a polymer by irradiating a radiation by carrying out the specific polymeric liquid crystal compound which has an acryl group between supports, and maintaining this compound in a liquid crystal state (refer patent document 1), or two types of superposition | polymerization which has an acryl group The method of adding a photoinitiator to the mixture of a crystalline liquid crystal compound or the composition which mixed the chiral liquid crystal to this mixture, and irradiating an ultraviolet-ray is known (refer patent document 2).

The polymer (film) obtained by each of the above methods is a film for a polarizing plate, a retardation plate, or the like, and is mounted on a display device used in a high temperature environment such as a car interior, as well as a display device such as a monitor or a television. For this reason, maintaining transparency in a high temperature environment is very important as a material for display devices.

However, in the film obtained from the polymerizable liquid crystal compound, when the glass transition temperature (hereinafter referred to as Tg) is below the temperature of the use environment, especially under a high temperature environment, the microscopic fluctuation of molecules occurs, so that the orientation is disturbed and the optical anisotropy. This may fall remarkably.

Moreover, in the field of a display, examination of the process simplification which uses these materials as an In Cell retardation film is actively advanced in recent years. The material used for this In Cell technology is requesting higher thermal stability and chemical resistance.

On the other hand, various orientation films, such as a horizontal, a vertical, and a hybrid orientation, are obtained by the difference of the orientation mode of a polymeric liquid crystal compound, and the hybrid orientation film which shows various average tilt angles is also reported (refer patent document 3). Among them, if the additive of the liquid crystal composition can be controlled at a low addition amount, the control of the average tilt angle of the obtained film can be widely applied in the field of liquid crystal display.

Japanese Patent Laid-Open No. 62-70407 Japanese Patent Application Laid-Open No. 9-208957 International Publication No. 08/052376

The present invention has been made in view of the above circumstances, and can provide a polymer having excellent optical anisotropy, stable retardation value and transparency even at high temperature, and excellent in chemical resistance and heat resistance, and low addition amount. It aims at providing the polymeric liquid crystal compound which can control the average angle of a hybrid alignment film, the polymeric liquid crystal composition containing this, the polymer obtained by this polymeric liquid crystal composition, and an orientation film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the predetermined polymeric liquid crystal compound which has a (alpha)-methylene- (gamma)-(butyrolactone) site | part has liquid crystallinity, and itself is polymerizable. It is excellent and can control the average angle of a hybrid orientation film with a low addition amount, and provides the stable liquid crystalline composition, and the polymer and film obtained from this liquid crystalline composition have the outstanding heat resistance in optical anisotropy and transparency. The present invention was completed.

That is, the present invention,

1. A polymerizable liquid crystal compound characterized by the following formula [1],

(In formula, X <^1> , X <^2> , X <^3> and X <^4> show a hydrogen atom or a fluorine atom independently from each other, R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or the alkoxycarbonyl group. , G represents a -C (= 0) O- or -OC (= 0)-group, and n represents an integer of 4 to 10.

A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound of 2. 1,

3. Moreover, the polymerizable liquid crystal composition of 2 containing the liquid crystalline compound which has 1 or more of polymerizable groups in 1 molecule,

4. Polymeric liquid crystal composition of 3 whose said liquid crystalline compound is a compound which has 1 or more of polymerizable groups represented by following formula [2] or [3] in 1 molecule,

(In the formula, the broken line represents the combined hand.)

5. 3 or 4 polymerizable liquid crystal composition whose said liquid crystalline compound is at least 1 sort (s) chosen from the group which consists of a compound represented by following formula [4] and [5],

(In formula, X represents a fluorine atom, a cyano group, or a C4-8 monovalent hydrocarbon group, f1 and f2 respectively independently represent the integer of 2-9, g represents the integer of 2-9, M ¹ , M ² and M ³ each independently represent a group represented by the following formula [2] or [3].)

(In the formula, the broken line represents the combined hand.)

6. Polymer obtained from polymerizable liquid crystal composition in any one of 2-5,

7. Film obtained from polymerizable liquid crystal composition in any one of 2-5,

8. Orientation film obtained from polymerizable liquid crystal composition in any one of 2-5,

9. an optical member having a polymer of 6 or an orientation film of 8,

10. A compound characterized by the following formula [6]

(In formula, Y represents -OH or -COOH and k represents the integer of 4-10.)

Lt; / RTI &gt;

The polymerizable liquid crystal compound and the composition containing the same of the present invention not only have excellent optical anisotropy, but also provide a polymer having stable anisotropy and transparency in a high temperature environment.

Moreover, the polymeric liquid crystal compound of this invention has the advantage that the tilt of the optical anisotropy of the composition containing this can be controlled with a small addition amount.

Therefore, the polymer obtained from the composition containing the said polymeric liquid crystal compound can be used suitably as optically anisotropic films, such as a polarizing plate and a retardation plate.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the retardation value angle dependency in wavelength 590nm of each film obtained by Examples 10-15 and Comparative Example 1. FIG.

The usage of the terms in this specification is as follows.

A "polymerizable liquid crystal compound" means a compound which has a polymerizable site | part and a liquid crystal structure site | part, such as an acryl group and the (alpha)-methylene lactone ring, in a molecule | numerator and shows a liquid crystal phase. This "liquid crystal structure" means the structure which has a spacer part and a mesogenic part generally used when showing a liquid crystal molecule. "Liquid crystal composition" means the composition which has a characteristic which shows a liquid crystal phase. "Liquid crystallinity" means showing a liquid crystal phase.

Hereinafter, the present invention will be described in more detail.

[Polymerizable Liquid Crystal Compound]

The polymerizable liquid crystal compound according to the present invention is represented by the following formula [1].

(In formula, X <^1> , X <^2> , X <^3> and X <^4> show a hydrogen atom or a fluorine atom independently from each other, R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or the alkoxycarbonyl group. , G represents a -C (= 0) O- or -OC (= 0)-group, and n represents an integer of 4 to 10.

The compound represented by Formula [1] is a compound which has a lactone ring and a liquid crystal structure site | part, and is a polymeric liquid crystal compound which has (alpha)-methylene- (gamma) -butyrolactone site | part.

[alpha] -methylene- [gamma] -butyrolactone can exert a very excellent effect of having high polymerizability and less influence by steric hindrance among [alpha] -alkylidene- [gamma] -butyrolactone having a polymerizable group. It is effective because it gives a high Tg and heat resistance to a polymer obtained by using this compound.

In formula [1], the repeating site | part of a methylene group is a site called a spacer part. Here, n represents the repeating number of a methylene group, Although it is an integer of 4-10, Preferably it is an integer of 4-6.

R in Formula [1] represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.

Here, as said halogen atom, a fluorine, a chlorine, a bromine, and an iodine atom are mentioned, A fluorine atom is preferable in this invention.

The alkyl group may be any linear, branched or cyclic one, and the carbon number is not particularly limited, but in the present invention, a linear C1-C10 alkyl group is preferable.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, n-pentyl group, Cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, etc. are mentioned.

The alkyl group constituting the alkoxy group may be any linear, branched or cyclic one, and the carbon number is not particularly limited, but in the present invention, an alkoxy group having a linear C1-C10 alkyl group is preferable.

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, n-pentoxy and n-hex A siloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, etc. are mentioned.

The alkyl group constituting the alkoxycarbonyl group may be any linear, branched or cyclic one, and the carbon number is not particularly limited, but in the present invention, an alkoxycarbonyl group having a linear C1-C10 alkyl group is preferable.

Specific examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, s-butoxycarbonyl group, t-butoxycarbonyl group and n-pen An oxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, etc. are mentioned.

In addition, each alkyl group of the said alkyl group, the alkoxy group, and the alkoxycarbonyl group may further be substituted by other substituents, such as a halogen atom, at least 1 of the hydrogen atom.

As said R, among the said substituents, a hydrogen atom, a halogen atom, and an alkoxycarbonyl group are especially preferable, and the alkoxycarbonyl group which has a hydrogen atom, a fluorine atom, and a C1-C5 linear alkyl group is more preferable.

The polymerizable liquid crystal compound represented by the formula [1] represents a liquid crystal phase such as a smectic phase or a nematic phase. This property is useful in the field of applications utilizing optical anisotropy such as polarizing plates and retardation plates.

Although the compound etc. which are represented by following formula (1)-(35) as a specific example of said polymeric liquid crystal compound are mentioned, It is not limited to these.

[Synthesis of polymerizable liquid crystal compound]

The polymeric liquid crystal compound of this invention can be synthesize | combined by combining the method in organic synthetic chemistry, The synthesis method is not specifically limited.

Compounds having an α-methylene-γ-butyrolactone structure, for example, use a technique proposed by Talaga et al. (P. Talaga, M. Schaeffer, C. Benezra and JL Stampf, Synthesis, 530 (1990)). Can be synthesized. This method is a method in which 2- (bromomethyl) acrylic acid (2- (bromomethyl) propenoic acid) is reacted with aldehyde or ketone using SnCl ₂ as represented by the following Synthesis Scheme (A1).

In addition, 2- (bromomethyl) acrylic acid can be obtained by a method proposed by Ramarajan et al. (K. Ramarajan, K. Kalamingam, DJ O'Donnell and KD Berlin, Organic Synthesis, vol. 61, 56-59 (1983). )).

(Wherein R 'represents a monovalent organic group, and Amberlyst® 15 is an ion exchange resin manufactured by Rohm and Haas Co., Et represents an ethyl group.)

In the reaction of 2- (bromomethyl) acrylic acid using SnCl ₂ , an α-methylene-γ-butyrolactone structure can also be obtained by reaction with acetal or ketal corresponding to aldehyde or ketone.

As acetal or ketal, the compound which has a dimethyl acetal group, a diethyl acetal group, a 1, 3- dioxane group, a 1, 3- dioxolane group, etc. is mentioned. The synthesis method and protecting group at the time of using acetal or a ketal for the following synthesis schemes (A2) are shown.

(In formula, R 'has the same meaning as the above. A dashed line shows a bond.)

The intermediate for synthesizing the compound represented by the formula [1] can be synthesized by the method of the following synthetic reaction formula (B) or (C) by applying the method of the above-described synthesis scheme (A1) or (A2).

(In formula, n represents the same meaning as the above. Me means a methyl group. PCC represents a pyridinium chloro chromate.)

(Wherein n has the same meaning as defined above).

Next, as shown to the following synthesis reaction formula (D) or (E), the polymeric liquid crystal compound represented by Formula [1] can be obtained by making the intermediate and a phenol type compound react and esterify.

(Wherein n, X ^{1 to} X ⁴ and R represent the same meaning as described above. DCC represents dicyclohexylcarbodiimide and DMAP represents N, N-dimethyl-4-aminopyridine.)

(Wherein, n, X ¹ ~X ⁴ and R are the same meanings as defined above.)

[Polymerizable Liquid Crystal Composition]

Although the polymeric liquid crystal composition which concerns on this invention should just contain at least 1 sort (s) of the polymeric liquid crystal compound represented by said Formula [1], In the polymeric liquid crystal composition of this invention, the polymeric liquid crystal compound of Formula [1], Since the hybrid orientation film is obtained by mixing the compound (henceforth a specific compound) which has a liquid crystal structure site | part, what contains at least 1 sort (s) of the polymeric liquid crystal compound represented by Formula [1], and the said specific compound is mentioned. Suitable.

In addition, the specific compound to mix may be used individually by 1 type or in combination of multiple types.

At this time, the specific compound may or may not have a polymerizable group such as an acryl group or a lactone ring. The specific compound having a polymerizable group may be monofunctional or multifunctional.

These specific compounds are compounds other than the polymeric liquid crystal compound of this invention as a compound which has liquid crystallinity as a compound which does not have a polymeric group, and has a polymeric group and shows liquid crystallinity.

As a polymeric group which the said specific compound may have, group represented by following formula [2] or [3] is mentioned.

(In the formula, the broken line represents the combined hand.)

Especially as a specific compound which has the said polymeric group, the compound represented by following formula [4] or [5] is preferable.

(In formula, M <^1> , M <^2> and M <^3> are respectively independently group represented by said Formula [2] or [3]. X is a fluorine atom, a cyano group, or a C4-8 monovalent hydrocarbon group. f1 and f2 respectively independently represent the integer of 2-9, g represents the integer of 2-9.)

Although the compounding ratio of the said specific compound is not specifically limited, It is 200-1,900 mass parts with respect to 100 mass parts of polymeric liquid crystal compounds of Formula [1], Preferably it is 100 mass parts of polymeric liquid crystal compounds of Formula [1] It is 400-900 mass parts with respect to.

Specific examples of the specific compound include compounds represented by the following formulas (36) to (126) described in International Publication No. 06/115033 Pamphlet and International Publication No. 06/115112 Pamphlet, nematic liquid crystal, ferroelectricity Although a liquid crystal and a commercial liquid crystal composition etc. are mentioned, it is not limited to these.

A photoinitiator, a thermal polymerization initiator, a photosensitizer, etc. can also be added to the polymeric liquid crystal composition of this invention in order to improve the polymerization reactivity.

Examples of the photopolymerization initiator include benzoin ethers such as benzoin methyl ether, acetophenones such as diethoxyacetophenone, benzyl ketal such as benzyl dimethyl ketal, and the like. The said photoinitiator can be used individually by 1 type or in combination of multiple types.

The amount of the photopolymerization initiator added is 5 parts by mass or less based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound represented by Formula [1] and the specific compound exhibiting liquid crystallinity (hereinafter, both are referred to as total liquid crystal compounds). Is preferable, More preferably, it is 0.5-2.0 mass parts.

As the thermal polymerization initiator, for example, 2,2'-azobisisobutyronitrile and the like can be given. The thermal polymerization initiator may be used alone or in combination of two or more thereof. The amount of the addition is preferably 5 parts by mass or less, more preferably 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the total liquid crystalline compound.

As said photosensitizer, anthracene type photosensitizers, such as anthracene, are mentioned, for example. A photosensitizer can also be used individually by 1 type or in combination of 2 or more types, and, as for the addition amount, 5 mass parts or less are preferable with respect to 100 mass parts of total liquid crystalline compounds.

The photopolymerization initiator may be used in combination with at least one of a thermal polymerization initiator and a photosensitizer.

To the polymerizable liquid crystal composition of the present invention, a stabilizer may be added for the purpose of improving the storage stability.

Examples of the stabilizer include hydroquinone monoalkyl ethers such as hydroquinone and hydroquinone monomethyl ether, 4-t-butyl catechol, and the like. A stabilizer can also be used individually by 1 type or in combination of 2 or more types, and, as for the addition amount, 0.1 mass part or less is preferable with respect to 100 mass parts of total liquid crystalline compounds.

In the polymerizable liquid crystal composition of the present invention, an adhesion promoter may be added for the purpose of improving the adhesion with the substrate.

Examples of the adhesion promoter include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; Alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane and phenyltriethoxysilane; Silane residues such as hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine and trimethylsilylimidazole; Vinyl trichlorosilane,? -Chloropropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? - (N- Silane compounds such as trimethylsilane; Benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, uracil, mercaptoimidazole, Heterocyclic compounds such as cyclopyrimidine and cyclopyrimidine; Urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea; Thiourea compounds, and the like.

An adhesion promoter may be used individually by 1 type or in combination of 2 or more types, and, as for the addition amount, 1 mass part or less is preferable with respect to 100 mass parts of total liquid crystalline compounds.

Moreover, an organic solvent can also be added to the polymeric liquid crystal composition of this invention for the purpose of viscosity adjustment, etc. In this case, liquid crystal properties may not be exhibited in a state containing an organic solvent.

As said organic solvent, For example, ether, such as tetrahydrofuran and a dioxane; Aromatic hydrocarbons, such as benzene, toluene, and xylene; Polar solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; Esters such as ethyl acetate, butyl acetate, and ethyl lactate; Alkoxy esters such as methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate and ethyl 2-ethoxypropionate; Glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether and dipropylene glycol dimethyl ether; Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; Diglycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether; Glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, carbitol acetate and ethyl cellosolve acetate; And ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These organic solvents may be used alone or in combination of two or more.

Of these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and ethyl lactate are preferred from the viewpoint of safety against the global environment and the working environment.

Moreover, it is suitable that the usage-amount of an organic solvent shall be about 60-95 mass% in a polymeric liquid crystal composition.

A surfactant may be added to the polymerizable liquid crystal composition of the present invention for the purpose of improving affinity with a substrate. Although it does not specifically limit as said surfactant, A fluorine-type surfactant, silicone type surfactant, nonionic surfactant, etc. are mentioned, A fluorine-type surfactant with high affinity improvement effect with a board | substrate is preferable.

As a specific example of the said fluorine-type surfactant (hereafter, brand name), F-top EF301, EF303, EF352 (made by Tochemproduks), Megapak F171, F173, R-30 (made by DIC Corporation), Florad FC430, FC431 (manufactured by Sumitomo Industries Co., Ltd.), Asahi Guard AG710, Saflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), etc. are mentioned. It is not limited to. Moreover, surfactant can also be used individually by 1 type or in combination of 2 or more types, and the addition amount is 5 mass parts or less with respect to 100 mass parts of total liquid crystalline compounds.

As a suitable example of the polymeric liquid crystal composition of this invention, the liquid crystal composition etc. which consist of 100 mass parts of polymeric liquid crystal compounds represented by Formula [1], 400-900 mass parts of specific compounds which show liquid crystal, and 5 mass parts or less of photoinitiators are mentioned. There is no limitation to this.

The polymerizable liquid crystal composition described above can be suitably used as a composition for forming an oriented film or a coating liquid.

The method for preparing the polymerizable liquid crystal composition of the present invention is not particularly limited, and each component constituting the polymerizable liquid crystal composition may be mixed at one time, or may be mixed successively. The order of addition of the respective components when mixing them in sequence is arbitrary.

In addition, when using multiple types of compounds for one component, you may mix the mixture which mixed them previously, and another component, and may mix with another component separately, respectively.

The polymerizable liquid crystal composition of the present invention is prepared at room temperature (20 to 40) in order to avoid unintentional thermal polymerization in the photopolymerization in the liquid crystal state and to easily fix the uniformly aligned state of the molecule when producing the optically anisotropic body. It is preferable to show a thixotropic liquid crystal phase at (degree. C., below.). Moreover, when a polymeric liquid crystal composition contains an organic solvent, when removing a solvent, it is preferable to show a tautomatic liquid crystal phase at room temperature.

[Polymers and films]

About the polymeric liquid crystal composition of this invention demonstrated above, a polymer is obtained by light irradiation or heat processing.

Moreover, a film is obtained by light-irradiating in the state which pinched the polymeric liquid crystal composition between two board | substrates, or the polymerizable liquid crystal composition being apply | coated to the board | substrate by spin coating, the casting method, etc.

In this case, a plastic sheet or film such as glass, quartz, color filter, triacetyl cellulose (TAC), or the like can be used for the substrate. Moreover, as one board | substrate, the belt or drum which plated or deposited metal, such as glass, a plastic sheet, a plastic film, or stainless steel, or chromium or aluminum, in which functional thin films, such as ITO, were formed was used as one board | substrate among two board | substrates. It is also possible.

In order to improve the hybrid orientation of the film obtained, it is preferable to give the board | substrate to be used the orientation process from which a tilt is obtained. As the method of orientation processing, the orientation material containing a polyimide precursor, a polyimide, polyvinyl cinnamate, etc. is apply | coated, the method of orientation treatment by obliquely irradiating rubbing or a polarized ultraviolet-ray, the method of forming the gradient film of silicon dioxide, Although it can select suitably from well-known methods, such as a method of forming an LB film, it is preferable to use the orientation method by which a tilt is obtained in all.

In the method of sandwiching a polymeric liquid crystal composition between two board | substrates, the cell which formed the space | gap between two board | substrates with a spacer etc. was produced, and it superposed | polymerized by the method of using a capillary phenomenon, or reducing the space | gap of a cell. After inject | pouring a crystalline liquid crystal composition into a cell, light is irradiated and it superposes | polymerizes.

As a simpler method, there is also a method of placing a polymerizable liquid crystal composition on a substrate provided with a spacer or the like, superposing one of the other substrates thereon to produce a cell, and irradiating light to polymerize it. In that case, what made the polymerizable liquid crystal composition fluidize may be used, and may be made to fluidize by heating after putting it on a board | substrate, but it is necessary to make a polymerizable liquid crystal composition fluidize before stacking another board | substrate.

Moreover, in the method of clamping a polymerizable liquid crystal composition between two board | substrates, in order to acquire hybrid orientation, one board | substrate needs to be processed so that there may be no orientation process or a vertical orientation may be obtained.

In the method of apply | coating a polymeric liquid crystal composition, you may add the process of heating with a hotplate etc. as needed in the middle of the process of apply | coating a polymeric liquid crystal composition, and the process of superposing | polymerizing with light or heat. This step is particularly effective as a means for removing the organic solvent from the composition when using a polymerizable liquid crystal composition (coating solution) containing an organic solvent.

In any of the above methods, a film having optically anisotropy oriented can be obtained by polymerizing the polymerizable liquid crystal composition in a state showing a liquid crystal phase.

In order to obtain the polymer of the multi-domain state which has a different orientation for every adjacent domain, the method of multi-domainization in the process of superposition | polymerization, or the method of multi-domainization of a board | substrate is used.

The method of multidomaining by the polymerization method includes a method in which a polymerized liquid crystal composition in a liquid crystal state is exposed to ultraviolet light through a mask to form a domain, and the remaining domain is polymerized in an isotropic liquid state. .

Moreover, the method of multi-domainization of a board | substrate, the method of rubbing to the orientation material formed in the board | substrate through the mask, the method of irradiating an ultraviolet-ray through a mask, etc. are mentioned.

By these methods, a multi-domained substrate is obtained in which the rubbed domain and the domain irradiated with ultraviolet rays are portions that are oriented, and the other portions are untreated portions. The polymerizable liquid crystal composition formed on the multi-domained substrate is multi-domained under the influence of the alignment material layer.

Moreover, you may use the method of using an electric field and a magnetic field other than the said orientation processing method.

By using the polymerizable liquid crystal composition of the present invention, a film having optical anisotropy can be obtained, and the film can be suitably used for a polarizing plate, a retarder, and the like. In addition, since the film has good transparency at high temperatures, the film can be suitably used in electronic devices used in high temperature environments such as on-vehicle display devices.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, the measuring method and measurement conditions of each physical property in an Example are as follows.

[1] NMR

The compound was dissolved in deuterated chloroform (CDCl ₃ ) or deuterated dimethylsulfoxide (DMSO-d6), and ¹ H-NMR was measured using a nuclear magnetic resonance apparatus (300 MHz, manufactured by Diol).

[2] Observation of liquid crystal phase

Identification of the liquid crystal phase was carried out by heating a sample on a hot stage (MATS-2002S, manufactured by Tokai Hit Co., Ltd.), and using a polarizing microscope (manufactured by Nikon Corporation). The phase transition temperature was measured under the condition of a scan rate of 10 ° C / min using a Bruker AX Corporation differential scanning thermal analysis apparatus (DSC 3100SR, hereinafter referred to as DSC).

[3] Haze value

The haze value of the film was measured using Spectral Haze Meter (TC-1800H) manufactured by Tokyo Denshoku Co., Ltd.

[4] Retardation value of the film

The retardation value at a wavelength of 590 nm was measured using a retardation measurement apparatus (RETS-100, manufactured by Otsuka Denshi Co., Ltd.).

[5] Average tilt angle of the film

Use AxoScan ^TM Mueller Matrix Polarimeter (AXOMETRIX Co., Ltd.) to measure the average tilt angle of the wavelength 590nm.

Synthesis Example 1 Synthesis of Polymerizable Liquid Crystal Compound (E1)

[1] synthesis of intermediate compound (A1)

In a 500 mL eggplant flask with a cooling tube, 9.8 g (50.0 mmol) of 4-cyano-4'-hydroxybiphenyl, 7.0 g (50.0 mmol) of 3-bromo-1-propanol, 13.8 g (100 mmol) of potassium carbonate, And 150 mL of acetone were added to form a mixture, and reacted with stirring at 64 ° C. for 48 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Then, this solid and 140 mL of water were mixed, and 100 mL of diethyl ether was added and extracted there. Extraction was carried out three times. The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was purified by recrystallization using a mixed solvent of hexane / ethyl acetate = 2/1 (v / v) to obtain 8.7 g of a white solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this white solid is an intermediate compound (A1) (yield 70%).

¹ H-NMR (CDCl ₃ ) δ: 2.09 (m, 2H), 3.90 (t, 2H), 4.20 (t, 2H), 6.99 (d, 2H), 7.52 (d, 2H), 7.66 (m, 4H )

[2] synthesis of polymerizable liquid crystal compound (E1)

12.0 g of the intermediate compound (A1) obtained above was dissolved in 40 mL of tetrahydrofuran (THF) together with 7.7 mL of triethylamine and a small amount of BHT (2,6-di-tert-butyl-p-cresol) and stirred at room temperature. Then, a solution obtained by dissolving 4.6 mL of acryloyl chloride in 40 mL of THF was added dropwise over 15 minutes under cooling by a water bath. After dripping, it stirred for 30 minutes, continued stirring overnight, removing the water bath and returning to room temperature, and filtered the triethylamine hydrochloride which precipitated. THF was distilled off about 3/4 from the obtained filtrate, 50 mL of methylene chlorides were added, and the organic layer was wash | cleaned sequentially with 50 mL of saturated sodium hydrogencarbonate aqueous solution, 50 mL of 0.5 mol / L hydrochloric acid, and 50 mL of saturated brine, and it dried with magnesium sulfate. Then, the solvent was distilled off and the product was obtained. After recrystallization with ethanol, 6.0 g of a polymerizable liquid crystal compound (E1) was obtained.

¹ H-NMR (CDCl ₃ ) δ: 2.20 (m, 2H), 4.10 (t, 2H), 4.40 (t, 2H), 5.81 (d, 1H), 6.15 (m, 1H), 6.41 (d, 1H ), 6.99 (d, 2H), 7.55 (d, 2H), 7.66 (m, 4H)

[Synthesis Example 2] Synthesis of polymerizable liquid crystal compound (E2)

[1] synthesis of intermediate compound (A2)

In a 100 mL eggplant flask with a cooling tube, 5.0 g (25.6 mmol) of 4-cyano-4'-hydroxybiphenyl, 4.6 g (25.6 mmol) of 6-bromo-1-hexanol, 7.0 g (50 mmol) of potassium carbonate , And 50 mL of acetone were added to form a mixture, and reacted at 64 ° C. for 24 hours with stirring. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Then, this solid and 70 mL of water were mixed, 50 mL of diethyl ether was added, and it extracted. Extraction was carried out three times.

The separated organic layer was dried by adding anhydrous magnesium sulfate, and after filtration, the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was dissolved in 3 mL of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, Merck agent, eluent: hexane / ethyl acetate = 1/1 (v / v)). The solvent was distilled off from the obtained solution and 6.9 g of white solid was obtained. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid is an intermediate compound (A2) (yield 91%).

¹ H-NMR (DMSO-d6) δ: 1.26 (m, 6H), 1.69 (m, 2H), 3.37 (t, 2H), 4.03 (t, 2H), 7.06 (d, 2H), 7.69 (d, 2H), 7.85 (m, 4H)

[2] synthesis of intermediate compound (B2)

Next cooling tubes attached to 200mL 3 neck flask PCC 2.2g (10.0mmol) and CH ₂ Cl ₂ was added a mixture of 30.0mL in stirring condition, an intermediate compound (A2) 2.95g (10.0mmol) obtained above CH ₂ Cl _The solution dissolved in ₂ 50.0 mL was dripped, and it stirred further at 40 degreeC for 0.5 hour. Thereafter, 90 mL of diethyl ether was added to the solution from which the oily substance adhering to the wall of the flask was removed, and the mixture was filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid.

This solid was dissolved in 3 mL of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, Merck agent, eluent: hexane / ethyl acetate = 1/1 (v / v)). The solvent of the obtained solution was distilled off to obtain 2.8 g of a colorless solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this colorless solid is an intermediate compound (B2) (yield 93%).

¹ H-NMR (CDCl ₃ ) δ: 1.84 (m, 6H), 2.50 (m, 2H), 4.02 (m, 2H), 6.99 (d, 2H), 7.53 (d, 2H), 7.91 (m, 4H ), 9.80 (s, 1 H)

[3] synthesis of polymerizable liquid crystal compound (E2)

Finally, in a 50 mL eggplant flask with a cooling tube, 1.6 g of 3.0 g (10.0 mmol) of the intermediate compound (B2) obtained above, 1.65 g (10.0 mmol) of 2- (bromomethyl) acrylic acid, and Amberlyst® 15 were obtained. , 16.0 mL of THF, 1.9 g (10.0 mmol) of tin chloride (II), and 4.0 mL of pure water were added to the mixture, followed by stirring at 70 ° C. for 7 hours. After completion | finish of reaction, the reaction liquid was filtered under reduced pressure, it mixed with 30 mL of pure waters, and 50 mL of diethyl ether was added and extracted there. Extraction was carried out three times. The organic layer after the extraction was dried over anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a yellow solid. This solid was dissolved in 2 mL of ethyl acetate and purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, Merck Co., eluent: hexane / ethyl acetate = 2/1 (v / v)). The solvent of the obtained solution was distilled off to obtain 1.5 g of a white solid. The NMR measurement results of this solid are shown below. From this result, it was confirmed that this white solid is the target polymeric liquid crystal compound (E2) (yield 41%).

¹ H-NMR (CDCl ₃ ) δ: 1.57 (m, 6H), 1.85 (m, 2H), 2.60 (m, 1H), 3.05 (m, 1H), 4.01 (t, 2H), 4.54 (m, 1H ), 5.63 (m, 1H), 6.23 (m, 1H), 7.00 (d, 2H), 7.52 (d, 2H), 7.68 (m, 4H)

Moreover, when the liquid crystallinity of this polymeric liquid crystal compound (E2) was observed, it became an isotropic liquid state at 84 degreeC and phase-transformed into the liquid crystal phase (nematic phase) at 61 degreeC at the time of temperature drop.

Synthesis Example 3 Synthesis of Polymerizable Liquid Crystal Compound (E3)

[1] synthesis of intermediate compound (A3)

To a 200 mL eggplant flask with a cooling tube, 7.61 g (50.0 mmol) of methyl 4-hydroxybenzoate, 9.1 g (50.0 mmol) of 6-bromo-1-hexanol, 13.8 g (100 mmol) of potassium carbonate, and 70 mL of acetone were added thereto. It was made into a mixture and reacted at 64 degreeC, stirring for 24 hours. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow wet solid. This solid was refine | purified by the silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, Merck make, eluent: hexane / ethyl acetate = 1/1 (v / v)). The solvent was distilled off from the obtained solution to obtain 11.3 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid is an intermediate compound (A3) (yield 90%).

¹ H-NMR (CDCl ₃ ) δ: 1.3-1.7 (m, 8H), 3.67 (m, 2H), 3.88 (s, 3H), 4.03 (t, 2H), 6.91 (d, 2H), 7.99 (d , 2H)

[2] synthesis of intermediate compound (B3)

Subsequently, 2.5 g (10.0 mmol) of the intermediate compound (A3) obtained above was added to a 100 mL three-necked flask equipped with a cooling tube in a state where PCC 2.2 g (10.0 mmol) and CH ₂ Cl ₂ were added and stirred and mixed. _The solution dissolved in 15.0 mL of ₂ Cl ₂ was added dropwise, and further stirred at room temperature for 6 hours. Thereafter, 90 mL of diethyl ether was added to the solution from which the oily substance adhered to the wall of the flask was filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid.

This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1 (v / v)). The solvent of the obtained solution was distilled off to obtain 1.3 g of a colorless solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this colorless solid is an intermediate compound (B3) (yield 50%).

¹ H-NMR (CDCl ₃ ) δ: 1.3-1.8 (m, 6H), 2.49 (t, 2H), 3.88 (s, 3H), 3.99 (t, 2H), 6.87 (d, 2H), 7.99 (d , 2H), 9.78 (s, 1H)

[3] synthesis of intermediate compound (C3)

In a 50 mL eggplant flask with a cooling tube, 1.25 g (5.0 mmol) of the intermediate compound (B3) obtained above, 0.83 g (5.0 mmol) of 2- (bromomethyl) acrylic acid, 0.8 g of Amberlyst (registered trademark) 15, 8.0 mL of THF, 0.95 g (5.0 mmol) of tin (II) chloride, and 2.0 mL of pure water were added to make a mixture, followed by reaction at 70 ° C. for 5 hours. After completion | finish of reaction, the reaction liquid was filtered under reduced pressure, it mixed with 40 mL of pure waters, and 50 mL of diethyl ether was added and extracted there. Extraction was carried out three times.

Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, and the colorless solid 1.5g was obtained. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this colorless solid is an intermediate compound (C3) (yield 94%).

¹ H-NMR (DMSO-d ₆ ) δ: 1.3-1.8 (m, 8H), 2.62 (m, 1H), 3.04 (s, 1H), 3.81 (s, 3H), 4.05 (t, 2H), 4.54 (m, 1H), 5.70 (s, 1H), 6.01 (s, 1H), 7.03 (d, 2H), 7.89 (d, 2H)

[4] synthesis of intermediate compound (D3)

To a 100 mL eggplant flask with a cooling tube, 35 mL of ethanol, 1.5 g (4.7 mmol) of the intermediate compound (C3) obtained above, and 5 mL of 10% by mass aqueous sodium hydroxide solution were added to form a mixture, and reacted with stirring at 85 ° C for 3 hours. After the completion of the reaction, 300 mL of water and a reaction solution were added to a 500 mL beaker, and the mixture was stirred at room temperature for 30 minutes. 5 mL of a 10% by mass aqueous HCl solution was then added dropwise and filtered to obtain 1.3 g of a white solid.

Next, 1.0 g of the obtained white solid, 1.0 g of Amberlyst (registered trademark) 15, and 20.0 mL of THF were added to a 50 mL eggplant flask with a cooling tube to form a mixture, and the mixture was stirred at 70 ° C for 5 hours to react. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off from the solution to obtain a yellow solid. The yellow solid was purified by recrystallization (hexane / ethyl acetate = 1/1 (v / v)) to obtain 0.9 g of a white solid. The NMR measurement result of this solid is shown below. From this result, it was confirmed that this white solid is an intermediate compound (D3) (yield 71%).

¹ H-NMR (DMSO-d6) δ: 1.2-1.8 (m, 8H), 2.60 (m, 1H), 3.09 (m, 1H), 4.04 (m, 2H), 4.55 (m, 1H), 5.69 ( s, 1H), 6.02 (s, 1H), 6.99 (d, 2H), 7.88 (d, 2H), 12.5 (s, broad, 1H)

[5] Synthesis of Compound (P3)

19.2 g (138.0 mmol) of 3-bromo-1-propanol were dissolved in 100 mL of THF with 18.9 mL of triethylamine and a small amount of BHT, stirred at room temperature, and 12.2 mL (150 mmol) dissolved in 50 mL of THF under cooling by a water bath. Acryloyl chloride) was added dropwise over 15 minutes, stirred for 30 minutes, and stirring was continued overnight while removing the water bath and returning to room temperature. The precipitated TEA hydrochloride was filtered, THF was distilled off from the filtrate, and 100 mL of diethyl ether was added, and the organic layer was washed sequentially with each 80 mL saturated aqueous sodium hydrogen carbonate solution, 0.5 mol / L hydrochloric acid and saturated brine, and sulfuric acid. After drying with magnesium, the solvent was distilled off to obtain 18.2 g of compound (P3). The result of measurement of this solid by NMR is shown below.

¹ H-NMR (CDCl ₃ ) δ: 2.20 (m, 2H), 3.45 (t, 2H), 4.33 (t, 2H), 5.84 (d, 1H), 6.13 (m, 1H), 6.44 (d, 1H )

[6] synthesis of intermediate compound (G3)

To a 500 mL eggplant flask with a cold tube, 17.6 g (94.3 mmol) of biphenol, 18.2 g (94.3 mmol) of compound (P3), 24.0 g (190 mmol) of potassium carbonate, and 250 mL of acetone were added to form a mixture. The reaction was carried out while stirring. After completion of the reaction, the reaction solution was filtered under reduced pressure, and the solvent was distilled off under reduced pressure to obtain a yellow wet solid. This solid was purified by column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: hexane / ethyl acetate = 2/1 (v / v)). The solvent was distilled off from the obtained solution to obtain 6.1 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid is an intermediate compound (G3) (yield 22%).

¹ H-NMR (CDCl ₃ ) δ: 2.21 (m, 2H), 4.13 (t, 2H), 4.40 (t, 2H), 4.99 (s, 1H), 5.87 (d, 1H), 6.15 (m, 1H ), 6.40 (d, 1H), 6.87 (d, 2H), 6.99 (d, 2H), 7.46 (m, 4H)

[7] synthesis of polymerizable liquid crystal compound (E3)

6.1 g (20.0 mmol) of the intermediate compound (D3) obtained above, 6.0 g (20.0 mmol) of the intermediate compound (G3), 0.08 g of DMAP and a small amount of BHT were suspended in 10 mL of methylene chloride under stirring at room temperature, followed by chlorination therein. 4.7 g (23.0 mmol) of DCC dissolved in 20 mL of methylene was added, and after stirring overnight, the precipitated DCC urea was separated by filtration, and the filtrate was sequentially saturated with 60 mL of 0.5 mol / L hydrochloric acid and saturated aqueous sodium hydrogen carbonate solution. After washing twice with brine, drying with magnesium sulfate, the solvent was distilled off and 8.8 g of a polymerizable liquid crystal compound (E3) was obtained by recrystallization with ethanol (yield 75%).

¹ H-NMR (CDCl ₃ ) δ: 1.53 (m, 6H), 1.81 (m, 2H), 2.20 (m, 2H), 2.60 (m, 1H), 3.07 (m, 1H), 4.06 (t, 2H ), 4.12 (t, 2H), 4.40 (t, 2H), 4.54 (m, 1H), 5.63 (d, 1H), 5.85 (d, 1H), 6.10 (m, 1H), 6.24 (d, 1H) , 6.42 (d, 1H), 6.97 (d, 2H), 7.25 (m, 2H), 7.54 (m, 2H), 7.59 (m, 2H), 8.17 (d, 2H)

Moreover, when the liquid crystal phase of a polymeric liquid crystal compound (E3) was observed, it phase-transformed to Smectic X phase at 109 degreeC at the time of temperature rising, phase-transformed to the nematic phase at 144 degreeC, and became an isotropic liquid state at 168 degreeC.

Example 1 Synthesis of Compound (Z1)

[1] synthesis of intermediate compound (P1)

In a 200 mL eggplant flask with a cooling tube, 12.1 g (50.0 mmol) of 4- (4-Hydroxyphenyl) Benzoic Acid Ethyl Ester, 12.5 g of 11-bromo-1-undecanol (50.0 mmol), 13.8 g (100 mmol) of potassium carbonate, and 100 mL of acetone were added to form a mixture, and the mixture was reacted at 64 ° C. for 24 hours with stirring. After the reaction was completed, the reaction solution was poured into 300 mL of pure water to obtain 20.3 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid is an intermediate compound (P1) (yield 98%).

¹ H-NMR (CDCl ₃ ) δ: 1.3-1.7 (m, 19H), 1.81 (m, 2H), 3.67 (m, 2H), 4. 02 (m, 2H), 4.42 (t, 2H), 6.97 (d, 2H), 7.57 (d, 2H), 7.62 (d, 2H), 8.09 (d, 2H)

[2] synthesis of intermediate compound (Q1)

Next, PCG 11 g (51 mmol) and 100 mL of CH ₂ Cl ₂ were added to a 500 mL three-necked flask equipped with a cooling tube, and 20 g (49 mmol) of the intermediate compound (P1) obtained above was added to 100 mL of CH ₂ Cl ₂ . The solution which melt | dissolved was dripped, and it stirred further at room temperature. Thereafter, 100 mL of diethyl ether was added to the solution from which the oily substance attached to the flask wall was removed, and the mixture was filtered under reduced pressure, and then the solvent was distilled off under reduced pressure to obtain a dark green wet solid.

This solid was purified by silica gel column chromatography (column: silica gel 60, 0.063-0.200 mm, manufactured by Merck, eluent: ethyl acetate). The solvent of the obtained solution was distilled off and the colorless solid 12.4g was obtained. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this colorless solid is an intermediate compound (Q1) (yield 62%).

¹ H-NMR (CDCl ₃ ) δ: 1.20-1.65 (m, 19H), 1.81 (m, 2H), 2.41 (t, 2H), 4.11 (t, 2H), 4.42 (m, 2H), 6.99 (d , 2H), 7.57 (d, 2H), 7.63 (d, 2H), 8.01 (d, 2H), 9.77 (s, 1H)

[3] synthesis of intermediate compound (R1)

In a 200 mL eggplant flask with a cooling tube, 12.4 g (30 mmol) of the intermediate compound (Q1) obtained above, 5.4 g (33 mmol) of 2- (bromomethyl) acrylic acid, 75 mL of THF, and 6.3 g (33 mmol) of tin chloride (II) ) And 24 mL of 10% by mass aqueous HCl solution were added to form a mixture, followed by stirring at 70 ° C for 24 hours. After the reaction was completed, the reaction solution was poured into 300 mL of pure water to obtain 15 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid is the target intermediate compound (R1).

¹ H-NMR (CDCl ₃ ) δ: 1.30 (m, 12H), 1.41 (t, 3H), 1.47 (m, 12H), 1.58 (m, 2H), 1.81 (m, 2H), 2.54 (m, 1H ), 3.06 (m, 1H), 4.13 (m, 2H), 4.48 (m, 2H), 4.55 (m, 1H), 5.66 (s, 1H), 6.23 (s, 1H), 7.00 (d, 2H) , 7.55 (d, 2H), 7.6 6 (d, 2H), 8.11 (d, 2H)

[4] synthesis of compound (Z1)

To a 500 mL eggplant flask with a cooling tube, 200 mL of ethanol, 15 g of the intermediate compound (R1) obtained above, and 80 mL of a 10 mass% sodium hydroxide aqueous solution were added to form a mixture, and reacted at 85 ° C. for 5 hours with stirring. After completion of the reaction, 500 mL of water and the reaction solution were added to a 1,000 mL beaker, stirred at room temperature for 30 minutes, and then 50 mL of 10 mass% aqueous HCl solution was added dropwise, followed by filtration to obtain a white solid.

Next, the obtained white solid, 200 mL of THF, and 10 mass% HCl aqueous solution were added to the 50 mL eggplant flask with a cooling tube, it was made into a mixture, and it stirred at 70 degreeC for 5 hours, and made it react. After the completion of the reaction, 500 mL of water and the reaction solution were added to a 1,000 mL beaker, and the resultant was filtered and 12 g of a white solid was obtained. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid is the target compound (Z1) (yield 89%, yield from Q1).

¹ H-NMR (DMSO-d6) δ: 1.32 (m, 14H), 1.57 (m, 2H), 1.71 (m, 2H), 2.54 (m, 1H), 3.09 (m, 1H), 4.01 (m, 2H), 4.55 (m, 1H), 5.69 (s, 1H), 6.02 (s, 1H), 7.05 (d, 2H), 7.67 (d, 2H), 7.73 (d, 2H), 7.97 (d, 2H), 12.89 (s, broad, 1H)

Example 2 Synthesis of Compound (Z2)

[1] synthesis of intermediate compound (P2)

15.0 g (72 mmol) of 4- (4-hydroxyphenyl) benzoate, 17.4 g (50.0 mmol) of 4-bromobutyl-1,3-dioxolane, 19.3 g (140 mmol) of potassium carbonate in a 500 mL eggplant flask with a cooling tube , And 200 mL of acetone were added to make a mixture, and reacted at 64 ° C. for 48 hours with stirring. After the reaction was completed, the reaction solution was poured into 500 mL of pure water to obtain 26.1 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid is an intermediate compound (P2) (yield 98%).

¹ H-NMR (CDCl ₃ ) δ: 1.41 (t, 3H), 1.55-2.00 (m, 6H), 3.86 (m, 2H), 3.99 (m, 4H), 4.39 (m, 2H), 4.89 (m , 1H), 6.97 (d, 2H), 7.61 (m, 4H), 8.07 (d, 2H)

[2] synthesis of intermediate compound (R2)

Next, 18.5 g (50 mmol) of the intermediate compound (P2) obtained above, 9.1 g (55 mmol) of 2- (bromomethyl) acrylic acid, 114 mL of THF, and 10.4 g (55 mmol) of tin chloride (II) were obtained in a 300 mL eggplant flask with a cooling tube. ) And 36 mL of 10 mass% HCl aqueous solution were added to form a mixture, followed by reaction at 70 ° C. for 20 hours. After the reaction was completed, the reaction solution was poured into 500 mL of pure water to obtain 18.7 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this colorless solid is an intermediate compound (R2) (yield 95%).

¹ H-NMR (CDCl ₃ ) δ: 1.42 (t, 3H), 1.60-1.95 (m, 6H), 2.64 (m, 1H), 3.11 (s, 1H), 4.03 (t, 2H), 4.42 (m , 2H), 4.58 (m, 1H), 5.64 (s, 1H), 6.24 (s, 1H), 6.99 (d, 2H), 7.63 (m, 4H), 8.12 (d, 2H)

[3] synthesis of compound (Z2)

200 mL ethanol, 18.7 g (47 mmol) of the intermediate compound (R2) obtained above, and 50 mL of 10 mass% sodium hydroxide aqueous solution were added to the 500 mL eggplant flask with a cooling tube, it was made into a mixture, and it reacted at 85 degreeC for 5 hours, stirring. After completion of the reaction, 600 mL of water and the reaction solution were added to a 1,000 mL beaker, stirred at room temperature for 30 minutes, and filtered to obtain a white solid.

Next, the obtained white solid, 200 mL of THF, and 50 mL of 10 mass% HCl aqueous solution were added to the 500 mL eggplant flask with a cooling tube, it was made into a mixture, and it stirred at 70 degreeC for 5 hours, and made it react. After the reaction was completed, the reaction solution was poured into 500 mL of pure water to obtain 15.9 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid is the target compound (Z2) (yield 92%).

¹ H-NMR (DMSO-d6) δ: 1.50 (m, 2H), 1.75 (m, 4H), 2.58 (m, 1H), 3.12 (m, 1H), 4.04 (m, 2H), 4.59 (m, 1H), 5.72 (s, 1H), 6. 03 (s, 1H), 7.04 (d, 2H), 7.76 (m, 4H), 7.97 (d, 2H), 12.91 (s, broad, 1H)

[Example 3] Synthesis of polymerizable liquid crystal compound (Z3)

1.0 g (2.7 mmol) of Compound (Z2) obtained in Example 2, 0.3 g (3.1 mmol) of phenol, 0.010 g of DMAP, and a small amount of BHT were suspended in 20 mL of methylene chloride under stirring at room temperature, and thereto 5 mL of methylene chloride. To the solution was dissolved 0.7 g (3.5 mmol) of DCC, and stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 mL of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off. It refine | purified by recrystallization by and obtained 0.4g of target polymerizable liquid crystal compounds (Z3) (yield 36%).

¹ H-NMR (CDCl ₃ ) δ: 1.6 to 1.9 (m, 6H), 2.63 (m, 1H), 3.07 (m, 1H), 4.06 (t, 2H), 4.57 (m, 1H), 5.64 (d , 1H), 6.24 (d, 1H), 6.99 (d, 2H), 7.24 (d, 3H), 7.45 (m, 2H), 7.59 (m, 2H), 7.71 (m, 2H), 8.25 (d, 2H)

Moreover, when the liquid crystal phase of a polymeric liquid crystal compound (Z3) was observed, it phase-transformed into a smectic phase at 101 degreeC at the time of temperature rising, phase-transformed to the nematic phase at 114 degreeC, and thermopolymerized at 122 degreeC.

[Example 4] Synthesis of polymerizable liquid crystal compound (Z4)

2.0 g (5.5 mmol) of compound (Z2) obtained in Example 2, 0.9 g (6.0 mmol) of compound (Q4) (methyl 4-hydroxybenzoate, manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.005 g of DMAP, and a small amount BHT was suspended in 25 mL of methylene chloride under stirring at room temperature, and a solution of 1.4 g (7.0 mmol) of DCC dissolved in 5 mL of methylene chloride was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 mL of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off. Purification by recrystallization with ethanol gave 2.1 g of the target polymerizable liquid crystal compound (Z4) (yield 76%).

¹ H-NMR (CDCl 3) δ: 1.60 to 1.95 (m, 6H), 2.61 (m, 1H), 3.07 (m, 1H), 3.98 (s, 3H), 4.01 (t, 2H), 4.54 (m, 1H), 5.64 (d, 1H), 6.25 (d, 1H), 6.99 (d, 2H), 7.26 (d, 2H), 7.62 (m, 2H), 7.71 (m, 2H), 8.15 (d, 2H) ), 8.24 (d, 2 H)

Moreover, when the liquid crystal phase of the polymeric liquid crystal compound (Z4) was observed, it phase-transformed into a smectic phase at 105 degreeC at the time of temperature rising, and thermopolymerized at 130 degreeC.

Example 5 Synthesis of Polymerizable Liquid Crystal Compound (Z5)

3.0 g (6.7 mmol) of compound (Z1) obtained in Example 1, 0.9 g (6.7 mmol) of 2,3-difluorophenol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 0.05 g of DMAP, and A small amount of BHT was suspended in methylene chloride 30 mL under stirring at room temperature, and a solution of 1.9 g (9.0 mmol) of DCC dissolved in 10 mL of methylene chloride was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 mL of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off. It refine | purified by recrystallization by and obtained 2.9 g of target polymerizable liquid crystal compounds (Z5) (yield 77%).

¹ H-NMR (CDCl ₃ ) δ: 1.25 to 1.95 (m, 18H), 2.55 (m, 1H), 3.08 (m, 1H), 4.04 (t, 2H), 4.54 (m, 1H), 5.62 (d , 1H), 6.23 (d, 1H), 6.99 (d, 2H), 7.13 (m, 3H), 7.62 (m, 2H), 7.72 (m, 2H), 8.23 (d, 2H)

Moreover, as a result of observing the liquid crystal phase of a polymeric liquid crystal compound (Z5), at the time of temperature rising, it phase-transformed to Smectic A phase and became isotropic liquid state at 106 degreeC.

[Example 6] Synthesis of polymerizable liquid crystal compound (Z6)

[1] synthesis of intermediate compound (Q6)

5.0 g (32 mmol) of compound (P6) (2-fluoro-4-hydroxybenzoic acid, manufactured by Tokyo Kasei Kogyo Co., Ltd.), 50 ml (55 mmol) of n-butanol, and 2 mL of sulfuric acid were added to a 100 mL eggplant flask with a cooling tube. It was made into a mixture and reacted by stirring at 105 ° C for 2 hours. After completion of the reaction, the reaction solution was poured into 500 mL of pure water, and 100 mL of diethyl ether was added thereto and extracted. Anhydrous magnesium sulfate was added to the organic layer after extraction, it dried, the solvent was distilled off from the solution after filtering under reduced pressure, and 6.6g of white solid was obtained. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this solid is intermediate compound (Q6) (yield 97%).

¹ H-NMR (CDCl ₃ ) δ: 0.98 (t, 3H), 1.47 (m, 2H), 1.74 (m, 2H), 4.32 (m, 2H), 6.27 (s, 1H), 6.47 (m, 2H ), 7.88 (m, 1 H)

[2] synthesis of polymerizable liquid crystal compound (Z6)

2.3 g (5.0 mmol) of the compound (Z1) obtained in Example 1, 1.1 g (5.0 mmol) of the intermediate compound (Q6) obtained above, 0.040 g of DMAP, and a small amount of BHT were suspended in 20 mL of methylene chloride under stirring at room temperature. Then, a solution in which DCC 1.4 g (7.0 mmol) was dissolved in 5 mL of methylene chloride was added thereto, and the mixture was stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 mL of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off. Purification by recrystallization with ethanol gave 2.5 g of the target polymerizable liquid crystal compound (Z6) (yield 76%).

¹ H-NMR (CDCl ₃ ) δ: 1.15 (t, 3H), 1.25 to 1.90 (m, 22H), 2.56 (m, 1H), 3.10 (m, 1H), 4.05 (t, 2H), 4.37 (t , 2H), 4.56 (m, 1H), 5.63 (d, 1H), 6.24 (d, 1H), 7.02 (d, 2H), 7.14 (m, 2H), 7.60 (d, 2H), 7.72 (d, 2H), 8.05 (m, 1H), 8.23 (d, 2H)

Moreover, as a result of observing the liquid crystal phase of a polymeric liquid crystal compound (Z6), at the time of temperature rising, it phase-transformed into the Smectic A phase at 58 degreeC, and thermopolymerized at 127 degreeC.

[Example 7] Synthesis of polymerizable liquid crystal compound (Z7)

2.5 g (7.4 mmol) of the compound (Z2) obtained in Example 2, 0.84 g (7.5 mmol) of 4-fluorophenol, 0.1 g of DMAP, and a small amount of BHT were suspended in 30 mL of methylene chloride under stirring at room temperature, and To 10 ml of methylene chloride was added a solution in which DCC 2.1 g (10.0 mmol) was dissolved and stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 mL of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off. It refine | purified by recrystallization by and obtained 1.4 g of target polymerizable liquid crystal compounds (Z7) (yield 41%).

¹ H-NMR (CDCl ₃ ) δ: 1.67 (m, 2H), 1.80 (m, 2H), 1.90 (m, 2H), 2.64 (m, 1H), 3.10 (m, 1H), 4.04 (m, 2H ), 4.57 (m, 1H), 5.65 (m, 1H), 6.25 (m, 1H), 6.99 (d, 2H), 7.10 (m, 2H), 7.20 (m, 2H), 7.61 (d, 2H) , 7.71 (d, 4H), 8.24 (d, 2H)

Moreover, when the liquid crystal phase of a polymeric liquid crystal compound (Z7) was observed, when it heated up, it phase-transformed into the smectic phase at 79 degreeC, phase-transformed to the nematic phase at 120 degreeC, and thermally polymerized at 129 degreeC.

Example 8 Synthesis of Compound (Z8)

[1] synthesis of intermediate compound (P8)

To a 500 mL eggplant flask with a cold tube, 18.6 g (100 mmol) of biphenol, 10.0 g (48 mmol) of 4-bromobutyl-1,3-dioxolane, 13.8 g (100 mmol) of potassium carbonate, and 200 mL of acetone were added to form a mixture. It was made to react, stirring at 64 degreeC for 24 hours. After the reaction was completed, the reaction solution was poured into 500 mL of pure water to obtain a white solid. This solid was mixed with 150 mL of methanol, and the solvent was distilled off after filtration to obtain a white solid. Next, this solid was mixed with 70 mL of chloroform, and the solvent was distilled off after filtration to obtain 7.2 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid is an intermediate compound (P8) (yield 48%).

_{^{1 H-NMR (CDCl 3)}} δ: 1.62 (m, 2H), 1.76 (m, 2H), 1.87 (m, 2H), 3.85 (m, 2H), 4.00 (m, 4H), 4.90 (m, 1H ), 6.87 (m, 4H), 7.42 (m, 4H)

[2] synthesis of compound (Z8)

Next, 7.2 g (23 mmol) of the intermediate compound (P8) obtained above, 4.1 g (25 mmol) of 2- (bromomethyl) acrylic acid, 60 mL of THF, and 4.7 g (25 mmol) of tin chloride (II) were obtained in a 300 mL eggplant flask with a cooling tube. ) And 19 mL of 10 mass% HCl aqueous solution were added to form a mixture, and the mixture was stirred at 70 ° C for 5 hours to react. After completion of the reaction, the reaction solution was poured into 200 mL of pure water to obtain 6.1 g of a white solid.

The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that this white solid is the target compound (Z8) (yield 78%).

¹ H-NMR (CDCl ₃ ) δ: 1.60-1.95 (m, 6H), 2.64 (m, 1H), 3.11 (s, 1H), 4.02 (t, 2H), 4.60 (m, 1H), 4.82 (s , 1H), 5.64 (s, 1H), 6.24 (s, 1H), 6.94 (d, 2H), 7.44 (m, 4H)

Example 9 Synthesis of Polymerizable Liquid Crystal Compound (Z9)

0.9 g (2.5 mmol) of Compound (Z8) obtained in Example 8, 0.45 g (2.5 mmol) of 4-fluorobenzoic acid, 0.03 g of DMAP, and a small amount of BHT were suspended in 15 mL of methylene chloride under stirring at room temperature, and To 5 ml of methylene chloride was added a solution in which DCC 0.7 g (3.5 mmol) was dissolved and stirred overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 50 mL of 0.5 mol / L hydrochloric acid, 50 mL of saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated saline solution, dried over magnesium sulfate, and then the solvent was distilled off. Purification by recrystallization with ethanol gave 0.9 g of the target polymerizable liquid crystal compound (Z9) (yield 82%). The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that it is a polymeric liquid crystal compound (Z9).

¹ H-NMR (CDCl ₃ ) δ: 1.59 (m, 2H), 1.70 (m, 2H), 1.86 (m, 2H), 2.59 (m, 1H), 3.08 (m, 1H), 4.00 (m, 2H ), 4.57 (m, 1H), 5.64 (m, 1H), 6.25 (m, 1H), 6.96 (d, 2H), 7.20 (m, 4H), 7.50 (d, 2H), 7.60 (d, 2H) , 8.20 (m, 2 H)

Moreover, when the liquid crystal phase of a polymeric liquid crystal compound (Z9) was observed, it phase-transformed into a smectic phase at 99 degreeC at the time of temperature rising, phase-transformed to the nematic phase at 112 degreeC, and thermally polymerized at 123 degreeC.

EXAMPLES 10-15, COMPARATIVE EXAMPLE 1 Polymerizable liquid crystal composition and its polymer (film)

The compounds used in the following Examples and Comparative Examples are as follows. In addition, the composition of the composition prepared in Examples 10-15 and Comparative Example 1 is shown in Table 1 (unit is mg).

Compound (mg) E1 E2 E3 Z3 Z4 Z5 Z7 Example 10 120 90 60 30 - - - Example 11 120 90 60 - 30 - - Example 12 90 90 60 - 60 - - Example 13 90 90 60 - - 60 - Example 14 120 90 60 - - - 30 Example 15 90 90 60 - - - 60 Comparative Example 1 120 120 60 - - - -

Example 10 Polymerizable Liquid Crystal Composition and Polymerized Material (Film)

120 mg of a polymerizable liquid crystal compound (E1), 90 mg of a polymerizable liquid crystal compound (E2), 60 mg of a polymerizable liquid crystal compound (E3), 30 mg of a polymerizable liquid crystal compound (Z3), Irgacure 369 (brand name) made by Chiba Chemical Co., Ltd. which is a photoinitiator. 4 mg and 0.6 mg of R30 (manufactured by DIC Corporation) as surfactants were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

This polymeric liquid crystal composition was apply | coated to the liquid crystal aligning film surface of the board | substrate with a liquid crystal aligning film by spin coating (1,000 rpm, 20 seconds), prebaked for 60 second on the 100 degreeC hotplate, and was cooled to room temperature. At this time, the polymerizable composition on the substrate was in a liquid crystal state. The board | substrate with a liquid crystal aligning film used here apply | coats a liquid crystal aligning agent (SE-1410 by Nissan Kagaku Kogyo Co., Ltd.) by spin coating to the ITO surface of a glass substrate with ITO, bakes at 230 degreeC, and is 100 nm in thickness. After forming a thin film, the rubbing process was performed.

Next, the coating film formed on the board | substrate with a liquid crystal aligning film was irradiated with the light of 2,000 mJ / cm <^2> intensity | strength using a metal halide lamp in the nitrogen atmosphere, and the polymeric liquid crystal composition was polymerized. The film obtained had a film thickness of 1.9 µm and observed with a polarizing microscope to confirm that the film was horizontally aligned with the substrate surface. The retardation value was 302 nm and the haze value was 0.32.

When this film was heated for 30 minutes on a 160 degreeC hotplate, the film thickness was 1.7 micrometers, the retardation value was 238 nm and haze value was 0.17. Moreover, when the film after heating for 160 degreeC and 30 minute (s) was heated on the 200 degreeC hotplate for 1 hour, the film thickness was 1.6 micrometers, the retardation value was 213 nm and haze value was 0.08.

Example 11 Polymerizable Liquid Crystal Composition and Polymerized Material thereof (Film)

A polymerizable liquid crystal composition was obtained in the same manner as in Example 10 except that the polymerizable liquid crystal compound (Z3) was changed to the polymerizable liquid crystal compound (Z4).

Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. In addition, the composition on the board | substrate after prebaking was a liquid crystal state.

The film thickness of the obtained film was 1.8 µm, and when observed with a polarizing microscope, it was confirmed that the film was horizontally aligned with the substrate surface. The retardation value was 29 nm and the haze value was 0.24.

When this film was heated for 30 minutes on a 160 degreeC hotplate, the film thickness was 1.7 micrometers, the retardation value was 30 nm and haze value was 0.24. Moreover, when the film after heating for 160 degreeC and 30 minute (s) was heated on the 200 degreeC hotplate for 1 hour, the film thickness was 1.6 micrometers, the retardation value was 33 nm and haze value was 0.16.

Example 12 Polymerizable Liquid Crystal Composition and Polymerized Material (Film)

90 mg of a polymerizable liquid crystal compound (E1), 90 mg of a polymerizable liquid crystal compound (E2), 60 mg of a polymerizable liquid crystal compound (E3), 60 mg of a polymerizable liquid crystal compound (Z4), Irgacure 369 (brand name) by Chibagaigi Inc. which is a photoinitiator. 4 mg and 0.6 mg of R30 (manufactured by DIC Corporation) as surfactants were dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. In addition, the composition on the board | substrate after prebaking was a liquid crystal state.

The film obtained had a film thickness of 1.8 µm and observed with a polarizing microscope to confirm that the film was horizontally aligned with the substrate surface. And the retardation value was 1 nm, and haze value was 0.00.

When this film was heated for 30 minutes on a 160 degreeC hotplate, the film thickness was 1.7 micrometers, the retardation value was 1 nm and haze value was 0.09. Moreover, when the film after heating for 160 degreeC and 30 minutes was heated on the 200 degreeC hotplate for 1 hour, the film thickness was 1.6 micrometers, the retardation value was 1 nm and haze value was 0.01.

Example 13 Polymerizable Liquid Crystal Composition and Polymerized Material thereof (Film)

A polymerizable liquid crystal composition was obtained in the same manner as in Example 12 except that the polymerizable liquid crystal compound (Z4) was changed to the polymerizable liquid crystal compound (Z5).

Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. In addition, the composition on the board | substrate after prebaking was a liquid crystal state.

The film obtained had a film thickness of 1.9 µm and was observed with a polarizing microscope to confirm that the film was horizontally aligned with the substrate surface. And the retardation value was 2 nm, and haze value was 0.21.

When this film was heated for 30 minutes on a 160 degreeC hotplate, the film thickness was 1.7 micrometers, the retardation value was 2 nm and haze value was 0.14. Moreover, when the film after heating for 160 degreeC and 30 minutes was heated on the 200 degreeC hotplate for 1 hour, the film thickness was 1.6 micrometers, the retardation value was 2 nm, and the haze value was 0.08.

Example 14 Polymerizable Liquid Crystal Composition and Polymerized Material thereof (Film)

A polymerizable liquid crystal composition was obtained in the same manner as in Example 10 except that the polymerizable liquid crystal compound (Z3) was changed to the polymerizable liquid crystal compound (Z7).

Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. In addition, the composition on the board | substrate after prebaking was a liquid crystal state.

The film obtained had a film thickness of 1.8 µm and observed with a polarizing microscope to confirm that the film was horizontally aligned with the substrate surface. The retardation value was 305 nm and the haze value was 0.29.

When this film was heated for 30 minutes on a 160 degreeC hotplate, the film thickness was 1.7 micrometers, the retardation value was 260 nm and haze value was 0.24. Moreover, when the film after heating for 160 degreeC and 30 minute (s) was heated for 1 hour on the 200 degreeC hotplate, the film thickness was 1.6 micrometers, the retardation value was 232 nm and haze value was 0.16.

[Example 15] Polymerizable liquid crystal composition and its polymer (film)

A polymerizable liquid crystal composition was obtained in the same manner as in Example 12 except that the polymerizable liquid crystal compound (Z4) was changed to the polymerizable liquid crystal compound (Z7).

Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. In addition, the composition on the board | substrate after prebaking was a liquid crystal state.

The film obtained had a film thickness of 1.8 µm and observed with a polarizing microscope to confirm that the film was horizontally aligned with the substrate surface. And the retardation value was 86 nm, and haze value was 0.09. When this film was heated for 30 minutes on a 160 degreeC hotplate, the film thickness was 1.7 micrometers, the retardation value was 86 nm and haze value was 0.08. Moreover, when the film after heating for 160 degreeC and 30 minutes was heated on the 200 degreeC hotplate for 1 hour, the film thickness was 1.6 micrometers, the retardation value was 85 nm and haze value was 0.08.

[Comparative Example 1] A polymerizable liquid crystal composition and its polymer (film)

120 mg of a polymerizable liquid crystal compound (E1), 120 mg of a polymerizable liquid crystal compound (E2), 60 mg of a polymerizable liquid crystal compound (E3), 4 mg of Irgacure 369 (trade name) manufactured by Chiba Co., Ltd., a photopolymerization initiator, and R30 (DIC) which is a surfactant. 0.6 mg of (manufactured) was dissolved in 0.7 g of cyclohexanone to obtain a polymerizable liquid crystal composition.

Using this polymerizable liquid crystal composition, a film was obtained in the same manner as in Example 10. In addition, the composition on the board | substrate after prebaking was a liquid crystal state.

The film obtained had a film thickness of 1.9 µm and was observed with a polarizing microscope to confirm that the film was horizontally aligned with the substrate surface. The retardation value was 299 nm and the haze value was 0.09.

When this film was heated for 30 minutes on a 160 degreeC hotplate, the film thickness was 1.7 micrometers, the retardation value was 234 nm and haze value was 0.08. Moreover, when the film after heating for 160 degreeC and 30 minutes was heated on the 200 degreeC hotplate for 1 hour, the film thickness was 1.7 micrometers, the retardation value was 205 nm and haze value was 0.08.

Table 2 shows the theorem of the above Examples 10 to 15 and Comparative Example 1.

Moreover, the retardation value angle dependence in wavelength 590nm of the film produced by the said Example 10-15 and the comparative example 1 is shown in FIG.

Moreover, the result of having measured the average tilt angle of wavelength 590nm of the film produced by the said Example 10-15 and the comparative example is shown in Table 2 together.

Δnd (nm) Haze value
(%) Average tilt angle
(°) After exposure Bake 1 Bake 2 Example 10 302 238 213 0.17 14 Example 11 29 30 33 0.24 61 Example 12 One One One 0.09 88 Example 13 2 2 2 0.14 85 Example 14 305 260 232 0.24 10 Example 15 86 86 85 0.08 50 Comparative Example 1 299 234 205 0.08 5

Bake 1: After heating at 160 ° C. for 30 minutes

Bake 2: 160 ° C, heated for 30 minutes → 200 ° C, heated for 1 hour

As shown in Table 2, in the films produced in Examples 10 to 15, the haze after baking was kept low (that is, the thermal stability was high), and the average angle could be controlled by adding the polymerizable liquid crystal compound of the present invention. I knew it was.

Claims (10)

It is represented by following formula [1], The polymeric liquid crystal compound characterized by the above-mentioned.

(In formula, X <^1> , X <^2> , X <^3> and X <^4> show a hydrogen atom or a fluorine atom independently from each other, R represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkoxy group, or the alkoxycarbonyl group. , G represents a -C (= 0) O- or -OC (= 0)-group, and n represents an integer of 4 to 10. The polymerizable liquid crystal composition containing the polymerizable liquid crystal compound according to claim 1. The polymerizable liquid crystal composition according to claim 2, further comprising a liquid crystal compound having at least one polymerizable group in one molecule. 4. The polymerizable liquid crystal composition according to claim 3, wherein the liquid crystal compound is a compound having at least one polymerizable group represented by the following formula [2] or [3] in one molecule.

(In the formula, the dashed line represents the bond.) The polymerizable liquid crystal composition according to claim 3 or 4, wherein the liquid crystal compound is at least one selected from the group consisting of compounds represented by the following formulas [4] and [5].

(In formula, X represents a fluorine atom, a cyano group, or a C4-C8 monovalent hydrocarbon group, f1 and f2 respectively independently represent the integer of 2-9, g represents the integer of 2-9, M ¹ , M ² and M ³ each independently represent a group represented by the following formula [2] or [3].)

(In the formula, the dashed line represents the bond.) The polymer obtained from the polymeric liquid crystal composition of any one of Claims 2-5. The film obtained from the polymeric liquid crystal composition of any one of Claims 2-5. The orientation film obtained from the polymeric liquid crystal composition of any one of Claims 2-5. The optical member provided with the polymer of Claim 6, or the oriented film of Claim 8. The compound represented by following formula [6].

(In formula, Y represents -OH or -COOH and k represents the integer of 4-10.)

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