TWI439537B - Liquid crystal compositions and their use - Google Patents

Description

Liquid crystal composition and use thereof

The present invention relates to a liquid crystal composition for producing an optical material for a circularly polarizing separation sheet or the like, and a circularly polarizing separation sheet produced from the liquid crystal composition, and a brightness enhancement film and a liquid crystal display device including the circular polarization separation sheet.

In order to enhance the brightness and the like of the display device such as a liquid crystal display device, it is known to provide a circularly polarized light separating sheet that reflects a specific circularly polarized light and reflects other light. In the circularly polarizing separator, it is known that a polymer exhibiting cholesteric liquid crystal property is applied onto a substrate, and it is aligned, dried, and the like; and a liquid combination containing a polymerizable monomer exhibiting cholesteric liquid crystallinity is known. The object is applied to a substrate, aligned, polymerized, and the like. There have been many conventional liquid crystal compositions as described above (Examples Patent Documents 1 to 3).

The circular polarizing separation sheet is preferably one in which the polymer is uniformly aligned from the viewpoint of obtaining high optical performance, and the selective reflection band is wide. However, when a liquid crystal composition containing a compound having a high value of Δn (inherent complex refractive index) of 0.18 or more is used to enlarge the selective reflection wavelength band, it is difficult to uniformly align the polymer even with a thick layer of about 5 μm or more. It is detrimental to the uniformity of the alignment. Conversely, in the case of a thinner layer, it is difficult to expand the selective reflection band. Therefore, in order to produce a circularly polarizing separator having a wide reflection band, it is necessary to adopt a method of laminating a plurality of layers having a uniform alignment of 3 μm in a plurality of times, and there is a problem that the steps are complicated.

[Patent Document 1] US Patent Application Publication No. 2005/0045854

[Patent Document 2] Japanese Patent No. 3776632 (Corresponding Bulletin, U.S. Patent Specification No. 5,863,457)

[Patent Document 3] Japanese Laid-Open Patent Publication No. Hei 8-3111 (corresponding publication, U.S. Patent Specification No. 5,863,457)

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal composition comprising a compound having a high Δn value, a uniform alignment, and a layer having a wide reflection band.

Another object of the present invention is to provide a circularly polarizing separation sheet which has a wide reflection band, uniform optical characteristics, and can be easily produced, and the use of the circularly polarizing separation sheet.

As a result of intensive studies to solve the above problems, the present inventors have found that a polymerizable liquid crystal compound having a specific liquid crystal primordial structure is used as a component of a liquid crystal composition, and a low molecular compound having a specific structure and a polymerizable pair are added. The palm compound and the photopolymerization initiator are other components, and a liquid crystal composition capable of simultaneously achieving high alignment uniformity and a wide selective reflection band can be obtained, and the present invention has been completed. That is, according to the present invention, the following can be provided.

[1] A liquid crystal composition comprising: a non-pivotic polymerizable liquid crystal compound (i) having Δn of 0.18 or more; and a non-pivotic polymerizable compound (ii) having Δn of 0.18 or more; a polymerizable palmitic compound; and a photopolymerization initiator, wherein the polymerizable liquid crystal compound (i) is a compound represented by the following formula (I): In the formula, Y ₁ ~Y ₆ are each independently represented as a single bond, -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC(=O)- O-, -NR ¹ -C(=O)-, -C(=O)-NR ¹ -, -OC(=O)-NR ¹ -, -NR ¹ -C(=O)-O-, - NR ¹ -C(=O)-NR ¹ -, -O-NR ¹ -, or -NR ¹ -O-, and R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; G ₁ and G ₂ Each of the two groups may independently represent a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent. The aliphatic group may also be interposed between -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC(=O)-O-, -NR ² -C ( =O)-, -C(=O)-NR ² -, -NR ² -, or -C(=O)- (except that -O- and -S- are respectively adjacent to each other); R ² system A hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Z ₁ and Z ₂ are each independently represented by an alkenyl group having 2 to 10 carbon atoms which may be substituted by a halogen atom; and A ₁ and A ₂ are each independently represented by carbon. a valence of 1 to 30 organic groups A; X ₁ to X ₈ are independently represented by a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cyano group, a nitro group, and -OR ³ , -OC(=O)-R ³ , -C(=O)-OR ³ , -OC(=O)-OR ³ , -NR ⁴ -C(=O)-R ³ , -C(=O -NR ³ R ⁴ , or -OC(=O)-R ⁴ , NR ³ R ⁴ ; R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, in the alkyl group In the case of the alkyl group, there may be -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC(=O)-O-, -NR ⁵ -C(=O)-, -C(=O)-NR ⁵ -, -NR ⁵ -, or -C(=O)- (wherein -O- and -S- are respectively adjacent to each other); ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; a and b each independently represent 0 or 1; and the above polymerization The compound (ii) is a compound represented by the following formula (II): Z ³ -MG-O(CH ₂ )n ₁ -Y ¹¹ -Z ⁴ (II), wherein the Z ³ group is selected from a hydrogen atom. a group of a group consisting of an alkyl group having 1 to 2 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an amine group, and a cyano group; and the MG group is selected from 4, 4'-binar Liquid crystal primordium of a group consisting of phenylene, 4,4'-bicyclohexylene, 2,6-naphthylene, and 4,4'-benzylidene: n ₁ represents an integer of 0-6 Y ¹¹ is represented by a single bond, -O-, -S-, -CO-, -CS-, -OCO-, -CH ₂ -, -OCH ₂ -, -NHCO-, -OCOO-, - CH ₂ COO-, and -CH ₂ OCO- are selected from the group consisting of the group; Z ⁴ represents an alkenyl group having 2 to 10 carbon atoms which may be substituted by a halogen atom.

[2] The above liquid crystal composition, wherein A ₁ and A ₂ of the polymerizable liquid crystal compound (i) each independently represent a phenylene group which may have a substituent, a diphenylene group which may have a substituent, or A naphthylene group having a substituent.

[3] The above liquid crystal composition, wherein Z ₁ and Z ₂ of the polymerizable liquid crystal compound (i) each independently represent CH ₂ =CH-, CH ₂ =C(CH ₃ )-, CH ₂ =CH-CH ₂ -, CH ₃ -CH=CH-, CH ₂ =CH-CH ₂ -CH ₂ -, CH ₂ =C(CH ₃ )-CH ₂ -CH ₂ -, (CH ₃ ) ₂ C=CH-CH ₂ -, (CH ₃ ) ₂ C=CH-CH ₂ -CH ₂ -, CH ₂ =C(Cl)-, CH ₂ =C(CH ₃ )-CH ₂ -,CH ₃ -CH=CH-CH ₂ - .

[4] The liquid crystal composition, wherein the ratio of the polymerizable liquid crystal compound (i) to the polymerizable compound (ii) is (the total weight of the polymerizable compound (ii)) / (the polymerizable liquid crystal compound (i) The total weight of the weight ratio is 0.05 to 1.

[5] The liquid crystal composition described above, wherein the polymerizable compound (ii) has a molecular weight of less than 600.

[6] The above liquid crystal composition further comprising a surfactant.

[7] A circularly polarizing separation sheet characterized in that the liquid crystal composition is applied to a transparent resin substrate and cured.

[8] A method for producing a circularly polarizing separation sheet, comprising the steps of: applying the liquid crystal composition to a transparent resin substrate to obtain a liquid crystal layer, and comprising irradiating and/or warming by at least one light irradiation; The step of hardening the above liquid crystal layer.

[9] A brightness enhancement film comprising: the above circularly polarizing separation sheet; and a phase difference film.

[10] A liquid crystal display device comprising: the brightness enhancement film; and a liquid crystal panel.

The cholesteric liquid crystal composition of the present invention is useful as a simple method A material of a circularly polarizing separator that is homogeneous and has a wide reflection band.

The circularly polarizing separator of the present invention is homogeneous and has a wide reflection band. Therefore, the liquid crystal display device of the present invention having the brightness enhancement film of the present invention having the circularly polarizing separation sheet has high luminance and can exhibit uniform display performance.

1. The liquid crystal composition of the present invention

The liquid crystal composition of the present invention comprises: a specific non-pivotic polymerizable liquid crystal compound (i) having a Δn of 0.18 or more; Δn of 0.18 or more a specific non-pivoting polymeric compound (ii); a polymerizable palmitic compound; and a photopolymerization initiator. Hereinafter, each component will be described in order.

1-1. Polymerizable liquid crystal compound (i)

The polymerizable liquid crystal compound (i) is a compound represented by the above formula (I), and is not a polymerizable compound (ii) to be described later, nor is it a polymerizable palmitic compound.

In the above formula (I), Y ₁ ~ Y ₆ are each independently represented, single bond, -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC (=O)-O-, -NR ¹ -C(=O)-, -C(=O)-NR ¹ -, -OC(=O)-NR ¹ -, -NR ¹ -C(=O) -O-, -NR ¹ -C(=O)-NR ¹ -, -O-NR ¹ -, or -NR ¹ -O-. Here, R ¹ means a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ¹ is preferably a hydrogen atom or a methyl group.

Particularly preferable as the combination of Y, Y ₁ and Y ₃ are -C(=O)-O-, and Y ₄ and Y ₆ are -OC from the viewpoints of ease of synthesis and better effect of the desired effect of the present invention. (=O)-, Y ₂ and Y ₅ are combinations of -O-; or, Y ₁ ~Y ₃ are -C(=O)-O-, and Y ₄ ~Y ₆ are -OC(=O)- combination.

Each of G ₁ and G ₂ is independently a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent, and preferably a divalent aliphatic group having 1 to 12 carbon atoms.

The divalent aliphatic group having 1 to 20 carbon atoms of G ₁ and G ₂ is preferably a chain-like aliphatic group having an alkylene group having 1 to 20 carbon atoms and an alkenylene group having 2 to 20 carbon atoms.

From the viewpoint of more satisfactorily exhibiting the desired effects of the present invention, an alkylene group such as an ethylene group, a butylene group, a hexylene group or an octylene group is preferred.

The substituent of the aliphatic group of G ₁ and G ₂ may, for example, be a halogen atom or an alkoxy group having 1 to 6 carbon atoms. The halogen atom is preferably a fluorine atom, and the alkoxy group is preferably a methoxy group or an ethoxy group.

Further, in the above aliphatic group, it may also be present in -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC(=O)-O-, -NR ² -C(=O)-, -C(=O)-NR ² -, -NR ² -, or -C(=O)- (wherein -O- and -S- are removed, respectively.) . Here, R ² means a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ² is preferably a hydrogen atom or a methyl group.

Z ₁ and Z ₂ each independently represent an alkenyl group having 2 to 10 carbon atoms which may be substituted by a halogen atom.

Specific examples of the alkenyl group having 2 to 10 carbon atoms of Z ₁ and Z ₂ include CH ₂ =CH-, CH ₂ =C(CH ₃ )-, CH ₂ =CH-CH ₂ -, and CH ₃ -CH= CH-, CH ₂ =CH-CH ₂ -CH ₂ -, CH ₂ =C(CH ₃ )-CH ₂ -CH ₂ -, (CH ₃ ) ₂ C=CH-CH ₂ -, (CH ₃ ) ₂ C =CH-CH ₂ -CH ₂ -, CH ₂ =C(Cl)-, CH ₂ =C(CH ₃ )-CH ₂ -, CH ₃ -CH=CH-CH ₂ -, and the like.

The number of carbon atoms of the alkenyl group is preferably from 2 to 6. The halogen atom of the substituent of the alkenyl group of Z ₁ and Z ₂ is preferably a chlorine atom.

Among them, from the viewpoint of more well showing the desired effect of the present invention, Z ₁ and Z ₂ are CH ₂ =CH ₂ -, CH ₂ =CH(CH ₃ )-, CH ₂ =C(Cl)-, CH ₂ More preferably, CH-CH ₂ -, CH ₂ =C(CH ₃ )-CH ₂ -, or CH ₂ =C(CH ₃ )-CH ₂ -CH ₂ -.

X ₁ to X ₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cyano group, a nitro group, -OR ³ , -OC(=O)-R ³ , -C(=O)-OR ³ , -OC(=O)-OR ³ , -NR ⁴ -C(=O)-R ³ , -C(=O)-NR ³ R ⁴ , or -OC(= O)-NR ³ R ⁴ . The substituent in the case where X ₁ to X ₈ are an alkyl group having a substituent may, for example, be a halogen atom, a hydroxyl group, a methyl group or an ethyl group. Here, R ³ and R ^{4 each} represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, and in the case of an alkyl group, the alkyl group may also be interposed in -O-, -S-, -OC ( =O)-, -C(=O)-O-, -OC(=O)-O-, -NR ⁵ -C(=O)-, -C(=O)-NR ⁵ -, -NR ⁵ -, or -C(=O)- (wherein -O- and -S- are removed, respectively.). Here, R ⁵ means a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. When R ³ and R ⁴ are a substituent group, the substituent may be independently a halogen atom, a hydroxyl group, a methyl group or an ethyl group.

From the viewpoint that the raw materials are easy to start, (1) X ₁ to X ₈ are each a hydrogen atom; (2) X ₁ to X ₅ and X ₇ are each a hydrogen atom, and X ₆ and X ₈ are -OCH ₃ , -OCH ₂ CH ₃ , or -CH ₃ ; (3) X ₁ ~X ₅ , X ₇ and X ₈ are each a hydrogen atom, and X ₆ is -C(=O)-OR ³ , -OCH ₃ , -OCH ₂ CH ₃ , -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ or a fluorine atom; (4) X ₁ ~X ₄ and X ₆ ~X ₈ are each a hydrogen atom, and X ₅ is -C(= O)-OR ³ , -OCH ₃ , -OCH ₂ CH ₃ , -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ or a fluorine atom is preferred.

Further, in the above formula (I), each is bonded to A ₁ and A ₂ in the formula: -Y ₂ -(G ₁ -Y ₁ )aZ ₁ and the formula: -Y ₅ -(G ₂ -Y ₆ )bZ Specific examples of the basis of ₂ are as follows. Further, the above a and b represent the number of (G ₁ -Y ₁ ) units and (G ₂ -Y ₆ ) units, and a and b are each independently represented by 0 or 1. As a particularly good combination of a and b, a both a and b are a total of 1 from the viewpoints of easiness of synthesis and better effect of the desired effect of the present invention.

An example in which a or b is 1, that is, a structure represented by the following formula (C) will be described below.

Wherein Y ₂ or Y ₅ is equivalent to -C(=O)-O-, G ₁ or G ₂ is a hexylene group, and Y ₁ or Y ₆ is equivalent to -OC(=O)-, Z ₁ or Z ₂ is equivalent to a vinyl group.

Further, specific examples thereof are shown below.

[Chemical 3]

[Chemical 4]

[Chemical 5]

An example of a or b = 0, that is, the configuration represented by the following formula (D) will be described below.

In the formula, Y ₂ or Y ₅ is -C(=O)-O-, and Z ₁ or Z ₂ is equivalent to a vinyl group.

Further, specific examples thereof are shown below.

[Chemistry 7]

The A ₁ and A ₂ systems independently represent a divalent organic group A having 1 to 30 carbon atoms. The carbon number of the organic group A is preferably 6 to 20. The organic group A of A ₁ and A ₂ is not particularly limited, and those having an aromatic ring are preferred.

Specific examples of A ₁ and A ₂ include the following.

The organic group exemplified as specific examples of A ₁ and A ₂ may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, and a -C(=O)-OR group. Here, R is an alkyl group having 1 to 6 carbon atoms. Among these, a halogen group, an alkyl group, an alkoxy group is preferable, a halogen atom is a fluorine atom, an alkyl group is a methyl group, an ethyl group, a propyl group, and an alkoxy group is more preferably a methoxy group or an ethoxy group.

The above A ₁ and A ₂ may have a substituent in the following formula (A ₁₁ ), (A ₂₁ ) and (A ₃₁ ), and may have a substituent, from the viewpoint of more clearly exhibiting the desired effect of the present invention. a phenylene group, a diphenylene group which may have a substituent, or a naphthylene group which may have a substituent, wherein the phenylene group which may have a substituent at the following formula (A ₁₁ ) may have a substituent The base is better.

In the present invention, the polymerizable liquid crystal compound (i) represented by the above formula (I) may be the same or different in the two groups represented by the following formula.

A preferred specific example of the polymerizable liquid crystal compound (i) represented by the above formula (I) is as follows. However, the polymerizable liquid crystal compound (i) of the present invention is not limited to the following compounds.

[Chemistry 13]

The polymerizable liquid crystal compound (i) used in the present invention has a Δn value of 0.18 or more and preferably 0.22 or more. When a compound having a Δn value of 0.30 or more is used, the absorption end of the long-wavelength side of the ultraviolet absorption spectrum has a visible region, and even if the absorption end of the spectrum reaches the visible region, It can also be used as long as it does not adversely affect the desired optical properties. By such a high value of Δn, a circularly polarizing separator having high optical properties (for example, circular polarization separation characteristics) can be imparted. The upper limit of Δn is not particularly limited and may be, for example, 0.35, preferably 0.30.

The polymerizable liquid crystal compound (i) used in the present invention can be formed by combination, -O-, -S-, -NH-C(=O)-, -C(=O)NH-, -NHC ( =O) A conventional method for various chemical bonding of NH-, -OC(=O)-, -C(=O)-O-, etc. (refer, for example, the synthesis method of the organic compound of the Shanluo Kazan functional group [ I], [II] Hirokawa Bookstore, issued in 1976). The polymerizable liquid crystal compound (i) typically has an ether bond (-O-), an ester bond (-C(=O)-O-), and a guanamine bond (-C(=O)NH-). And the formation reaction of ruthenium chloride (-COCl) is produced by suitably bonding a plurality of conventional compounds having a desired structure to a modification.

The formation of an ether bond can be carried out, for example, as follows.

1) A compound represented by the formula: Q ₁ -X (X represents a halogen atom) and a compound represented by the formula: Q ₂ -OM (M: an alkali metal (mainly sodium)) are mixed and condensed. In the formula, Q ₁ and Q _{2 each} represent an arbitrary organic group B (hereinafter, the same). This reaction is generally referred to as Williamson synthesis.

2) A compound represented by the formula: Q ₁ -X (X represents a halogen atom) and a compound represented by the formula: Q ₂ -OH are mixed and condensed in the presence of a base such as sodium hydroxide or potassium hydroxide.

3) A compound represented by the formula: Q ₁ -E (E represents an epoxy group) and a compound represented by the formula: Q ₂ -OH are mixed and condensed in the presence of a base such as sodium hydroxide or potassium hydroxide. .

4) A compound represented by the formula: Q ₁ -OFN (OFN represents a group having an unsaturated bond), and a formula: Q ₂ -OM (M: an alkali metal (mainly sodium)) in sodium hydroxide, In the presence of a base such as potassium hydroxide, the mixture is mixed to form an addition reaction.

5) a compound represented by the formula: Q ₁ -X (X represents a halogen atom), and a compound represented by the formula: Q ₂ -OM (M: alkali metal (mainly sodium)) in copper or chloride In the presence of copper, the mixture is condensed. This reaction is generally referred to as Ullmann condensation.

The ester bond and the guanamine bond formation can be carried out, for example, as follows.

1) a compound represented by the formula: Q ₁ -COOH, and a compound represented by the formula: Q ₂ -OH or Q ₂ -NH ₂ in a dehydrating condensing agent (N,N-dicyclohexylmethaneimine, etc.) Dehydration condensation in the presence of ).

2) By reacting a halogenating agent with a compound of the formula: Q ₁ -COOH, a formula: Q ₁ -COX (X represents a halogen atom) is obtained, and a formula: Q ₂ -OH or Q ₂ -NH ₂ is used. The compound shown is reacted with the compound in the presence of a base.

3) The compound represented by the formula: Q ₂ -OH or Q ₂ -NH ₂ is reacted by reacting an acid anhydride with a compound of the formula: Q ₁ -COOH to obtain a mixed acid anhydride.

4) A compound represented by the formula: Q ₁ -COOH and a compound represented by the formula: Q ₂ -OH or Q ₂ -NH ₂ are dehydrated and condensed in the presence of an acid catalyst or a base catalyst.

The formation of ruthenium chloride can be carried out, for example, as follows.

1) The phosphorus trichloride or phosphorus pentachloride is allowed to act on a compound of the formula: Q ₁ -COOH.

2) The action of the hydrazine chloride on the compound represented by the formula: Q ₁ -COOH.

3) The action of the compound represented by the formula: Q ₁ -COOH is made.

4) The action of chlorine or bromine on a compound represented by the formula: Q ₁ -COOAg (Ag: silver element).

5) A solution of red oxidized mercury carbon tetrachloride is applied to a compound of the formula: Q ₁ -COOH.

In the synthesis of the polymerizable liquid crystal compound used in the present invention, the yield can be improved by protecting the hydroxyl group present in the intermediate. The method of protecting the hydroxyl group can be produced by a conventional method (see, for example, Greene's Protective Groups in Organic Synthesis, 3rd edition: Wiley-Interscience, issued in 1999).

The protection of the hydroxyl group can be carried out, for example, as follows.

1) A compound represented by the formula: Q ₁ Q ₂ Q ₃ -Si-X (X represents a halogen atom), and a compound represented by the formula: Q ₄ -OH are mixed in the presence of an imidazole or the like. The reaction. Further, in the formula, Q ₁ to Q ₄ represent an arbitrary organic group B (hereinafter, the same).

2) mixing a vinyl ether such as 3,4-dihydro 2H-pyran and a compound represented by Q ₂ -OH in the presence of an acid such as p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium or hydrogen chloride; reaction.

3) a compound represented by the formula: Q ₁ -C(=O)-X (X represents a halogen atom), and a compound represented by the formula: Q ₄ -OH in the presence of a base such as triethylamine or pyridine , mixing to make it react.

4) reacting an acid anhydride compound represented by the formula: Q ₁ -C(=O)-OC(=O)-Q ₂ and a compound represented by the formula: Q ₃ -OH to react, or in sodium hydroxide, three In the presence of a base such as ethylamine, the mixture is allowed to react.

5) A compound represented by Q ₁ -X (X represents a halogen atom) and a compound represented by the formula: Q ₂ -OH, and a base such as triethylamine are mixed and reacted.

6) a compound represented by the formula: Q ₁ -O-CH ₂ -X (X represents a halogen atom), and a compound represented by the formula: Q ₂ -OH in sodium hydride, sodium hydroxide, triethylamine, In the presence of a base such as pyridine, it is mixed and allowed to react.

7) a compound represented by Q ₁ -O-CH ₂ -C(=O)-X (X represents a halogen atom), and a compound represented by the formula: Q ₄ -OH in potassium carbonate, sodium hydroxide, or the like In the presence of a base, the mixture is allowed to react.

8) a compound represented by the formula: Q ₁ -OC(=O)-X (X represents a halogen atom), and a compound represented by the formula: Q ₂ -OH in the presence of a base such as triethylamine or pyridine , mixing to make it react.

Deprotection can be carried out by a conventional method according to the structure and type of the protecting group.

1) Deprotection is carried out by mixing fluoride ions such as tetrabutylammonium fluoride.

2) Deprotection is carried out by mixing in the presence of an acid such as p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, hydrogen chloride or acetic acid.

3) Deprotection is carried out by mixing in the presence of a base such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine.

4) Deprotection by hydrogenation in the presence of a catalyst such as Pd-C.

In either reaction, after the end of the reaction, a usual post-treatment operation in organic synthesis chemistry is carried out, and a conventional separation by means of column chromatography, recrystallization, distillation, etc., may be performed as desired. , the object is separated.

The structure of the target can be identified by measurement of NMR spectrum, IR spectrum, mass spectrometry, etc., elemental analysis, and the like.

The liquid crystal composition of the present invention may be one or more selected from the group consisting of the above-mentioned polymerizable liquid crystal compound (i), and may be optionally contained in JP-A-11-130729, JP-A-8-104870, and JP-A-2005- 309255, JP-A-2005-263789, JP-A-2002-533742, JP-A-2002-308832, JP-A-2002-265421, JP-A-62-070406, JP-A-11-100575, and the like. Other polymerizable liquid crystal compounds.

The content of the other polymerizable liquid crystal compound to be added to the liquid crystal compound of the present invention is preferably 50% by weight or less, more preferably 30% by weight or less, based on the total amount of the polymerizable liquid crystal compound.

1-2. Polymerizable compound (ii)

The polymerizable compound (ii) is a compound represented by the above formula (II).

In the above formula (II), Z ³ represents a group consisting of a hydrogen atom, an alkyl group having 1 to 2 carbon atoms which may have a substituent, a halogen atom, a hydroxyl group, a carboxyl group, an amine group, and a cyano group. base. The substituent in the case where Z ³ is an alkyl group having a substituent may, for example, be a halogen atom. Z ³ is preferably a cyano group.

MG is represented by a group selected from 4,4'-biphenylene, 4,4'-bicyclohexylene, 2,6-naphthylene, and 4,4'-benzylidene (-C ₆ H ₄ A liquid crystal primordium of the group consisting of -CH-=NN=CH-C ₆ H ₄ -, here -C ₆ H ₄ -p-phenylene). MG is preferably 4,4'-biphenylene.

The n ₁ system represents 0 to 6, and is preferably an integer of 0 to 2.

Y ¹¹ represents a group selected from the group consisting of a single bond, -O-, -S-, -CO-, -CS-, -OCO-, -CH ₂ -, -OCH ₂ -, -NHCO-, -OCOO-, -CH ₂ The group of COO-, and -CH ₂ OCO-. Y ¹¹ is preferably OCO-.

Z ⁴ represents an alkenyl group having 2 to 10 carbon atoms which may be substituted by a halogen atom. Z ^{4 is} preferably CH ₂ =CH-.

The Δn of the polymerizable compound (ii) is preferably 0.18 or more, and more preferably 0.22 or more. By having such a high Δn value, the Δn of the liquid crystal composition can be improved, and a wide-band circularly polarizing separator can be produced. The upper limit of Δn is not particularly limited, and may be, for example, 0.35, preferably 0.30.

Preferable examples of the polymerizable compound (ii) include the following compounds (2-1) to (2-4).

The method for producing the polymerizable compound (ii) is not particularly limited, and it can be synthesized by a method known in the art, for example, a method described in JP-A-62-70406 and JP-A-H11-100575. .

In the liquid crystal composition of the present invention, the weight ratio of (the total weight of the polymerizable compound (ii)) / (the total weight of the polymerizable liquid crystal compound (i)), It is preferably 0.05 to 1, more preferably 0.1 to 0.65, and further preferably 0.15 to 0.45. When the weight is less than 0.05, the alignment uniformity is insufficient. If the amount is more than one, the alignment uniformity is lowered, the stability of the liquid crystal phase is lowered, and the Δn of the liquid crystal composition is lowered, so that it is difficult to obtain the desired one. The optical properties (for example, circular polarization separation characteristics) are not good. In addition, when the total weight is used, the weight is used, and when one type or more is used, the total weight is shown.

In the liquid crystal composition of the present invention, the molecular weight of the polymerizable compound (ii) is less than 600, and the molecular weight of the polymerizable liquid crystal compound (i) is preferably 600 or more. When the molecular weight of the polymerizable compound (ii) is less than 600, the gap between the rod-like liquid crystal compounds having a larger molecular weight can be entered, and the alignment uniformity can be improved. The molecular weight of the polymerizable liquid crystal compound (i) is preferably 750 to 950. The molecular weight of the polymerizable compound (ii) is preferably from 250 to 450.

1-3. Polymeric versus palm compound

The polymerizable palmitic compound used in the liquid crystal composition of the present invention is a compound which can be polymerized with the polymerizable liquid crystal compound of the present invention as long as it has a palm atom in the molecule, and does not disturb the polymerization of the present invention. The alignment of the liquid crystal compound is not particularly limited.

Here, "polymerization" means a chemical reaction that is broadly encompassed by a bridging reaction in addition to a usual polymerization reaction.

In the liquid crystal composition of the present invention, the polymerizable palmitic compound may be used alone or in combination of two or more.

The polymerizable liquid crystal compound (i) constituting the liquid crystal composition of the present invention can exhibit a cholesterol phase by mixing and polymerizing the palm compound.

For the polymerizable compound, for example, a commercially available product (for example, "LC756" manufactured by BASF Corporation), and the like can be used, for example, JP-A-H11-193287 and JP-A-2003-137887. The well-known person. The palmitic compound may, for example, be a compound represented by the following three general formulas, but is not limited thereto.

In the above formula, R ⁶ and R ⁷ may, for example, be a hydrogen atom, a methyl group or a methoxy group. Y ⁹ and Y ¹⁰ may, for example, be -O-, -OC(=O)-, -OC(=O)-O- or the like. Further, m ¹ and m ² are each independently represented by 2, 4 or 6. Specific examples of the compound represented by the above formula include the compounds shown below.

[化18]

In the polymerizable liquid crystal composition of the present invention, the blending ratio of the polymerizable property to the palm compound is preferably 0.1 to 100 parts by weight per 100 parts by weight of the polymerizable liquid crystal compound (i), and preferably 0.5 to 10 parts by weight.

1-4. Photopolymerization initiator

The liquid crystal composition of the present invention contains a photopolymerization initiator from the viewpoint of more efficiently conducting a polymerization reaction.

The photopolymerization initiator to be used may be selected and used as appropriate depending on the type of the polymerizable group present in the polymerizable liquid crystal compound to be used. For example, a radical polymerization initiator is used as the radical polymerizable group, an anionic polymerization initiator is used as the anionic polymerizable group, and a cationic polymerization initiator is used as the cationic polymerizable group.

As the photopolymerization initiator, a conventional compound which can generate a radical or an acid by ultraviolet rays or visible light can be used. Specifically, it may be benzoin, biphenyl dimethyl dimethyl ketone, benzophenone, acetophenone, acetophenone, methyl ketone, biphenyl hydrazine, decyl isobutyl ether, tetraethyl thiuram disulfide , 2,2-azobisisobutyronitrile, 2,2-azo-2,4-dimethylvaleronitrile, benzoyl peroxide, di-tert-butyl peroxide, 1-hydroxycyclohexylphenyl Ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, thioxan Ketone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, methyl benzhydrazide, 2,2-diethoxyacetophenone, β-ionia Ketone, β-bromostyrene, diazoaminobenzene, α-amylcinnamaldehyde, p-dimethylaminoacetophenone, p-dimethylaminopropiophenone, 2-chlorobenzophenone, pp' -dichlorobenzophenone, pp'-bisdiethylaminobenzophenone, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin n-butyl ether, diphenyl sulfide, double (2,6-Methoxybenzyl)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzimidyldiphenyl-diphenylphosphine oxide , bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinylpropane- 1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, benzophenone, α-chloropurine, diphenyl Thioether, hexachlorobutadiene, pentachlorobutadiene, octachlorobutene, 1-chloromethylnaphthalene, 1,2-octanedione, 1-[4-(phenylthio)-, 2-( O-benzylidene hydrazide)] or 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone 1-(o-acetamidine) Anthraquinone compound, (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate, 3-methyl-2-butenetetramethylguanidine Hexafluoroantimonate, diphenyl-(p-phenylthiophenyl)phosphonium hexafluoroantimonate, and the like. Further, two or more kinds of compounds may be mixed according to the desired physical properties, and a third-order amine compound as a photosensitizer or a polymerization accelerator may be added as needed to control the curability.

Specific examples of the photoradical polymerization initiator include, for example, the product name Irgacure 907 manufactured by Ciba Speciality Chemicals Co., Ltd., trade name Irgacure 184, trade name Irgacure 369, trade name Irgacure 651, and trade name Irgacure OXE02.

The anionic polymerization initiator may, for example, be an alkyllithium compound; a monolithium salt or a monosodium salt of a hydrazine, naphthalene or pyran pyrene; a polyfunctional initiator such as a dilithium salt or a trilithium salt; .

Further, examples of the cationic polymerization initiator include protonic acid such as sulfuric acid, phosphoric acid, perchloric acid, and trifluoromethanesulfonic acid; boron trifluoride, aluminum chloride, titanium tetrachloride, and tin tetrachloride; Lewis acid; aromatic sulfonium salt or aromatic sulfonium salt, combined with a rejuvenating agent.

These polymerization initiators may be used alone or in combination of two or more.

In addition, when the (co)polymerization of the polymerizable liquid crystal compound and other copolymerizable monomers used as needed is carried out, an ultraviolet absorber, an infrared absorber, an oxidation inhibitor or the like may be used as needed. Sex compounds.

In the liquid crystal composition of the present invention, the photopolymerization initiator is usually used in a liquid crystal composition, and the photopolymerization initiator is usually 0.03 to 7% by weight.

1-5. Other ingredients

In the liquid crystal composition of the present invention, in order to adjust the surface tension, it is preferred to blend the surfactant. The surfactant is not particularly limited, and usually a nonionic surfactant is preferred. For the non-ionic surfactant, a commercially available product may be used. For example, a nonionic surfactant having an oligomer having a molecular weight of several thousands, for example, KH-40 manufactured by Seimi Chemical Co., Ltd., may be mentioned. In the liquid crystal composition of the present invention, the blending ratio of the surfactant is preferably 0.01 to 10 parts by weight, and preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polymerizable liquid crystal compound (i).

The liquid crystal composition of the present invention may be blended in addition to the above components. Metals, metal complexes, dyes, pigments, fluorescent materials, phosphorescent materials, smoothing agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, oxidation Other additives such as metal oxides such as titanium. In the liquid crystal composition of the present invention, the blending ratio of the other additives is usually 0.1 to 20 parts by weight per 100 parts by weight of the polymerizable liquid crystal compound (i).

1-6. Modulation method

The liquid crystal composition of the present invention can be generally obtained by using a predetermined amount of the polymerizable liquid crystal compound (i), the polymerizable compound (ii), a polymerizable palmitic compound, a photopolymerization initiator, and other additives as desired. It is prepared by dissolving in an appropriate organic solvent.

The organic solvent to be used may, for example, be a ketone such as cyclopentanone, cyclohexanone or methyl ethyl ketone; an acetate such as butyl acetate or amyl acetate; or a halogenated hydrocarbon such as chloroform, dichloromethane or dichloroethane. An ether such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran or tetrahydropyran. The proportion of the solvent may be 50 to 75% by weight based on the total amount of the solid content other than the solvent.

2. Circular polarized separator

In the circularly polarizing separator of the present invention, the cholesteric liquid crystal composition of the present invention is applied onto a transparent resin substrate to obtain a liquid crystal layer, which is cured.

The transparent resin substrate is not particularly limited, and a substrate having a thickness of 1 mm and a total light transmittance of 80% or more can be used. Specifically, it may be an alicyclic olefin polymer, a chain olefin polymer such as polyethylene or polypropylene, cellulose triacetate, polyvinyl alcohol, polyimide, polyacrylate, polyester, or polycarbonate. , polyfluorene, polyether oxime, denatured acrylic polymer, epoxy resin, polystyrene A single layer or a laminated film composed of a synthetic resin such as an olefin or an acrylic resin. Among these, an alicyclic olefin polymer or a chain olefin polymer is preferred, and an alicyclic olefin polymer is particularly preferable from the viewpoints of transparency, low hygroscopicity, dimensional stability, and lightness. .

The transparent resin substrate may have an alignment film as needed. By having an alignment film, the cholesteric liquid crystal composition coated thereon can be aligned in a desired direction. The alignment film is attached to the surface of the substrate, and after applying corona discharge treatment or the like as needed, the cellulose, the oxime coupling agent, the polyimine, the polyamine, the polyvinyl alcohol, the epoxy acrylate, the sterol Oligomer, polyacrylonitrile, phenol resin, polyoxazole, cyclized polyisoprene, etc. dissolved in water or solvent, etc., coated in reverse gravure, direct gravure coating, die coating, bar coating A conventional method such as cloth is applied, dried, and then subjected to a bristles treatment of the dried coating film. The thickness of the alignment film may be 0.001 to 5 μm, more preferably 0.01 to 2 μm, as long as the desired film thickness uniformity of the liquid crystal layer can be obtained.

The application of the liquid crystal composition to the transparent resin substrate can be carried out by a conventional method such as reverse gravure coating, direct gravure coating, die coating, or bar coating. The thickness of the coating layer of the liquid crystal composition can be suitably adjusted so that the desired film thickness of the liquid crystal layer to be described later can be obtained.

Before the coating layer obtained by the above coating is hardened, an alignment treatment may be applied as needed. For the alignment treatment, for example, the coating layer can be heated at 50 to 150 ° C for 0.5 to 10 minutes. By applying the alignment treatment, the cholesteric liquid crystal layer can be well aligned.

After the aligning treatment is carried out as needed, the cholesteric liquid crystal composition is cured by light irradiation and/or warming treatment to obtain a hardened layer having a cholesteric liquid crystal composition (hereinafter referred to as a "hardened liquid crystal layer"). Case.) Round polarized separation piece. The hardening step can be carried out by a combination of one or more light irradiations and a warming treatment. The heating conditions are, for example, a temperature of 40 to 200 ° C, preferably 50 to 200 ° C, more preferably 50 to 140 ° C, and a time of 1 to 3 minutes, preferably 5 to 120 seconds. In the light for light irradiation of the present invention, not only visible light but also ultraviolet rays and other electromagnetic waves are included. The light irradiation can be specifically performed, for example, by irradiating light having a wavelength of 200 to 500 nm for 0.01 second to 3 minutes. Further, for example, a weak ultraviolet ray irradiation of 0.01 to 50 mJ/cm ² is alternately repeated with heating to form a circularly polarizing separation sheet having a wide reflection band. After the reflection band is expanded by the above-described weak ultraviolet irradiation or the like, the liquid crystal compound is completely polymerized by relatively strong ultraviolet rays of 50 to 10,000 mJ/cm ² to form a cured liquid crystal layer. The expansion of the above reflection band and the irradiation of strong ultraviolet rays may be performed under air, or one or all of the steps may be used to control the oxygen concentration. The atmosphere is controlled (for example, under a nitrogen atmosphere).

In the present invention, the step of coating and hardening the cholesteric liquid crystal composition on the transparent resin substrate is not limited to one, and a hardened liquid crystal layer having two or more layers which is applied and cured several times may be formed. According to the present invention, even if the cholesteric liquid crystal composition is applied and cured only once, a hardened liquid crystal layer having a thickness of 5 μm or more containing a rod-like liquid crystal compound having a good alignment of Δn of 0.18 or more can be easily formed. .

In the circularly polarizing separator of the present invention, the dried film thickness of the cured liquid crystal layer is preferably from 3.0 μm to 10.0 μm, more preferably from 3.5 to 8 μm. Hardening fluid When the dried film thickness of the crystal layer is thinner than 3.0 μm, the reflectance is lowered. Conversely, when it is thicker than 10.0 μm, the hardened liquid crystal layer is colored when viewed in an oblique direction, which is not preferable. Further, when the thickness of the dried film is 2 or more, the thickness of each layer is the total thickness of each layer, and when the layer of the cured liquid crystal layer is one layer, the film thickness is referred to.

3. Brightness lifting film

The brightness enhancement film of the present invention comprises the above-described circularly polarized light separation sheet and phase difference film of the present invention. Specifically, a circularly polarizing separator and a phase difference film can be laminated to form a brightness enhancement film of the present invention. This layering is achieved by integrating a circularly polarizing separator and a retardation film via an adhesive or an adhesive. Further, for the purpose of improving the durability and rigidity of the brightness enhancement sheet, the additional transparent resin substrate may be further integrated on the transparent resin substrate and/or the retardation film via an adhesive or an adhesive.

The phase difference film used in the present invention can be used by (i) coating a film-like polymer extender or (ii) a slurry liquid crystal material on a transparent resin substrate to cause alignment and hardening. When the phase difference film of (ii) is used, the liquid crystal material can be coated on a suitable substrate to be aligned, and the phase difference film and the circularly polarizing separation sheet which are hardened can be integrated to form a brightness enhancement film. Alternatively, on the circularly polarizing separation sheet of the present invention, an alignment film is provided for various alignment treatments as needed, and a liquid crystal material is applied thereon to be aligned and hardened, and a phase difference film integrated with the circularly polarizing separation sheet is provided. Layer as a brightness enhancement film.

Preferred examples of the phase difference film used in the present invention include the optical anisotropic elements described below.

In the present invention, the optical anisotropic element can have a retardation Re in the front direction (hereinafter, abbreviated as "Re"), which is about 1/4 wavelength of the transmitted light. Here, the wavelength range of the transmitted light may be a desired range required for the brightness enhancement film of the present invention, specifically, for example, 400 nm to 700 nm. Further, the retardation Re in the front direction is about 1/4 wavelength of the transmitted light, and the Re value is the center value of the wavelength range of the transmitted light, and the value of 1/4 of the center value is ±65 nm, preferably ±30 nm. It is preferably in the range of ±10 nm.

Further, the optically anisotropic element is preferably a retardation Rth in the thickness direction (hereinafter, abbreviated as "Rth"). Preferably, it is less than 0 nm. The value of the retardation Rth in the thickness direction is the center value of the wavelength range of the transmitted light, preferably 30 nm to -1000 nm, more preferably 50 nm to 300 nm. By using an optically anisotropic element having such a Re value and Rth, the brightness can be increased to reduce the luminance halo, and the halo of the emitted light can be reduced.

Here, the retardation Re in the front direction is expressed by the formula I: Re = (nx - ny) × d (wherein nx represents the refractive index in the direction in which the maximum refractive index is given in the direction perpendicular to the thickness direction (front direction)). The ny system indicates the refractive index in the direction perpendicular to the thickness direction (in-plane direction) and the direction orthogonal to nx, and d indicates the film thickness.) The value shown in the thickness direction, the retardation Rth in the thickness direction, and the formula II: Rth={ (nx+ny)/2-nz}×d (wherein nx represents a refractive index in a direction in which a direction perpendicular to the thickness direction (in-plane direction) is given to the maximum refractive index, and ny is a direction perpendicular to the thickness direction (face) The inner direction is the refractive index in the direction orthogonal to nx, the refractive index in the thickness direction of nz is the thickness, and d is the value shown in the film thickness.

Furthermore, the delay in the front direction and the retardation in the thickness direction Rth By using a commercially available phase difference measuring device, the optical anisotropic element is spaced at a distance of 100 mm in the longitudinal direction and the wide direction (when the length in the longitudinal direction or the lateral direction is less than 200 mm, the direction is specified at three equal intervals) ), in the form of lattice points, the measurement is comprehensive and the average value is taken.

The material constituting the optically anisotropic element is not particularly limited, and a layer composed of a styrene resin can be preferably used. Here, the styrene resin is a polymer resin having a styrene structure as one or all of the reversing units, and examples thereof include polystyrene, styrene, α-methylstyrene, o-methylstyrene, and para Styrene, p-chlorostyrene, p-nitrostyrene, p-aminostyrene, p-carboxystyrene, p-phenylstyrene, etc., styrenic monomers, and ethylene, propylene, butadiene, isoprene Diene, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, Other monomer copolymers such as vinyl acetate. Among these, polystyrene or a copolymer of styrene and maleic anhydride can be preferably used.

The molecular weight of the styrene resin used in the optically anisotropic element can be appropriately selected according to the purpose of use, and the weight average molecular weight (Mw) of the polyisoprene measured by gel permeation chromatography using cyclohexane as a solvent, It is usually 10,000 to 300,000, preferably 15,000 to 250,000, and more preferably 20,000 to 200,000.

The optically anisotropic element preferably has a layered structure of a layer composed of the styrene resin and a layer containing another thermoplastic resin. By having the laminated structure, it can be made into a styrene resin. Optical properties, components of mechanical strength with other thermoplastic resins. Other thermoplastic resins include alicyclic olefin polymers, methacrylic resins, polycarbonates, acrylate vinyl aromatic copolymer resins, methacrylate vinyl aromatic copolymer resins, and poly Ether oxime and the like. Among these, a resin having an alicyclic structure or a methacrylic resin can be preferably used.

The alicyclic olefin polymer is an amorphous olefin polymer having a naphthene structure or a cycloolefin structure in a main chain and/or a side chain. Specifically, (1) a norbornene-based polymer, (2) a monocyclic cyclic olefin polymer, (3) a cyclic conjugated diene polymer, and (4) a vinyl alicyclic hydrocarbon polymer, And such hydrides and the like. Among these, the original borneol-based polymer is more preferable from the viewpoint of transparency or formability. The resin having such an alicyclic structure is described in JP-A-H05-310845, JP-A-2005-097978, and JP-A No. 6,511,756.

The norbornene-based polymer may specifically be a ring-opening polymer of an original borneol-based monomer; a ring-opening copolymer of a norbornene-based monomer and another monomer which can be ring-opened copolymerized, and the like a hydride; an addition polymer of an original borneol-based monomer; an addition copolymer of an original borneol-based monomer and another monomer copolymerizable, and the like.

The methacrylic resin is a polymer containing methacrylate as a main component, and may be a single polymer of methacrylate or a copolymer of methacrylate and other monomers, methacrylate, usually, using a Alkyl acrylate. In the case of a copolymer, other monomers copolymerized with methacrylate may be used as an acrylate or an aromatic vinyl compound or a vinyl group. Cyanide compounds, etc.

A preferred embodiment of the optically anisotropic element of the present invention is a film formed by laminating another thermoplastic resin on both sides of a film (layer a) composed of a polystyrene resin. The b layer) is formed by stretching a multi-layer film to form an extended laminated film. Hereinafter, this aspect will be specifically described.

The polystyrene resin constituting the above a layer can be the same as the above-mentioned "styrene resin".

The polystyrene resin constituting the a layer has a glass transition temperature of preferably 120 ° C or higher, more preferably 120 to 200 ° C, and further preferably 120 to 140 ° C.

In the present invention, the polystyrene resin and the other thermoplastic resin satisfy Tg(a)>Tg when the glass transition temperatures are Tg(a) (°C) and Tg(b) (°C), respectively. (b) The relationship of +20 °C is preferred. By satisfying such a relationship, optical anisotropy can be effectively imparted to the a layer composed of the polystyrene resin during stretching, and a good optical anisotropic element can be obtained.

The method of laminating the above-mentioned other thermoplastic resin of the polystyrene resin of the a-layered lipid material and the material of the b-layer to form a double-layered film is not particularly limited, and can be suitably used, and the T-die method can be used in common. A method of forming a co-extrusion by a blowing method, a co-extrusion lamination method, a film lamination molding method such as dry lamination, and a conventional method such as a coating forming method. Among them, a molding method by co-extrusion is preferred from the viewpoint of production efficiency or a volatile component such as a solvent remaining in the film. The extrusion temperature can be appropriately selected depending on the type of the above-mentioned polystyrene resin to be used and the other thermoplastic resins mentioned above.

The stratified film is formed by laminating the b layer on both sides of the a layer. Between the a layer and the b layer, although an adhesive layer or an adhesive layer may be provided, it is preferable to directly laminate the a layer and the b layer (that is, a laminate of a three-layer structure of the b layer/a layer/b layer). . Further, the thickness of the double layer film laminated on the a layer and the b layers on both sides thereof is not particularly limited, and is preferably 10 to 300 μm and 10 to 400 μm, respectively.

The above-mentioned extended multi-layer film is formed by extending the above-mentioned multi-layer film. The extended cladding film may include an A layer provided by extension of the a layer and a B layer provided by extension of the b layer. The extended laminated film is formed by extending a laminated body of a three-layer structure of a b layer/a layer/b layer of the double layer film, and a stretching film of a three layer structure of a B layer/A layer/B layer is good.

Preferably, the extension may be performed by one axial extension or oblique extension, and further preferably one of the extension or the oblique extension of the extension machine.

The retardation Re in the front direction or the retardation Rth in the thickness direction of the optically anisotropic element can be produced by appropriately adjusting the stretching conditions such as the stretching temperature or the stretching ratio. The extension temperature is preferably from the above Tg(a) - 10 ° C to the above Tg (a) + 20 ° C, and more preferably in the range of the above Tg (a) - 5 ° C to the above Tg (a) + 15 ° C. The stretching ratio is preferably 1.05 to 30 times, and more preferably 1.1 to 10 times. When the stretching temperature or the stretching ratio is out of the above range, the alignment is not sufficient, and the anisotropy of the refractive index and the retardation are not sufficiently exhibited, and the laminate is broken.

The thickness of the optical anisotropic element is preferably 50 to 1000 μm, more preferably 50 to 600 μm.

4. Liquid crystal display device

The liquid crystal display device of the present invention is provided with the brightness enhancement of the present invention described above Film and liquid crystal panel.

The liquid crystal panel is not particularly limited, and can be suitably used for a liquid crystal display device. For example, TN (Twisted Nematic) liquid crystal panel, STN (Super Twisted Nematic) type liquid crystal panel, HAN (Hybrid Alignment Nematic) type liquid crystal panel, IPS (In Plane Switching) : Horizontal electric field effect type liquid crystal panel, VA (Vertical Alignment) type liquid crystal panel, MVA (Multiple Vertical Alignment) type liquid crystal panel, OCB (Optical Compensated Bend) type liquid crystal panel, etc. .

The liquid crystal display device of the present invention may further include a backlight, and may be configured to have a brightness enhancement film disposed between the backlight and the liquid crystal panel. More specifically, the brightness enhancement film of the present invention is disposed between the backlight of the liquid crystal display device and the liquid crystal cell, and the layer of the circularly polarizing film is disposed on the backlight side of the layer of the retardation film to achieve brightness enhancement.

[Examples]

The production method of the present invention will be described in more detail by way of examples, and the present invention is not limited to the following examples. Furthermore, the department and % do not specifically mention the weight basis.

(Production Example 1) Synthesis of Polymerizable Liquid Crystal Compound 1 represented by the following formula (1)

Step 1: Synthesis of Intermediate A represented by the following formula (1a)

A 4-port reactor equipped with a cooler, a thermometer and a dropping funnel was subjected to a nitrogen stream, and 15-methionic acid 15 g (0.09 mol), methanol 14.5 g (0.45 mol), N,N-dimethylamino group. 2.2 g (0.018 mol) of pyridine was dissolved in 200 ml of tetrahydrofuran. To the solution, 37.3 g (0.18 mol) of N,N-dicyclohexylmethyleneimine dissolved in 100 ml of tetrahydrofuran was slowly added to the solution at room temperature. Thereafter, the reaction was carried out at room temperature for 6 hours. After the completion of the reaction, the mixture was filtered under reduced pressure, and then evaporated to dryness. The yellow oil was purified by silica gel chromatography (hexane: THF: 9:1) to afford 13.4 g (yield: 82.4%) The structure of Intermediate A was identified by ¹ H-NMR.

^{1 H-NMR (500MHz, CDCl} 3, TMS, δ ppm): 11.36 (s, 1H), 9.88 (s, 1H), 8.39 (s, 1H), 8.00 (d, 1H, J = 9.0Hz), 7.11 (d, 1H, J = 9.0 Hz), 4.01 (s, 3H).

Step 2: Synthesis of Intermediate B represented by the following formula (1b)

A 4-port reactor equipped with a cooler, a thermometer and a dropping funnel was dissolved in N-hydroxybenzaldehyde 30 g (0.25 mol) and 34.4 g of tert-butyldimethylphosphonium chloride (0.29 mol) under a nitrogen stream. , N-dimethylformamide 400ml. Under the water bath, 41.8 g (0.61 mol) of imidazole dissolved in 200 ml of N,N-dimethylformamide was slowly added as a dropping funnel. Thereafter, the reaction was carried out at room temperature for 4 hours. After the completion of the reaction, the reaction mixture was poured into 6 mL of a saturated aqueous sodium hydrogen carbonate solution and extracted three times with 500 ml of n-hexane. After the n-hexane layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration. The n-hexane layer was concentrated under a reduced pressure rotary concentrator to give a pale yellow oil. The pale yellow oil was purified by silica gel chromatography (hexane: ethyl acetate = 9:1) to afford 30% (yield: 50.8%) of Intermediate B. The structure of Intermediate B was identified by ¹ H-NMR.

¹ H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 9.87 (s, 1H), 7.78 (d, 2H, J = 7.8 Hz), 6.93 (d, 2H, J = 7.8 Hz), 0.98 (s) , 9H), 0.23 (s, 6H).

Step 3: Synthesis of Intermediate C represented by the following formula (1c)

To a four-port reactor equipped with a cooler, a thermometer, and a dropping funnel, 10.6 g (0.21 mol) of hydrazine 1 water and a solution were dissolved in 50 ml of tetrahydrofuran under a nitrogen stream. To the solution, 10.0 g (0.042 mol) of Intermediate B dissolved in 50 ml of tetrahydrofuran was slowly added to the solution at room temperature. Thereafter, the reaction was carried out at room temperature for 3 hours. After the completion of the reaction, the reaction mixture was concentrated under a reduced pressure rotary concentrator to give a yellow oil. The yellow oil was dissolved in 200 ml of chloroform, and washed twice with saturated sodium bicarbonate water (500 ml). After 6 ml of triethylamine was added to the chloroform layer, it was dried over magnesium sulfate. Thereafter, magnesium sulfate was removed by filtration. The chloroform layer was concentrated under a reduced pressure rotary concentrator to give a pale yellow oil. The yellow oil was dissolved in 50 ml of tetrahydrofuran, and 6 ml of triethylamine was added. To the solution, 7.2 g (0.04 mol) of Intermediate A dissolved in 50 ml of tetrahydrofuran was slowly added in a dropping funnel at room temperature. Thereafter, the reaction was carried out at room temperature for 12 hours. After the completion of the reaction, the mixture was concentrated under reduced pressure and evaporated to dryness to dryness. The yellow oil was purified by silica gel chromatography (n-hexane: THF: 2:1) to afford 10.76 g (yield: 65.2%) of Intermediate C. The structure of Intermediate C was identified by ¹ H-NMR.

^{1 H-NMR (400MHz, CDCl} 3, TMS, δ ppm): 11.08 (s, 1H), 8.61 (s, 1H), 8.58 (s, 1H), 8.26 (d, 1H, J = 2.0), 8.01 ( Dd, 1H, J = 2.0 Hz, J = 8.8 Hz), 7.73 (d, 1H, J = 8.8 Hz), 7.06 (d, 1H, J = 8.4 Hz), 6.90 (d, 3H, J = 8.4 Hz) , 4.00 (s, 3H), 0.98 (s, 9H), 0.24 (s, 6H).

Step 4: Synthesis of intermediate D represented by the following formula (1d)

A four-port reactor equipped with a cooler, a thermometer and a dropping funnel was charged with a solution of a solution of 1 mol/L tetrabutylammonium fluoride in tetrahydrofuran at a concentration of 1 mol/L. To the solution, 10.0 g (0.024 mol) of Intermediate C dissolved in 50 ml of tetrahydrofuran was slowly added to the solution at room temperature. Thereafter, the reaction was carried out at room temperature for 3 hours. After the completion of the reaction, the reaction solution was poured into water, and 250 ml of a 5% aqueous citric acid solution was added to make it acidic. The solution was extracted twice with 300 ml of chloroform and extracted. After the chloroform layer was dried over anhydrous sodium sulfate, sodium sulfate was removed by filtration. The chloroform layer was concentrated under a reduced pressure rotary concentrator to give a yellow oil. The yellow oil was purified by silica gel chromatography (n-hexane: THF: 2:1) to afford 3% (yield: 88.1%). The structure of Intermediate D was identified by ¹ H-NMR.

^{1 H-NMR (400MHz, CDCl} 3, TMS, δ ppm): 11.10 (s, 1H), 8.61 (s, 1H), 8.58 (s, 1H), 8.27 (d, 1H, J = 2.2Hz), 8.01 (dd, 1H, J = 2.0 Hz, J = 8.6 Hz), 7.75 (d, 2H, J = 8.6 Hz), 7.06 (d, 1H, J = 8.4 Hz), 6.90 (d, 2H, J = 8.4 Hz) ), 5.21 (s, 1H), 4.00 (s, 3H).

Step 5: Synthesis of the polymerizable liquid crystal compound 1 represented by the above formula (1)

For a 4-port reactor equipped with a cooler, a thermometer and a dropping funnel, an intermediate D 3.0 g (0.01 mol), 4-(6-acrylo-hexan-1-yloxy)benzoic acid (Japanese Siber Hegner) was added under a nitrogen stream. 7.35 g (0.025 mol) was dissolved in 100 ml of N,N-dimethylformamide. To the solution was added 1-ethyl-3-(3-dimethylaminopropyl)methyleneimine hydrochloride (WSC) 4.8 g (0.025 mol) at room temperature. Thereafter, the reaction was carried out at room temperature for 9 hours. After the completion of the reaction, the reaction solution was poured into water and extracted twice with 300 ml of chloroform. After the chloroform layer was dried over magnesium sulfate, magnesium sulfate was removed by filtration. The chloroform layer was concentrated under a reduced pressure rotary concentrator to give a yellow oil. The yellow oil was purified by silica gel chromatography (toluene:ethyl acetate = 9:1, toluene:ethyl acetate = 8:2) to give a pale yellow solid of 7.5 g (yield of polymerizable liquid crystal compound 1). Yield: 88.6%). The structure of the polymerizable liquid crystal compound 1 was identified by ¹ H-NMR.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ ppm): 8.70 (s, 2H), 8.49 (s, 1H), 8.18-8.11 (m, 4H), 7.93 (d, 2H, J = 7.6 Hz) , 7.40-7.26 (m, 4H), 6.99 (d, 4H, J = 6.8 Hz), 6.41 (d, 2H, J = 17.2 Hz), 6.13 (dd, 2H, J = 13.2 Hz, 21.2 Hz), 5.83 (d, 2H, J = 13.0 Hz), 4.20 - 4.06 (m, 8H), 3.60 (s, 3H), 1.85-1.70 (m, 8H), 1.57-1.20 (m, 8H).

(Production Example 2) Synthesis of Polymerizable Liquid Crystal Compound 2 represented by the following formula (2)

Step 1: Synthesis of intermediate H represented by the following formula (2a)

For a 4-port reactor equipped with a cooler, a thermometer and a dropping funnel, 15 g (0.09 mol) of 5-carboxylic acid, 28.1 g (0.27 mol) of ethylene glycol monopropyl ether, p-toluenesulfonic acid under a nitrogen stream 1 Water and 1.7 g (0.009 mol) were dissolved in 1000 ml of toluene. Thereafter, the reaction was carried out under reflux for 8 hours. The water to be produced in the reaction is extracted by azeotropic dehydration with toluene, and on the other hand, toluene is added for reaction. After the completion of the reaction, the reaction solution was washed with water, and the toluene layer was dried over magnesium sulfate. The toluene layer was concentrated under a reduced pressure rotary concentrator to give a yellow oil. The yellow oil was purified by silica gel chromatography (hexane: tetrahydrofuran = 3:1) to afford intermediate H. Light yellow solid 12.6 g (yield: 55.5%). The structure of Intermediate H was identified by ¹ H-NMR.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm) 11.34 (s, 1H), 9.89 (s, 1H), 8.42 (d, 1H, J = 2.0 Hz), 8.01 (dd, 1H, J = 2.0) Hz, J = 8.6 Hz), 7.11 (d, 1H, J = 8.6 Hz), 4.56 (t, 2H, J = 4.6), 3.80 (t, 2H, J = 4.6 Hz), 3.49 (t, 2H, J) = 6.6 Hz), 1.68-1.59 (m, 2H), 0.94 (t, 3H, J = 7.6 Hz).

Step 2: Synthesis of intermediate I represented by the following formula (2b)

In the synthesis of the intermediate C in the step 3 of the synthesis of the polymerizable liquid crystal compound 1, the intermediate I was synthesized in the same manner except that the intermediate A was changed to the intermediate H (yield: 50.8%). The structure of Intermediate I was identified by ¹ H-NMR.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm) 11.04 (s, 1H), 8.60 (s, 1H), 8.58 (s, 1H), 8.26 (d, 1H, J = 2.0 Hz), 8.04 ( Dd, 1H, J = 2.0 Hz, J = 8.6 Hz), 7.73 (d, 2H, J = 8.6 Hz), 7.06 (d, 1H, J = 8.6 Hz), 6.90 (d, 2H, J = 8.6 Hz) , 4.54 (t, 2H, J = 4.8 Hz), 3.80 (t, 2H, J = 4.8 Hz), 3.50 (t, 2H, J = 6.6 Hz), 1.68-1.60 (m, 2H), 1.00 (s, 9H), 0.95 (t, 3H, J = 7.4 Hz), 0.24 (s, 6H).

Step 3: Synthesis of intermediate J represented by the following formula (2c)

In the synthesis of the intermediate D in the step 4 of the synthesis of the polymerizable liquid crystal compound 1, the intermediate J was changed to the intermediate I, and the intermediate J was synthesized in the same manner (yield: 75.6%). The structure of Intermediate J was identified by ¹ H-NMR.

¹ H-NMR (400 MHz, CD ₃ OD, TMS, δ ppm) 8.46 (s, 1H), 8.45 (s, 1H), 8.21. (d, 1H, J = 2.2 Hz), 7.94 (dd, 1H, J = 2.2 Hz, J = 8.8 Hz), 7.62 (d, 2H, J = 8.8 Hz), 6.97 (dd, 1H, J = 2.2 Hz, J = 8.8 Hz), 6.80 (d, 2H, J = 8.8 Hz), 4.47-4.45(m,2H), 3.76-3.74(m,2H), 3.45(t,2H,J=6.6Hz),1.61-1.52(m,2H),0.89(t,3H,J=7.4Hz) .

Step 4: Synthesis of polymerizable liquid crystal compound 2 represented by the above formula (2)

In the synthesis of the polymerizable liquid crystal compound 1 in the step 5 of the synthesis of the polymerizable liquid crystal compound 1, the polymerizable liquid crystal compound 2 (yield: 82.8%) was synthesized in the same manner except that the intermediate D was changed to the intermediate J. The structure of Compound 2 was identified by ¹ H-NMR.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ ppm): 8.69 (s, 2H), 8.49 (m, 1H), 8.19-8.13 (m, 5H), 7.94-7.92 (m, 2H), 7.34 7.18 (m, 3H), 6.84 (d, 4H, J = 6.4 Hz), 6.41 (d, 2H, J = 17.4 Hz), 6.13 (dd, 2H, J = 10.4 Hz, J = 17.4 Hz), 5.83 ( d, 2H, J = 10.4 Hz), 4.37-4.35 (m, 2H), 4.19 (t, 4H, J = 6.2 Hz), 4.06 (t, 4H, J = 6.2 Hz), 3.56-3.54 (m, 2H) ), 3.33-3.30 (m, 2H), 1.87-1.72 (m, 8H), 1.58-1.43 (m, 10H), 0.90 (t, 3H, J = 7.4 Hz).

(Production Example 3) Synthesis of Polymerizable Liquid Crystal Compound 3 represented by the following formula (3)

Step 1: Synthesis of intermediate K represented by the following formula (3a)

In the synthesis of the intermediate C in the step 3 of the synthesis of the polymerizable liquid crystal compound 1, the intermediate K was changed to ethyl vanillin (3-ethyl-4-hydroxybenzaldehyde), and the intermediate K was synthesized in the same manner. (Yield: 60.3%). The structure of the intermediate K was identified by ¹ H-NMR.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ ppm): 8.59 (s, 1H), 8.56 (s, 1H), 7.73 (s, 1H), 7.71 (s, 1H), 7.50 (s, 1H) , 7.21 (d, 1H, J = 8.0 Hz), 7.00-6.89 (m, 3H), 4.23 (t, 2H, J = 6.8 Hz), 1.49 (t, 3H, J = 6.8 Hz), 1.00 (s, 9H), 0.23 (s, 6H).

Step 2: Synthesis of intermediate L represented by the following formula (3b)

In the synthesis of the intermediate D in the step 4 of the synthesis of the polymerizable liquid crystal compound 1, the intermediate L was synthesized in the same manner except that the intermediate C was changed to the intermediate K (yield: 88.1%). The structure of the intermediate L was identified by ¹ H-NMR.

¹ H-NMR (400 MHz, CDCl ₃ -CD ₃ OD, TMS, δ ppm): 8.58 (s, 1H), 8.54 (s, 1H), 7.70 (d, 2H, J = 8.6 Hz), 7.49 (s, 1H), 7.21 (d, 1H, J = 8.6 Hz), 6.98-6.88 (m, 3H), 4.24 - 4.19 (m, 2H), 1.49 (t, 3H, J = 7.0 Hz).

Step 3: Synthesis of the polymerizable liquid crystal compound 3 represented by the above formula (3)

In the synthesis of the polymerizable liquid crystal compound 1 in the step 5 of the synthesis of the polymerizable liquid crystal compound, the polymerizable liquid crystal compound 4 was synthesized in the same manner except that the intermediate D was changed to the intermediate L (yield: 86.4%). The structure of the polymerizable liquid crystal compound 4 was identified by ¹ H-NMR.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δ ppm): 8.68 (s, 1H), 8.63 (s, 1H), 8.17-8.14 (m, 4H), 7.92 (d, 2H, J = 8.2 Hz) , 7.62 (s, 1H), 7.36-7.23 (m, 4H), 6.98 (d, 4H, J = 8.2 Hz), 6.41 (d, 2H, J = 17.6 Hz), 6.13 (dd, 2H, J = 10.4) Hz, J = 17.6 Hz), 5.83 (d, 2H, J = 10.4 Hz), 4.20 - 4.13 (m, 6H), 4.06 (t, 4H, J = 6.2 Hz), 1.88 - 1.82 (m, 4H), 1.77-1.70 (m , 4H), 1.57-1.48 (m, 8H), 1.34 (t, 3H, J = 7.0 Hz).

(Production Example 4) Synthesis of Polymerizable Liquid Crystal Compound 4 represented by the following formula (4)

Synthesis of polymerizable liquid crystal compound 4

In the step 3 of the synthesis of the polymerizable liquid crystal compound 3, 4-(6-acrylo-hexan-1-yloxy)benzoic acid (manufactured by Siber Hegner, Japan) was changed to 4-(4-acryloyl-butan-1-yl). Polymerizable liquid crystal compound 4 (yield: 80.1%) was synthesized in the same manner except for oxybenzoic acid (manufactured by Siber Hegner, Japan). The structure of the polymerizable liquid crystal compound 4 was identified by ¹ H-NMR.

^{1 H-NMR (500MHz, CDCl} 3, TMS, δ ppm): 8.67 (s, 1H), 8.62 (s, 1H), 8.17-8.14 (m, 4H), 7.93 (m, 2H), 7.61 (s, 1H), 7.35-7.30 (m, 2H), 7.25-7.22 (m, 2H), 6.98-6.95 (m, 4H), 6.41 (d, 2H, J = 17.5 Hz), 6.12 (dd, 2H, J = 10.3 Hz, J = 17.5 Hz), 5.83 (d, 2H, J = 10.3 Hz), 4.25 (t, 4H, J = 6.0 Hz, J = 4.6 Hz), 4.15 (dd, 2H, J = 6.9 Hz, J =13.4 Hz), 4.09 (t, 4H, J = 4.6 Hz, J = 6.0 Hz), 1.92 (m, 8H), 4.09 (t, 3H, J = 6.9 Hz).

(Production Example 5) Synthesis of the polymerizable liquid crystal compound 5 represented by the following formula (5)

[化33]

Step 1: Synthesis of intermediate M represented by the following formula (5a)

A 4-port reactor equipped with a cooler, a thermometer and a dropping funnel was charged with a solution of 50 g (0.23 mol) of 2-propenyloxyethyl succinic acid in a nitrogen stream, and slowly dissolved in tetrahydrofuran at room temperature in a dropping funnel. 300 ml of grass chlorohydrate 292 g (2.3 mol). Thereafter, the reaction was carried out at room temperature for 24 hours. After the completion of the reaction, the unreacted grass chlorobenzene was distilled off under reduced pressure on a reduced pressure rotary concentrator to obtain 54 g of 2-propenyloxyethyl amber sulfonium chloride as a yellow oil. This hydrazine chloride was not purified and used directly in the next reaction.

Next, a 4-port reactor equipped with a cooler, a thermometer, and a dropping funnel was charged with 10 g (53.1 mmol) of 6-hydroxy-2-naphthoic acid in a nitrogen stream, and dissolved in 200 ml of tetrahydrofuran.

11.3 g (111.5 mmol) of triethylamine was slowly added dropwise to the solution under ice bath.

Further, 13.7 g (58.4 mmol) of the previously synthesized 2-propenyloxyethylammonium chloride was added dropwise to the solution under ice bath for 30 minutes. After reacting for 30 minutes in an ice bath, the reaction was carried out at room temperature for 3 hours. After the completion of the reaction, the reaction solution was poured into 2 L of a 1N-hydrochloric acid aqueous solution to make it acidic, and then extracted three times with 500 ml of ethyl acetate. Ethyl acetate layer After drying over magnesium sulfate, magnesium sulfate was removed by filtration. The ethyl acetate layer was concentrated under a reduced pressure rotary concentrator to give a pale yellow oil.

The pale yellow oil was purified by silica gel chromatography (chloroform:methanol = 95:5) to yield 17 g of pale yellow solid. Further, the pale yellow solid was recrystallized from chloroform:toluene = 1:4 to give a pure intermediate M 12.5 g (yield: 61%).

¹ H-NMR (400 MHz, CDCl ₃ , TMS, δ ppm): 8.76 (s, 1H), 8.21-7.69 (m, 4H), 7.37 (dd, J = 8.8 Hz, J = 2.4 Hz, 1H), 6.43 (dd, J = 17.2 Hz, J = 1.2 Hz, 1H), 6.12 (dd, J = 17.2 Hz, J = 10.6 Hz, 1H), 5.83 (dd, J = 10.8 Hz, J = 1.2 Hz 1H), 4.40 ( s, 4H), 2.98 (t, J = 6.6 Hz, 2H), 2.83 (t, J = 6.6 Hz, 2H).

Step 2: Synthesis of intermediate N represented by the following formula (5b)

The previously synthesized intermediate M12g (31 mmol) was dissolved in 300 ml of tetrahydrofuran in a 4-port reactor equipped with a cooler, a thermometer and an introduction funnel. To the solution, 20 g (158 mmol) of chlorophyll chloride dissolved in 25 ml of tetrahydrofuran was added dropwise thereto for 30 minutes. Thereafter, the mixture was heated to 40 ° C using a water bath and stirred for 24 hours. After the completion of the reaction, the unreacted grass chlorobenzene was distilled off under reduced pressure on a reduced pressure rotary concentrator to obtain 13 g of hydrazine chloride as intermediate M of a yellow oil. This hydrazine chloride was not purified and used directly in the next reaction.

Next, a four-port reactor equipped with a cooler, a thermometer, and a dropping funnel was charged with 1.25 g (6.1 mmol) of 3,7-dihydroxy-2-naphthoic acid and 1.85 g (18 mmol) of triethylamine in a nitrogen stream. Tetrahydrofuran 200 ml. The solution was cooled to 0 ° C to 5 ° C in an ice bath, and 7.5 g (19 mmol) of the previously synthesized intermediate M in chlorobenzene was added dropwise to a solution of 100 ml of tetrahydrofuran using a dropping funnel for 30 minutes. After the completion of the dropwise addition, the reaction was further carried out at room temperature for 12 hours. After the completion of the reaction, the reaction solution was poured into 500 ml of a 1N-hydrochloric acid aqueous solution to make it acidic, and then extracted three times with 500 ml of ethyl acetate. After the ethyl acetate layer was dried over magnesium sulfate, the magnesium sulfate was removed by filtration. Ethyl acetate layer The mixture was concentrated under a reduced pressure rotary concentrator to give 18 g of a yellow oil. The yellow oil was purified by silica gel chromatography (chloroform:methanol = 98:2) to afford white crystals (yield: 34.8%) of Intermediate N. ¹ H-NMR (400MHz, CDCl ₃ , TMS, δ ppm): 8.81-7.27 (m, 17H), 6.32-6.28 (m, 2H), 6.09-6.02 (m, 2H), 5.74-5.70 (m, 2H) ), 4.29-4.20 (m, 8H), 2.86-2.83 (m, 4H), 2.80-2.65 (m, 4H).

Step 3: Synthesis of polymerizable liquid crystal compound 5 (esterification of intermediate N)

The previously synthesized intermediate N 2g (2.1 mmol) was dissolved in 50 ml of tetrahydrofuran in a 4-neck reactor equipped with a cooler, a thermometer and an introduction funnel. The solution was added dropwise to 1.35 g (10.6 mmol) of hawthorn chlorine dissolved in 25 ml of tetrahydrofuran at room temperature for 30 minutes. Thereafter, the mixture was heated to 40 ° C using a water bath and stirred for 24 hours. After the completion of the reaction, the unreacted grass chlorobenzene was distilled off under reduced pressure using a reduced pressure rotary concentrator to obtain 2 g of chlorobenzene as the intermediate N of the yellow oil. This hydrazine chloride was not purified and used directly in the next reaction.

Next, a 4-port reactor equipped with a cooler, a thermometer, and a dropping funnel was charged with 0.5 g (4.3 mmol) of 2-hydroxyethyl acrylate, 4.3 g (42.6 mmol) of triethylamine, and 50 ml of tetrahydrofuran in a nitrogen chloride stream. . The solution was warmed to 40 ° C, and 2 g (2.1 mmol) of the previously synthesized intermediate N was dissolved in a 50 ml portion of tetrahydrofuran using a dropping funnel for 10 minutes. After the completion of the dropwise addition, the mixture was further reacted at room temperature for 2 hours. After the completion of the reaction, the reaction solution was poured into 1 L of a 1 N aqueous solution of hydrochloric acid to acidify, and then extracted three times with 300 ml of ethyl acetate. After the ethyl acetate layer was dried over magnesium sulfate, the magnesium sulfate was removed by filtration. The ethyl acetate layer was concentrated under a reduced pressure rotary concentrator to obtain 2.4 g of a yellow oil. The yellow oil was purified by silica gel chromatography (chloroform:methanol = 98:2) to yield white crystals (yield: 17.4%) of the crystalline liquid crystal compound 5. ^{1 H-NMR (400MHz, CDCl} 3, TMS, δ ppm): 8.85-7.38 (m, 17H), 6.45-5.82 (m, 9H), 4.48-4.29 (m, 12H), 3.00-2.97 (m, 4H ), 2.86-2.82 (m, 4H).

(Example 1)

(Modulation of transparent resin substrate with alignment film)

Both surfaces of a membrane film made of an alicyclic olefin polymer (manufactured by OPTES, trade name "ZEONOR membrane ZF14-100") were subjected to corona discharge treatment. An aqueous solution of 5% polyvinyl alcohol was applied to one side of the film using a #2 wire bar, and the coating film was dried to form an alignment film having a film thickness of 0.1 μm. The alignment film is then bristled to prepare a transparent resin substrate having an alignment film.

(made by circular polarized separation film)

On the surface of the transparent resin substrate having the alignment film prepared above, which had an alignment film, a cholesteric liquid crystal composition in which each component was mixed and prepared at a blending ratio shown in Table 1 was applied by a #10 wire bar. The coating film was treated at 100 ° C for 5 minutes, and the coating film was overlaid twice, irradiated with a weak ultraviolet ray of 0.1 to 45 mJ/cm ² , and heated at 100 ° C for 1 minute. After the preparation, ultraviolet rays of 800 mJ/cm ² were irradiated in a nitrogen atmosphere to prepare a circularly polarizing separator having a cholesteric liquid crystal layer having a dry film thickness of 5 μm.

(Evaluation of circular polarized separation tablets)

For the circularly polarizing separator prepared as described above, a transmission spectrum was measured using a spectroscope (manufactured by Otsuka Electronics Co., Ltd., instantaneous multi-function photometric system MCPD-3000) and a microscope (manufactured by NIKON Co., Ltd., polarized-head micro-mirror ECLIPSE E600-POL). The half-wave width of the selective reflection band is shown in Table 1.

Further, the haze value was measured in accordance with JIS K7136, and the alignment uniformity was evaluated. Those who have a haze value of less than 2.0% are evaluated as "good", those with a haze value of 2.0% or less and less than 3.0% are evaluated as "medium", and those having a haze value of 3.0% or more are evaluated as "poor". The evaluation results are shown in Table 1.

(Examples 2 to 5 and Comparative Example 1)

A circularly polarizing separator was produced and evaluated in the same manner as in Example 1 except that the composition of the cholesteric liquid crystal composition was as shown in Table 1. The evaluation results are shown in Table 1.

From the results of the examples and the comparative examples, it is understood that the circularly polarizing separator of the present invention has a good uniformity of alignment and a wide selective reflection band.

In Table 1, the composition all represents the weight portion. Also, the abbreviation in Table 1 is as follows:

Compound (1): Polymerizable liquid crystal compound 1 of Production Example 1, Δn 0.18

Compound (2): Polymerizable liquid crystal compound 2 of Production Example 2, Δn 0.18

Compound (3): Polymerizable liquid crystal compound 3 of Production Example 3, Δn0.20

Compound (4): Polymerizable liquid crystal compound 4 of Production Example 4, Δn0.20

Compound (5): Polymerizable liquid crystal compound 5 of Production Example 5, Δn 0.22

Compound (2-1): a compound represented by the following formula (2-1), non-liquid crystalline, Δn0.22

Compound (2-2) is a compound represented by the following formula (2-2), liquid crystal, Δn0.22

For palm: product name LC756, made by BASF

Polymerization starter: trade name IRGACURE OXE02, manufactured by Ciba Speciality Chemicals

Surfactant: fluorine-based surfactant, trade name KH40, Seimi Chemical

(ii) / (i) compound ratio: polymerizable compound (ii) (compound (2-1) to compound (2-2)) to polymerizable liquid crystal compound (i) (compounds (1) to (5)) Ratio (weight ratio)

(Examples 6 to 10)

(modulation of phase difference film)

A monomer composition composed of 99.8% by weight of methacrylic acid methyl group and 2.2% by weight of acrylic acid methyl group was polymerized by a total polymerization method to obtain resin micelles.

Rubber particles were produced in accordance with Example 3 of JP-A-55-27576. The rubber particle has a spherical three-layer structure, an inner core layer, a bridging polymer of methyl methacrylate and a small amount of allyl methacrylate, and an inner layer of a main component of butyl acrylate with styrene and a small amount of acrylic acid. The acid allylic copolymer bridged copolymerized soft inert copolymer, and the outer layer is a hard polymer of methyl methacrylate and a small amount of ethyl acrylate. Again, the average of the inner layers The particle diameter was 0.19 μm, and the particle diameter of the outer layer was 0.22 μm.

70 parts by weight of the above-mentioned resin micelles were mixed with the weight of the rubber particles 30, and melt-kneaded by a biaxial extruder to obtain a methacrylate polymer composition A (glass transition temperature: 105 ° C).

The above-mentioned methacrylate polymer composition A (b layer) and styrene maleic anhydride copolymer (glass transition temperature 130 ° C) (layer a) were co-extruded at a temperature of 280 ° C to form a b layer/a. The three-layer structure of the layer/b layer gives a multi-layer film having an average thickness of 45/70/45 (μm) for each layer. The laminated film was stretched and stretched in a direction in which the zigzag axis was inclined by 45 degrees in the MD direction at an extension temperature of 134 ° C and a stretching magnification of 1.8 times to obtain an optically anisotropic layer.

The retardation in the front direction of the optically anisotropic layer was 140 nm, and the retardation in the thickness direction was -85 nm (measured value after extension of each numerical value). Further, one side of the optically anisotropic layer was subjected to corona discharge treatment to have a wetness index of 56 dyne/cm. This optically anisotropic layer was used as a retardation film as follows.

(modulation of brightness enhancement film)

Each of the circularly polarizing separators obtained in Examples 1 to 5 was bonded to the above-mentioned retardation film by an adhesive to form a brightness enhancement film (3-1) to (3-5).

Here, regarding the adhesive, first, 40 parts by weight of an ethylene-vinyl acetate copolymer latex (40% by weight of a nonvolatile matter, 40% by weight of a vinyl acetate), and a petroleum resin latex (40% by weight of a nonvolatile matter) were prepared. Resin softening point 85 ° C) 35 parts by weight, and paraffin hydrocarbon latex (nonvolatile content 40% by weight , resin softening point: 64 ° C) 10 parts by weight, at 23 ° C, a shear storage elastic modulus of 10 MPa of the adhesive composition, used in the adhesive composition, mixing particles of 4 μm diameter (shape: spherical, material: Polystyrene, refractive index: 1.59) The haze (measured by using a haze GURAD II (manufactured by Toyo Seiki Co., Ltd., in accordance with JIS K7136) was 70%. The adhesive was laminated on the hardened liquid crystal layer of the circularly polarizing separator to have an average thickness of 20 μm, and the surface and the corona-treated surface of the retardation film were laminated at 80 ° C, 2 kgf / 50 mm. The gap pressure is adhered to obtain a brightness enhancement film (3-1)~(3-5).

(liquid crystal display device)

The commercially available liquid crystal display device (Sharp, AQUOS, LC-37BE1W) is decomposed, and the respective brightness enhancement films (3-1) to (3-5) are reassembled to make the liquid crystal display device white display, and the front direction at this time The brightness (hereinafter, the front side brightness) was measured using a viewing angle measurement evaluation device (manufacturer: manufactured by Autronic-MELCHERS, trade name: ErgoScope). The liquid crystal display device is configured in the order of a backlight, a diffusion plate, a diffusion sheet, a cymbal sheet, an optical composite element, and a liquid crystal panel.

The front luminance when the luminance enhancement film is not mounted is 1, and the front luminance when the luminance enhancement films (3-1) to (3-5) are respectively configured is shown in Table 2 as a relative value.

Light glare and color halo are visually evaluated by the state of the brightness enhancement film. The glare is evaluated as "good" when the sudden change in brightness is removed when the observation angle is changed, and "bad" when it is eliminated. When the color halo system was not observed, it was evaluated as "good", and when it was observed, it was evaluated as "medium" when it was observed, and the display quality was observed. When the deterioration occurs, it is evaluated as "bad".

(Comparative Example 2)

In the same manner as in the circularly polarizing separation sheet of the above-described Example 6, except that the circularly polarizing separation sheet of Comparative Example 1 was used, the brightness enhancement film (3-6) was produced under the same conditions, and the test was carried out in the same manner. The results are shown in Table 2.

As a result of the results of Examples 6 to 10 and Comparative Example 2, it is understood that the liquid crystal display device including the brightness enhancement film including the circularly polarizing separation sheet of the present invention has high front luminance and reduced glare and haze.

Claims (10)

A liquid crystal composition comprising: a non-pivotic polymerizable liquid crystal compound (i) having Δn of 0.18 or more; a non-pivotic polymerizable compound (ii) having Δn of 0.18 or more; and a polymerizable property pair a palmitic compound; and a photopolymerization initiator, wherein the polymerizable liquid crystal compound (i) is a compound represented by the following formula (I): In the formula, Y ₁ ~Y ₆ are each independently represented as a single bond, -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC(=O)- O-, -NR ¹ -C(=O)-, -C(=O)-NR ¹ -, -OC(=O)-NR ¹ -, -NR ¹ -C(=O)-O-, - NR ¹ -C(=O)-NR ¹ -, -O-NR ¹ -, or -NR ¹ -O-, and R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; G ₁ and G ₂ Each of the two groups may independently represent a divalent aliphatic group having 1 to 20 carbon atoms which may have a substituent. The aliphatic group may also be interposed between -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC(=O)-O-, -NR ² -C ( =O)-, -C(=O)-NR ² -, -NR ² -, or -C(=O)- (except that -O- and -S- are respectively adjacent to each other); R ² system A hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Z ₁ and Z ₂ are each independently represented by an alkenyl group having 2 to 10 carbon atoms which may be substituted by a halogen atom; and A ₁ and A ₂ are each independently represented by carbon. a valence of 1 to 30 organic groups A; X ₁ to X ₈ are each independently represented by a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cyano group, a nitro group, and -OR ³ , -OC(=O)-R ³ , -C(=O)-OR ³ , -OC(=O)-OR ³ , -NR ⁴ -C(=O)-R ³ , -C(=O -NR ³ R ⁴ , or -OC(=O)-R ⁴ , NR ³ R ⁴ ; R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may have a substituent, in the alkyl group In the case of the alkyl group, there may be -O-, -S-, -OC(=O)-, -C(=O)-O-, -OC(=O)-O-, -NR ⁵ -C(=O)-, -C(=O)-NR ⁵ -, -NR ⁵ -, or -C(=O)- (wherein -O- and -S- are respectively adjacent to each other); ⁵ represents a hydrogen atom or a carbon-based alkyl group of 1 to 6; and A each independently represent lines b 0 or 1; and said polymerizable Compound (ii) The compound shown by the following formula ^{(II): Z 3 -MG-} O (CH 2) n 1 -Y 11 -Z 4 (II), wherein, Z ³ represents a system selected from the group consisting of a hydrogen atom, a group of a group consisting of an alkyl group having 1 to 2 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group, an amine group, and a cyano group; and the MG group is selected from 4,4'-linked di a liquid crystal primordium of a group consisting of a phenyl group, a 4,4'-bicyclohexylene group, a 2,6-naphthylene group, and a 4,4'-benzylidene group: n ₁ means an integer of 0 to 6; Y ¹¹ represents a group selected from the group consisting of a single bond, -O-, -S-, -CO-, -CS-, -OCO-, -CH ₂ -, -OCH ₂ -, -NHCO-, -OCOO-, -CH ₂ COO-, and -CH ₂ OCO- are selected from the group consisting of the group; Z ⁴ means an alkenyl group having 2 to 10 carbon atoms which may be substituted by a halogen atom. The liquid crystal composition according to claim 1, wherein the A ₁ and A ₂ of the polymerizable liquid crystal compound (i) each independently represent a phenylene group which may have a substituent, and may have a substituent. A phenylene group or a naphthylene group which may have a substituent. The liquid crystal composition according to claim 1, wherein the Z ₁ and Z ₂ of the polymerizable liquid crystal compound (i) independently represent CH ₂ =CH-, CH ₂ =C(CH ₃ )-, CH ₂ =CH-CH ₂ -, CH ₃ -CH=CH-, CH ₂ =CH-CH ₂ -CH ₂ -, CH ₂ =C(CH ₃ )-CH ₂ -CH ₂ -, (CH ₃ ) ₂ C=CH-CH ₂ -, (CH ₃ ) ₂ C=CH-CH ₂ -CH ₂ -, CH ₂ =C(Cl)-, CH ₂ =C(CH ₃ )-CH ₂ -,CH ₃ -CH =CH-CH ₂ -. The liquid crystal composition according to the first aspect of the invention, wherein the polymerizable liquid crystal compound (i) and the polymerizable compound (ii) are blended in a ratio of (the total weight of the polymerizable compound (ii)) / (polymerized) The weight ratio of the total weight of the liquid crystal compound (i) is 0.05 to 1. The liquid crystal composition according to claim 1, wherein the polymerizable compound (ii) has a molecular weight of less than 600. The liquid crystal composition according to claim 1, which further comprises a surfactant. A circularly polarizing separation sheet characterized in that the liquid crystal composition according to claim 1 is applied to a transparent resin substrate and cured. A method for producing a circularly polarizing separation sheet, comprising: a step of applying a liquid crystal composition according to claim 1 to a transparent resin substrate to obtain a liquid crystal layer; The step of hardening the liquid crystal layer by at least one light irradiation and/or warming treatment is included. A brightness enhancement film comprising: the circularly polarized light separation sheet according to item 7 of the patent application; and a phase difference film. A liquid crystal display device comprising: the brightness enhancement film according to claim 9; and a liquid crystal panel.