JP2010159324A - Polymerizable liquid crystal composition containing polymerizable liquid crystalline compound, and optically anisotropic film containing polymer of the polymerizable liquid crystalline composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystalline composition having excellent solubility in an organic solvent, providing good liquid crystallinity and transparency after polymerization, exhibiting excellent heat resistance and orientation control, and enabling thin film formation of the obtained optically anisotropic body. <P>SOLUTION: The polymerizable liquid crystalline composition contains one or more kinds of the polymerizable liquid crystalline compounds, for example, obtained by a reaction formula represented by the formula, and one or more kinds of polymerizable liquid crystalline compounds, for example, produceable by an esterification reaction of a benzoic acid ester having an acryloyl group with a phenol having the acryloyl group, in combination. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to polymerization comprising a polymerizable liquid crystal compound having a plurality of ring structures arranged on a straight chain containing at least one condensed ring, having a substituent on the ring, and having a (meth) acryloyloxy group The present invention relates to a functional liquid crystal composition and an optically anisotropic film containing a polymer of the polymerizable liquid crystal composition.

  A liquid crystal compound having a polymerizable functional group (hereinafter referred to as “polymerizable liquid crystal compound”) or a liquid crystal composition containing at least one polymerizable liquid crystal compound (hereinafter referred to as “polymerizable liquid crystal composition”) After uniform alignment in the state, when irradiated with active energy rays such as ultraviolet rays while maintaining the liquid crystal state, an optically anisotropic film containing a polymer in which the alignment state structure of liquid crystal molecules is fixed semi-permanently is created. I can do it. The polymer obtained in this manner has anisotropy of physical properties such as refractive index, dielectric constant, magnetic susceptibility, elastic modulus, and thermal expansion coefficient. It can be applied as a molded body having optical anisotropy such as a plate, a polarizing prism, a brightness enhancement film, a low-pass filter, various optical filters, an optical fiber coating material, a waveguide, a piezoelectric element, and a nonlinear optical element. In the optical anisotropic body (polymer) obtained by polymerization, characteristics other than anisotropy are also important. The properties include polymerization rate, polymer transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, melting point, glass transition point, clearing point, chemical resistance, heat resistance. And the like.

  In the above polymerizable liquid crystal composition, when the liquid crystal phase expression temperature is high, not only photopolymerization by active energy rays but also unintentional thermal polymerization is induced and the uniform alignment state of liquid crystal molecules is lost. It is difficult to fix. Accordingly, there is a need for a polymerizable liquid crystal composition that exhibits a liquid crystal phase near room temperature in order to facilitate temperature control during curing.

  The optically anisotropic film can be obtained by coating the polymerizable liquid crystal composition on a substrate and polymerizing it. However, when a non-polymerizable compound is contained, the obtained film has insufficient strength, There is a drawback that stress strain remains. Further, when the non-polymerizable compound is removed with a solvent or the like, there is a problem that the uniformity of the film cannot be maintained and unevenness occurs. Therefore, in order to obtain an optically anisotropic film having a uniform film thickness, a method in which a polymerizable liquid crystal composition is dissolved in a solvent is preferably used, and a liquid crystal compound or a polymerizable liquid crystal composition containing the same is used. Good solvent solubility of the product is required.

  The retardation R related to the contrast ratio of the optically anisotropic film is represented by R = Δn · d (wherein, Δn is optical (refractive index) anisotropy and d is a film thickness). Since R needs to be set to a specific value according to the application, d can be reduced by increasing Δn. This reduction in the thickness of the optically anisotropic film makes it easy to control the orientation of the liquid crystal during polymerization, improving the yield during production and improving the production efficiency.

  In addition, a polymerizable liquid crystal compound in which the polymerizable functional group is a (meth) acryl group or a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound has high polymerization reactivity, and the obtained polymer has high transparency and Since it has mechanical strength, its use as an optical anisotropic body has been actively studied (for example, see Patent Documents 1 to 10). However, the polymerizable liquid crystal compositions disclosed in these documents have a problem that it is difficult to control film formation when the film thickness is reduced.

JP-A-11-116534 Japanese National Patent Publication No. 11-130729 Japanese National Patent Publication No. 11-513360 Japanese Patent No. 3228348 JP 2005-015473 A JP 2005-206579 A JP 2002-265421 A JP 2002-308831 A JP 2002-308832 A JP 2007-119415 A

  In general, when the thickness of the optically anisotropic film is large, it is difficult to control the orientation of the liquid crystal molecules in the polymerizable liquid crystal composition, resulting in problems such as a decrease in film transmittance and coloring. On the other hand, if an attempt is made to produce a polymer film with a small film thickness, good orientation control can be obtained over the entire range of the film by thinning, but the film thickness control is difficult and the surface becomes non-uniform, and crystallization tends to occur. There was a problem to do. In addition, the stability of the liquid crystal state in which the orientation is controlled during film formation is poor, and the orientation may be disturbed before curing by ultraviolet irradiation or the like, and a conventionally known polymerizable liquid crystal composition cannot provide a satisfactory polymer film.

  Therefore, the object of the present invention is to exhibit a liquid crystal phase near room temperature (the temperature range showing the liquid crystal phase is wide) and crystals do not precipitate, and is excellent in solubility in organic solvents not containing halogen such as cyclohexanone and methyl ethyl ketone. A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound having excellent mechanical strength, applicability, orientation, shrinkage, water absorption, chemical resistance, and the like, and excellent transparency after polymerization. A polymerizable liquid crystal composition that maintains a uniform film state even when the polymer film is thinned, and has excellent heat resistance, orientation control, and optical characteristics, with respect to a polymer film obtained by curing the polymerizable liquid crystal composition, and An object of the present invention is to provide an optically anisotropic film obtained by using a polymer of the polymerizable liquid crystal composition.

  In order to solve the above problems, the present invention has been studied for various polymerizable liquid crystal compounds. As a result, it has been found that the above object can be achieved by combining polymerizable liquid crystal compounds having specific chemical structures, and the present invention has been completed. It came to do.

  That is, the present invention is a polymerizable liquid crystal composition comprising at least one polymerizable liquid crystal compound represented by the following general formula (I) and at least one polymerizable liquid crystal compound represented by the following general formula (II). The above object is achieved by providing a product.

（式中、環Ａ¹、Ａ²及びＡ³は、それぞれ独立に、ベンゼン環、シクロヘキサン環又はナフタレン環を表し、
Ｓ¹は、ハロゲン原子で置換されていてもよく、分岐を有してもよい炭素原子数２〜８のアルキレン基を表し、該アルキレン基は少なくとも酸素原子で１回中断されており、
Ｘ¹及びＸ²は、それぞれ独立に、水素原子又はメチル基を表し、
Ｚ¹及びＺ²は、それぞれ独立に、直接結合、−Ｌ¹−、−Ｏ−ＣＯ−、−ＣＯ−Ｏ−、−Ｌ¹Ｏ−、−ＯＬ¹−、−Ｌ¹Ｏ−ＣＯ−、−Ｌ¹ＣＯ−Ｏ−、−Ｌ¹Ｏ−ＣＯ−Ｏ−、−Ｏ−ＣＯＬ¹−、−ＣＯ−ＯＬ¹−又は−Ｏ−ＣＯ−ＯＬ¹−を表し、
Ｌ¹は、ハロゲン原子で置換されていてもよく、分岐を有してもよい炭素原子数１〜１０のアルキレン基を表し、該アルキレン基は酸素原子で１〜３回中断されていてもよく、
Ｙ¹、Ｙ²及びＹ³は、それぞれ独立に、酸素原子、硫黄原子若しくは−ＣＯ−で中断されていてもよい炭素原子数１〜６のアルキル基、ハロゲン原子で置換されていてもよい炭素原子数１〜８のアルコキシ基、ハロゲン原子又はシアノ基を表し、ａ、ｂ及びｃはそれぞれ独立に０か１であり、ａ＋ｂ＋ｃは１以上３以下である。）

(Wherein the rings A ¹ , A ² and A ³ each independently represent a benzene ring, a cyclohexane ring or a naphthalene ring,
S ¹ represents an alkylene group having 2 to 8 carbon atoms which may be substituted with a halogen atom and may have a branch, and the alkylene group is interrupted at least once by an oxygen atom;
X ¹ and X ² each independently represent a hydrogen atom or a methyl group,
Z ¹ and Z ² are independently a direct ^{bond, -L 1 -, - O-} CO -, - CO-O -, - L 1 O -, - OL 1 -, - L 1 O-CO-, ^{-L 1 CO-O -, -} L 1 O-CO-O -, - O-COL 1 -, - CO-OL 1 - or -O-CO-OL ¹ - represents,
L ¹ represents an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogen atom and may have a branch, and the alkylene group may be interrupted 1 to 3 times with an oxygen atom. ,
Y ¹ , Y ² and Y ³ are each independently an oxygen atom, a sulfur atom or an alkyl group having 1 to 6 carbon atoms which may be interrupted by —CO—, or a carbon atom which may be substituted with a halogen atom. An alkoxy group having 1 to 8 atoms, a halogen atom or a cyano group is represented, a, b and c are each independently 0 or 1, and a + b + c is 1 or more and 3 or less. )

（式中、Ｒ¹及びＲ²は、それぞれ独立に、水素原子、メチル基又はハロゲン原子を表し、
環Ａ⁴、環Ａ⁵及び環Ａ⁶は、それぞれ独立に、ベンゼン環、シクロヘキサン環、シクロヘキセン環、ナフタレン環、デカヒドロナフタレン環、テトラヒドロナフタレン環又はフェナントレン環を表し、これらの環中の−ＣＨ＝は−Ｎ＝で、−ＣＨ₂−は−Ｓ−又は−Ｏ−で中断されていてもよく、
Ｙ⁴、Ｙ⁵及びＹ⁶は、それぞれ独立に、ハロゲン原子若しくはシアノ基で置換されていてもよい炭素原子数１〜６のアルキル基、ハロゲン原子又はシアノ基を表し、該アルキル基中のメチレン基は−Ｏ−、−ＣＯ−、−Ｏ−ＣＯ−又は−ＣＯ−Ｏ−で中断されていてもよく、
Ｌ²及びＬ³は、それぞれ独立に、直接結合、−ＣＯＯ−、−（ＣＥ₂）_p−、−ＣＥ＝ＣＥ−、−（ＣＥ₂）_pＯ−、−ＣＥ＝ＣＥＣＥ₂Ｏ−、−Ｃ≡Ｃ−、−（ＣＥ₂）_pＣＯＯ−、−（ＣＥ₂）_pＯＣＯ−Ｏ−又は−（ＣＥ₂）_qＯ（ＣＥ₂）_rＯ−を表し、
Ｌ⁴及びＬ⁵は、それぞれ独立に、直接結合、−ＯＣＯ−、−（ＣＥ₂）_p−、−ＣＥ＝ＣＥ−、−Ｏ（ＣＥ₂）_p−、−ＯＣＥ₂ＣＥ＝ＣＥ−、−Ｃ≡Ｃ−、−ＯＣＯ（ＣＥ₂）_p−、−ＯＣＯ−Ｏ（ＣＥ₂）_p−、−（ＣＥ₂）_qＯ（ＣＥ₂）_rＯ−又は−Ｏ（ＣＥ₂）_qＯ（ＣＥ₂）_r−を表し、Ｌ²及びＬ⁵におけるＥは、水素原子、メチル基又はエチル基を表し、Ｌ³及びＬ⁴におけるＥは、水素原子を表し、複数あるＥは同一でも異なっていてもよく、
ｄ、ｅ及びｆは、それぞれ環Ａ⁴、環Ａ⁵及び環Ａ⁶における置換基の数であって、それぞれの置換される単環又は縮合環に含まれる６員環の数をｔとすると、ｄ、ｅ及びｆは、それぞれ独立に、２ｔ＋２以下の整数で、且つｅは１以上の整数を表し、
ｐはそれぞれ独立に１〜８の整数を表し、ｑ及びｒは、それぞれ独立に、１〜３の整数を表す。）

(Wherein R ¹ and R ² each independently represents a hydrogen atom, a methyl group or a halogen atom,
Ring A ⁴ , Ring A ⁵ and Ring A ⁶ each independently represent a benzene ring, a cyclohexane ring, a cyclohexene ring, a naphthalene ring, a decahydronaphthalene ring, a tetrahydronaphthalene ring or a phenanthrene ring, and —CH in these rings = Is —N═, —CH ₂ — may be interrupted by —S— or —O—,
Y ⁴ , Y ⁵ and Y ⁶ each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom or a cyano group, a halogen atom or a cyano group, and methylene in the alkyl group The group may be interrupted by —O—, —CO—, —O—CO— or —CO—O—,
L ² and L ³ are each independently a direct bond, —COO—, — (CE ₂ ) _p —, —CE═CE—, — (CE ₂ ) _p O—, —CE═CECE ₂ O—, — C≡C—, — (CE ₂ ) _p COO—, — (CE ₂ ) _p OCO—O— or — (CE ₂ ) _q O (CE ₂ ) _r O—
L ⁴ and L ⁵ each independently represent a direct _{bond, -OCO -, - (CE 2} ) p -, - CE = CE -, - O (CE 2) p -, - OCE 2 CE = CE -, - C≡C—, —OCO (CE ₂ ) _p —, —OCO—O (CE ₂ ) _p —, — (CE ₂ ) _q O (CE ₂ ) _r O— or —O (CE ₂ ) _q O (CE ₂ ) _r- represents, E in L ² and L ⁵ represents a hydrogen atom, a methyl group or an ethyl group, E in L ³ and L ⁴ represents a hydrogen atom, and a plurality of E may be the same or different. Well,
d, e, and f are the number of substituents in ring A ⁴ , ring A ^5, and ring A ⁶ , respectively, where t is the number of 6-membered rings included in each substituted monocyclic or condensed ring. , D, e and f are each independently an integer of 2t + 2 or less, and e represents an integer of 1 or more,
p represents each independently an integer of 1 to 8, and q and r each independently represents an integer of 1 to 3. )

  The present invention also provides an optically anisotropic film containing a polymer obtained by photopolymerizing the polymerizable liquid crystal composition.

  The polymerizable liquid crystal composition of the present invention is obtained because of its excellent solubility in organic solvents, good liquid crystallinity and transparency after polymerization, and high optical (refractive index) anisotropy (Δn). The optical anisotropic body can be made thin, and the selective reflection wavelength bandwidth of the cholesteric liquid crystal is widened.

  Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.

Examples of the alkylene group in the above general formula may be substituted with a halogen atom represented by S ¹ in (I), optionally from 2 to 8 carbon atoms which may have a branch, ethylene, propylene, trimethylene, tetramethylene Methylene, butane-1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylbutane-1,3-diyl, pentane-2,4-diyl, pentane-1,4-diyl, 3-methylbutane -1,4-diyl, 2-methylpentane-1,4-diyl, linear or branched alkylene groups such as pentamethylene, hexamethylene, heptamethylene, octamethylene and the like, and a halogen atom represented by L ¹ in may be substituted, the alkylene group number 1 to 10 of good carbon atoms have a branched, an alkylene group having 2 to 8 carbon atoms represented by the S ¹ Another group exemplified Te, methylene, nonamethylene, decamethylene and the like.

The Y ^1, Y ² and alkyl groups having 1 to 6 carbon atoms represented by Y ³ in the general formula (I), methyl, chloromethyl, trifluoromethyl, cyanomethyl, ethyl, dichloroethyl, propyl, Isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-methylpentyl, 3-methylpentyl, cyclohexyl, bicyclohexyl, 1-methylcyclohexyl, etc. Examples of the alkoxy group having 1 to 8 carbon atoms include methyloxy, chloromethyloxy, trifluoromethyloxy, cyanomethyloxy, ethyloxy, dichloroethyloxy, propyloxy, isopropyloxy, butyloxy, sec-butyloxy, Tributyloxy, isobu Tiloxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, cyclohexyloxy, heptyloxy, isoheptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, tert-octyloxy, 2-ethylhexyloxy, etc. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

In the above general formula (II), examples of the halogen atom represented by R ¹ , R ² , Y ⁴ , Y ⁵ and Y ⁶ include the groups exemplified as the halogen atom represented by Y ¹ , Y ² and Y ^3. Examples of the alkyl group having 1 to 6 carbon atoms represented by Y ⁴ , Y ⁵ and Y ⁶ are examples of the alkyl group having 1 to 6 carbon atoms represented by Y ¹ , Y ² and Y ^3. Group.

Among the polymerizable liquid crystal compounds represented by the general formula (I) or (II), the ring A ¹ , the ring A ² and the ring A ³ in the general formula (I) are 1,4-phenylene; In the general formula (II), ring A ⁴ , ring A ⁵ and ring A ⁶ are 1,4-phenylene or 2,6-naphthylene; in the above general formula (II), L ² is — (CE ₂ ) _P OCO—O— or — (CE ₂ ) _p O—, and L ⁵ is —OCO—O (CE ₂ ) _p — or —O (CE ₂ ) _p —, particularly the above general formula In (II), L ² is — (CH ₂ ) _p OCO—O— or — (CH ₂ ) _p O—, and L ⁵ is —OCO—O (CH ₂ ) _p — or —O ( CH _{2) p} - in which one (E those are all hydrogen atoms); the general formula (II), any one of L ² and L ⁵ is a direct binding What the preferable because solubility in the polymerizable liquid crystal composition is good.

  Specific examples of the polymerizable liquid crystal compound represented by the general formula (I) include compounds having the following structures. However, the present invention is not limited by the following compounds.

  Specific examples of the polymerizable liquid crystal compound represented by the general formula (II) include compounds having the following structures. However, the present invention is not limited by the following compounds.

  The production method of the polymerizable liquid crystal compound represented by the general formula (I) is not particularly limited and can be produced by applying a known reaction. For example, 4-acryloylbenzoic acid, a phenol compound, A phenol compound having an acryloyl group can be synthesized by the esterification reaction, and can be produced by an esterification reaction between the phenol compound and benzoic acid having an acryloyl group. Similarly, the production method of the polymerizable liquid crystal compound represented by the general formula (II) is not particularly limited and can be produced by applying a known reaction. For example, it has an acryloyl group. It can be produced by an esterification reaction between a benzoic acid ester and a phenol having an acryloyl group.

  In the polymerizable liquid crystal composition of the present invention, the polymerizable liquid crystal compound represented by the general formula (I) may be used singly or in combination of two or more, and the general formula (II). Similarly, the polymerizable liquid crystal compound represented by may be used alone or in combination of two or more.

  In the polymerizable liquid crystal composition of the present invention, the mass ratio of the total amount of the polymerizable liquid crystal compound represented by the general formula (I) and the total amount of the polymerizable liquid crystal compound represented by the general formula (II) is The ratio is preferably 10/90 to 99.9 / 0.1 (the former / the latter), more preferably 25/75 to 90/10, still more preferably 30/70 to 70/30. If the ratio of the polymerizable liquid crystal compound represented by the general formula (I) is less than 10, sufficient solvent solubility or stability of the liquid crystal phase cannot be obtained, and the ratio of the polymerizable liquid crystal compound represented by the general formula (I). If it is larger than 99.9, the liquid crystal phase may not be exhibited or the optical properties may be deteriorated.

  In the polymerizable liquid crystal composition of the present invention, the polymerizable liquid crystal compound represented by the general formula (I) and the polymerizable liquid crystal compound represented by the general formula (II) The content of the liquid crystal composition) is preferably 5 to 80% by mass, and preferably 25 to 60% by mass. If the amount is less than 5% by mass, sufficient solvent solubility and stability of the liquid crystal phase cannot be obtained. If the amount is more than 80% by mass, the liquid crystal phase may not be exhibited or optical properties may be deteriorated.

  The polymerizable liquid crystal composition containing the polymerizable liquid crystal compound according to the present invention can be converted into a liquid crystal polymer by polymerization. When forming an optically anisotropic film, the polymer of the polymerizable liquid crystal composition exhibits a liquid crystal phase at least near room temperature, and exhibits a liquid crystal phase at 25 ° C. or lower when forming a coating film. Is preferable because of its high operability.

  The polymerizable liquid crystal composition of the present invention has a liquid crystal compound other than the polymerizable liquid crystal compound, for example, a liquid crystalline monomer having an ethylenically unsaturated bond other than the polymerizable liquid crystal compound according to the present invention, and an optically active group. A monomer and a compound having an ethylenically unsaturated bond such as (meth) acrylic acid ester can be added. However, the amount of the compound having an ethylenically unsaturated bond is 30% by mass in the polymerizable liquid crystal composition of the present invention in order to maintain the heat resistance of the polymer prepared using the polymerizable liquid crystal composition. Hereinafter, 10% by mass or less is particularly preferable.

  Specific examples of the other liquid crystal monomers include compounds described in paragraphs [0049] to [0062] of JP-A No. 2007-119415.

  Examples of the monomer having an optically active group include those having an ethylenically unsaturated bond among compounds exemplified later as an optically active compound, as well as epoxide groups such as an epoxy group and an oxetane group. Also included are compounds having more than one species and having an optically active group.

  Examples of the compound having an ethylenically unsaturated bond such as (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and second butyl (meth) ) Acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, allyl (meth) acrylate, allyloxyl (meth) Acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 1-phenylethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, furfuryl (meth) acrylate, diphenylmethyl (meth) ) Acrylate, naphthyl (meth) acrylate, pentachlorophenyl (meth) acrylate, 2-chloroethyl (meth) acrylate, methyl-α-chloro (meth) acrylate, phenyl-α-bromo (meth) acrylate, trifluoroethyl (meth) ) Acrylate, tetrafluoropropyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Meth) acrylic acid esters such bets, diacetone acrylamide, styrene, vinyltoluene, divinylbenzene and the like.

  To the polymerizable liquid crystal composition of the present invention, a radical polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator can be added for the purpose of improving the polymerization reactivity. When adding these, it is preferable that it is 10 mass% or less in the polymeric liquid crystal composition of this invention, 5 mass% or less is still more preferable, and the range of 0.5-4 mass% is the most preferable.

  As the thermal polymerization initiator, known ones can be used without particular limitation, and examples thereof include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di (t-butylperoxy) -3. , 3,5-trimethylcyclohexane, 4,4-di (t-butylperoxy) butyl valerate, dicumyl peroxide, and other peroxides; 2,2′-azobisisobutyronitrile and other azo compounds And tetramethyltyrium disulfide.

  Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin propyl ether, and benzoin butyl ether; benzyl ketals such as benzyldimethyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2 -Diethoxy-2-phenylacetophenone, 1-benzyl-1-dimethylamino-1- (4'-morpholinobenzoyl) propane, 2-morpholy-2- (4'-methylmercapto) benzoylpropane, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-1-benzoylcyclohexane, 2-hydroxy-2-benzoylpropane, 2-hydro Acetophenones such as ci-2- (4′-isopropyl) benzoylpropane, N, N-dimethylaminoacetophenone, 1,1-dichloroacetophenone, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane; 2-methylanthraquinone, Anthraquinones such as 1-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; acetophenone dimethyl ketal, benzyldimethyl Ketals such as ketals; benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michlerzke And benzophenones such as 4-benzoyl-4′-methyldiphenyl sulfide; oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; 3 Carbazoles such as-(2-methyl-2-morpholinopropionyl) -9-methylcarbazole; α-dicarbonyls such as benzyl and methyl benzoylformate; JP-A-2000-80068, JP-A-2001-233842, Α-acyl oxime esters such as compounds described in JP-A-2005-97141, JP-T-2006-516246, JP-A-3860170, JP-A-3798008, and WO2006 / 018933; p-methoxyphenyl -2, -Bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl Triazines such as -4,6-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -s-triazine; benzoyl peroxide, 2,2'-azobisisobutyronitrile, ethyl anthraquinone 1,7-bis (9′-acridinyl) heptane, thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, benzophenone, phenylbiphenyl ketone, 4-benzoyl-4′-methyldiphenyl sulfide, 2- (P-butoxystyryl) -5-trichlorome Examples include til-1,3,4-oxadiazole, 9-phenylacridine, 9,10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, and thioxanthone / amine. A photoinitiator may be used independently or may use 2 or more types together.

  An optically active compound can also be added to the polymerizable liquid crystal composition of the present invention for the purpose of obtaining a polymer having a helical structure of a liquid crystal skeleton inside. The addition amount is preferably in the range of 0.1 to 10% by mass, more preferably in the range of 0.2 to 7.0% by mass in the polymerizable liquid crystal composition of the present invention. Examples of the optically active compound include compounds represented by [Chemical Formula 5] and [Chemical Formula 5A].

  When the polymerizable liquid crystal composition of the present invention is used for a polarizing film, a raw material for an alignment film, printing ink and paint, a protective film, or the like, depending on the purpose, the polymerizable liquid crystal composition includes a metal, Metal complexes, dyes, pigments, pigments, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, titanium oxide, etc. Metal oxides, polymerization inhibitors, storage stabilizers, photosensitizers, cross-linking agents, liquid crystal alignment aids, fine particles of inorganic and organic substances, functional compounds such as polymers, and the like can also be added.

  The polymerizable liquid crystal composition of the present invention can be polymerized to obtain an optically anisotropic film containing a polymer of the polymerizable liquid crystal composition. The optically anisotropic film contains, for example, the above-described various additive components such as the polymerizable liquid crystal compound according to the present invention and other liquid crystal compounds as necessary, and further dissolves them by adding a solvent as necessary. The polymerizable liquid crystal composition thus prepared is coated on a support, dried, and then polymerized by applying heat or irradiating ultraviolet rays or the like to align and fix the polymerizable liquid crystal compound. The optically anisotropic film may be formed on the support, or may be transferred after being formed on the support.

  The support is not particularly limited, but preferred examples thereof include glass plates, polyethylene terephthalate plates, polycarbonate plates, polyimide plates, polyamide plates, polymethyl methacrylate plates, polystyrene plates, polyvinyl chloride plates, cycloolefin polymers. Examples thereof include a plate, a polytetrafluoroethylene plate, a cellulose plate, a silicon plate, a reflecting plate, and a calcite plate.

  As a method of applying the polymerizable liquid crystal composition of the present invention to the support, known methods can be used. For example, a curtain coating method, an extrusion coating method, a roll coating method, a spin coating method, a dip coating method, A bar coating method, a spray coating method, a slide coating method, a blade coating method, a gravure coating method, a print coating method, or the like can be used.

  Examples of the solvent that can be used in producing the polymer of the polymerizable liquid crystal composition of the present invention include methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclopentanone, Ketones such as cyclohexanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate Ester solvents such as ethylene glycol monomethyl ether, ethyl-l-propyl, isopropyl acetate, n-butyl acetate, methoxybutyl acetate, methyl lactate, ethyl lactate Cellosolve solvents such as lenglycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, butyl cellosolve; methanol, ethanol, iso- or alcohol solvents such as n-propanol, iso- or n-butanol, amyl alcohol, t-butyl alcohol, diacetone alcohol, glycerin, monoacetylene, ethylene glycol, triethylene glycol, hexylene glycol; benzene, toluene, xylene, Aromatics such as n-butylbenzene, diethylbenzene, methoxybenzene, 1,2-dimethoxybenzene, mesitylene, tetralin Hydrocarbon solvents: Aliphatic hydrocarbon solvents such as hexane, heptane, octane, cyclohexane; Terpene hydrocarbon oils such as turpentine oil, D-limonene, and pinene; Mineral Spirit, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.) ), Parasol solvents such as Solvesso # 100 (Exxon Chemical Co., Ltd.); halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, tetrachloroethylene, methylene chloride; halogenation such as chlorobenzene Aromatic hydrocarbon solvents: carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, γ-butyrolactone, N, N-dimethylformamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, etc. Cited, medium Also, ketones or cellosolve solvent is preferable because of its excellent safety and solubility. These solvents can also be used as one or a mixture of two or more.

  The method for aligning the polymerizable liquid crystal compound in the polymerizable liquid crystal composition when preparing the optically anisotropic film containing the polymer of the polymerizable liquid crystal composition of the present invention includes, for example, the above-mentioned support. And a method of performing an orientation treatment in advance. As a preferred method of performing an alignment treatment on the support, a method of performing a rubbing or the like by providing a liquid crystal alignment layer composed of various polyimide alignment films, polyamide alignment films, polyvinyl alcohol alignment films, etc. on the support. Is mentioned. Examples of the method for aligning the polymerizable liquid crystal compound include a method of applying a magnetic field or an electric field to the polymerizable liquid crystal compound on the support. In addition, although the film thickness of the said optically anisotropic film is suitably selected according to the use etc. of the molded object which has optical anisotropy, Preferably it selects from the range of 0.01-100 micrometers. Also, when a plurality of the optically anisotropic films are used in a stacked manner, the film thickness is preferably within the above range.

  The polymerizable liquid crystal composition of the present invention can be polymerized by a known method using heat, light or electromagnetic waves. As the polymerization reaction by light or electromagnetic waves, radical polymerization in which ultraviolet light is irradiated using the photopolymerization initiator is preferable. It is also preferable to perform polymerization while applying a magnetic field or an electric field. The liquid crystal polymer formed on the support may be used as it is, but if necessary, it may be peeled off from the support or transferred to another support.

Preferred types of the light are ultraviolet rays, visible rays, infrared rays and the like. You may use electromagnetic waves, such as an electron beam and an X-ray. Usually, ultraviolet rays or visible rays are preferable. A preferable wavelength range is 150 to 500 nm. A more preferable range is 250 to 450 nm, and a most preferable range is 300 to 400 nm. Low light mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high pressure discharge lamps (high pressure mercury lamps, metal halide lamps), short arc discharge lamps (super high pressure mercury lamps, xenon lamps, mercury xenon lamps), etc. Among them, a high-pressure mercury lamp and an ultra-high pressure mercury lamp can be preferably used. Light from the light source may be irradiated to the polymerizable liquid crystal composition as it is, or a specific wavelength (or a specific wavelength region) selected by a filter may be irradiated to the polymerizable liquid crystal composition. A preferable irradiation energy density is 10 to 50000 mJ / cm ² , and a more preferable range is 10 to 20000 mJ / cm ² . A preferable illuminance is 0.1 to 5000 mW / cm ² , and a more preferable illuminance is 1 to 2000 mW / cm ² . When the exposure amount is small, polymerization is insufficient, and when the exposure amount is large, rapid curing may cause yellowing or deterioration.

  The polymer of the polymerizable liquid crystal composition of the present invention is formed into an optically anisotropic film, and is a retardation film for a liquid crystal display, an optical compensator for a liquid crystal display (retardation plate), an alignment film for a liquid crystal display, a polarizing plate, It can be used as a molded product having optical anisotropy, such as an optical element such as a viewing angle widening plate, a reflective film, a color filter, a holographic element, a light polarizing prism, an optical head, a low-pass filter, a brightness enhancement film, and a polarizing beam splitter.

  EXAMPLES Hereinafter, although an Example etc. are shown and this invention is demonstrated further in detail, this invention is not limited by these Examples.

In the following synthesis examples 1 to 3, polymerizable liquid crystal compounds according to the present invention were synthesized.
In Example 1 and Comparative Example 1 described below, polymerizable liquid crystal compositions having different contents of these compounds were prepared using the polymerizable liquid crystal compound according to the present invention or the polymerizable liquid crystal compound for comparison. The coating film liquid crystal phase stability of the composition was comparatively evaluated.
In Example 2 and Comparative Example 2 below, a polymerizable liquid crystal composition containing the compound is prepared using the polymerizable liquid crystal compound according to the present invention or the polymerizable liquid crystal compound for comparison, and the solvent for the polymerizable liquid crystal composition Solubility was comparatively evaluated.
In Example 3 below, an optically anisotropic film was prepared by respectively preparing a polymerizable liquid crystal composition of the present invention that expresses a cholesteric liquid crystal phase using a plurality of polymerizable liquid crystal compounds and optically active compounds according to the present invention having different compositions. In Example 4 below, an optically anisotropic film was prepared by preparing a polymerizable liquid crystal composition containing the compound using the polymerizable liquid crystal compound according to the present invention or the polymerizable liquid crystal compound for comparison. .

[Synthesis Example 1] Compound No. 1 Synthesis of Compound 1 In accordance with the procedure of Steps 1 to 3 shown below, Compound No. 1 was synthesized.

<Step 1>
Intermediate benzoic acid 1 was synthesized by the following procedure according to the reaction formula shown in the following [Chemical Formula 6].

４−ヒドロキシ安息香酸メチル１００ｇ（６５７．３ｍｍｏｌ）、水酸化カリウム３２９．２ｇ（３．０ｍｏｌ）、沃化カリウム１０．９ｇ（６５．７ｍｍｏｌ）、メタノール４４６ｇ、及び水４４６ｇを冷却管付反応フラスコに量りとり６０℃まで加熱した後、２−クロロエトキシエタノール３４３．３ｇ（２．８ｍｏｌ）を滴下し、還流下迄加熱し、そのまま４０時間反応を行なった。反応終了後、冷却し水酸化カリウム３８．８ｇ（６５７ｍｍｏｌ）と水８０ｇをゆっくり加えた後、昇温し、更に還流下にて４時間反応を継続した。室温迄冷却後、塩酸５５ｍＬ及び水１００ｇを滴下し、酸性になっていることを確認（ｐＨ＝１）後、５℃まで冷却しそのまま３０分間攪拌し、析出物を濾取した。濾過物を水５００ｇに加え、１５分間攪拌、濾取する操作を２回繰り返し、得られた濾過物を乾燥させ目的物である中間体安息香酸１の１１４．２ｇ（収率７６．８％）を得た。

100 g (657.3 mmol) of methyl 4-hydroxybenzoate, 329.2 g (3.0 mol) of potassium hydroxide, 10.9 g (65.7 mmol) of potassium iodide, 446 g of methanol, and 446 g of water were placed in a reaction flask equipped with a condenser tube. After weighing and heating to 60 ° C., 343.3 g (2.8 mol) of 2-chloroethoxyethanol was added dropwise, heated to reflux, and reacted for 40 hours. After completion of the reaction, the reaction mixture was cooled, 38.8 g (657 mmol) of potassium hydroxide and 80 g of water were slowly added, the temperature was raised, and the reaction was further continued under reflux for 4 hours. After cooling to room temperature, 55 mL of hydrochloric acid and 100 g of water were added dropwise, and after confirming that it was acidic (pH = 1), the mixture was cooled to 5 ° C. and stirred as it was for 30 minutes, and the precipitate was collected by filtration. The operation of adding the filtrate to 500 g of water, stirring for 15 minutes, and filtering was repeated twice, and the obtained filtrate was dried to obtain 114.2 g (yield 76.8%) of the target intermediate benzoic acid 1. Got.

<Step 2>
According to the reaction formula shown in the following [Chemical Formula 7], intermediate benzoic acid 2 was synthesized by the following procedure using intermediate benzoic acid 1 obtained in Step 1.

ステップ１で得られた中間体安息香酸１の５０ｇ（２２１ｍｍｏｌ）、アクリル酸１５６．３ｇ（２．２１ｍｏｌ）、ｐ−トルエンスルホン酸一水和物１６．８ｇ（８８．４ｍｍｏｌ）、ハイドロキノン２．４ｇ（２２．１ｍｍｏｌ）、及び１，２−ジクロロエタン３１０ｇを冷却管付き反応フラスコに量りとり、還流下まで加温し、そのまま３時間還流した。減圧下溶媒を留去し、残渣に水６２０ｇに加え、５℃に冷却後、析出物を濾取した。濾物を水で洗浄した後に、アセトンで洗浄、乾燥することで目的物である中間体安息香酸２の５４．６ｇ（収率８８．１％）を得た。

50 g (221 mmol) of the intermediate benzoic acid 1 obtained in Step 1, 156.3 g (2.21 mol) of acrylic acid, 16.8 g (88.4 mmol) of p-toluenesulfonic acid monohydrate, 2.4 g of hydroquinone (22.1 mmol) and 310 g of 1,2-dichloroethane were weighed into a reaction flask equipped with a condenser, heated to reflux, and refluxed for 3 hours. The solvent was distilled off under reduced pressure, the residue was added to 620 g of water, cooled to 5 ° C., and the precipitate was collected by filtration. The filtrate was washed with water, then washed with acetone and dried to obtain 54.6 g (yield 88.1%) of the target intermediate benzoic acid 2.

<Step 3>
In accordance with the reaction formula shown in the following [Chemical Formula 8], using the intermediate benzoic acid 2 obtained in Step 2, the polymerizable liquid crystal compound No. 1 was prepared by the following procedure. 1 was synthesized.
That is, first, an ester body (1) of 4-acryloylbenzoic acid and 4-benzyloxyphenol having a substituent in the ortho position was synthesized, and a phenol body (2) was obtained by debenzylation. 2) and the intermediate benzoic acid 2 (3) obtained in Step 2 are esterified with the target compound No. 1 (4) was obtained.

メタンスルホニルクロリド１９．７ｇ（１７１．７ｍｍｏｌ）、及びテトラヒドロフラン（ＴＨＦ）１９ｇを反応フラスコに仕込み撹拌しながら−４０℃以下まで冷却し、４−アクリロイルオキシ安息香酸３０ｇ（１５６．１ｍｍｏｌ）、及びトリエチルアミン１９．０ｇ（１８７．３ｍｍｏｌ）をＴＨＦ７６ｇに溶解した混合液を−２０℃以下で滴下しそのまま１時間反応を継続した。反応終了後、４−ジメチルアミノピリジン（ＤＭＡＰ）１８１ｍｇ（１．６ｍｍｏｌ）、及びトリエチルアミン１９．０ｇ（１８７．３ｍｍｏｌ）を追加し、４−ベンジルオキシ−２−プロピルフェノール３９．７ｇ（１６３．９ｍｍｏｌ）をＴＨＦ３８ｇに溶解した混合液を−４０℃以下で滴下し、そのまま更に１時間反応を継続した。反応終了後室温に戻し、反応液を水洗、有機層を脱溶媒し、残渣をトルエン／メタノール混合溶媒で再結晶することによってエステル体（１）の４８．２ｇ（収率７４．１％）を得た。
塩化アルミニウム３．８ｇ（２８．８ｍｍｏｌ）をアニソール９４ｇに溶解させ、氷水冷下で先に合成したエステル体（１）４０ｇ（９６．０ｍｍｏｌ）をアニソール９４ｇに溶解させた混合液を１５℃以下で滴下し、そのまま１時間反応させた。反応終了後、塩酸、及び酢酸エチルを追加し水洗、脱溶媒した後、残渣をヘキサンに滴下し、析出物を濾取、乾燥させ、フェノール体（２）の２９．６ｇ（収率９４．５％）を得た。
メタンスルホニルクロリド３．６ｇ（３１．４ｍｍｏｌ）、及びＴＨＦ１７ｇを反応フラスコに仕込み−４０℃以下まで冷却後、ステップ２で得られた中間体安息香酸２（３）８．０ｇ（２８．５ｍｍｏｌ）、トリエチルアミン３．５ｇ（３４．３ｍｍｏｌ）、及びＴＨＦ７０ｇ混合液を−３０℃以下で滴下し、そのまま１時間反応を行なった。反応終了後、ＤＭＡＰ３５ｍｇ（０．２９ｍｍｏｌ）、及びトリエチルアミン３．５ｇ（３４．３ｍｍｏｌ）を追加し、フェノール体（２）９．８ｇ（３０．０ｍｍｏｌ）をＴＨＦ３４ｇに溶解させた溶液を−３０℃以下で滴下し、更に１時間反応を継続した。反応終了後、反応液を水洗し有機層を脱溶媒した。残渣をシリカゲルカラムクロマトグラフィー（展開液：酢酸エチル／トルエン＝１／９）で処理し、更にアセトン／メタノール混合溶媒で再結晶することによって無色不定形結晶１２．３１ｇ（収率７３．２％）を得た。¹Ｈ−ＮＭＲ（重クロロホルム溶媒）測定を行い、目的の化合物Ｎｏ．１（４）であることを確認した。
また、得られた化合物Ｎｏ．１について、相転移挙動を観察した。相転移温度（℃）は、ＤＳＣ測定（走査速度５℃／分）と偏光顕微鏡観察による光学組織の確認によって決定した。結果を下記〔化９〕に示す。尚、Ｃｒは結晶相を、Ｎはネマチック相を、Ｉは等方性液体相をそれぞれ表す。

19.7 g (171.7 mmol) of methanesulfonyl chloride and 19 g of tetrahydrofuran (THF) were charged into a reaction flask and cooled to −40 ° C. or lower with stirring, and 30 g (156.1 mmol) of 4-acryloyloxybenzoic acid and triethylamine 19 A mixture solution of 0.0 g (187.3 mmol) dissolved in 76 g of THF was dropped at −20 ° C. or lower and the reaction was continued for 1 hour. After completion of the reaction, 181 mg (1.6 mmol) of 4-dimethylaminopyridine (DMAP) and 19.0 g (187.3 mmol) of triethylamine were added, and 39.7 g (163.9 mmol) of 4-benzyloxy-2-propylphenol was added. Was added dropwise at −40 ° C. or lower, and the reaction was continued for another hour. After completion of the reaction, the temperature is returned to room temperature, the reaction solution is washed with water, the organic layer is desolvated, and the residue is recrystallized with a toluene / methanol mixed solvent to obtain 48.2 g (yield 74.1%) of the ester (1). Obtained.
A mixed solution in which 3.8 g (28.8 mmol) of aluminum chloride was dissolved in 94 g of anisole, and 40 g (96.0 mmol) of the ester (1) synthesized earlier under ice-water cooling was dissolved in 94 g of anisole at 15 ° C. or lower. The solution was added dropwise and allowed to react for 1 hour. After completion of the reaction, hydrochloric acid and ethyl acetate were added, washed with water, and the solvent was removed. Then, the residue was added dropwise to hexane, the precipitate was collected by filtration and dried, and 29.6 g of phenol (2) (yield 94.5). %).
After charging 3.6 g (31.4 mmol) of methanesulfonyl chloride and 17 g of THF into a reaction flask and cooling to −40 ° C. or lower, 8.0 g (28.5 mmol) of the intermediate benzoic acid 2 (3) obtained in Step 2, A mixed solution of 3.5 g (34.3 mmol) of triethylamine and 70 g of THF was dropped at −30 ° C. or less, and the reaction was carried out for 1 hour as it was. After completion of the reaction, 35 mg (0.29 mmol) of DMAP and 3.5 g (34.3 mmol) of triethylamine were added, and a solution in which 9.8 g (30.0 mmol) of the phenol compound (2) was dissolved in 34 g of THF was −30 ° C. or lower. The reaction was continued for another hour. After completion of the reaction, the reaction solution was washed with water to remove the organic layer. The residue was treated with silica gel column chromatography (developing solution: ethyl acetate / toluene = 1/9), and further recrystallized with a mixed solvent of acetone / methanol to give 12.31 g of colorless amorphous crystals (yield 73.2%). Got. ¹ H-NMR (deuterated chloroform solvent) measurement was performed, and the target compound No. 1 (4) was confirmed.
In addition, the obtained compound No. For 1, the phase transition behavior was observed. The phase transition temperature (° C.) was determined by DSC measurement (scanning speed 5 ° C./min) and confirmation of the optical structure by polarization microscope observation. The results are shown in the following [Chemical 9]. Cr represents a crystal phase, N represents a nematic phase, and I represents an isotropic liquid phase.

(Measurement result)
¹ H-NMR [CDCl ₃ ] (ppm)
0.9 (t; 3H), 1.7 (q; 2H), 2.6 (t; 2H), 3.8-3.9 (m; 4H), 4.2-4.4 (m; 4H), 5.9 (d; 1H), 6.1-6.2 (m; 2H), 6.3-6.5 (m; 2H), 6.7 (d; 1H), 7.0 (D; 2H), 7.1-7.2 (m; 3H), 7.3 (d; 2H), 8.2-8.3 (q; 4H)
IR [ATR] (cm ^-1 )
402, 522, 556, 607, 631, 650, 659, 675, 694, 759, 782, 796, 808, 833, 852, 882, 907, 974, 991, 1018, 1036, 1074, 1115, 1147, 1187, 1216, 1255, 1294, 1340, 1377, 1404, 1442, 1471, 1493, 1513, 1605, 1635, 1720, 2882, 2959, 3071

[Synthesis Example 2] Compound No. Synthesis of Compound 2 According to the procedure of Steps 1 and 2 shown below, Compound No. 2 was prepared. 2 was synthesized.

<Step 1>
According to the reaction formula shown in the following [Chemical Formula 10], an intermediate phenol was synthesized by the following procedure.

メタンスルホニルクロリド４．５０ｇ（３７．５ｍｍｏｌ）、及び（Ｎ，Ｎ‘−ジメチルホルムアミド）ＤＭＦ３０ｇを反応フラスコに仕込み、−４０℃以下まで冷却後、原料安息香酸１０ｇ（３５．７ｍｍｏｌ）、ジイソプロピルエチルアミン５．５３ｇ（４２．８ｍｍｏｌ）、及びＤＭＦ３０ｇの混合液を−４０℃以下で滴下し、そのまま攪拌した。続けてＤＭＦ６０ｇに溶解させた２，５−ジヒドロキシアセトフェノン５．７０ｇ（３７．５ｍｍｏｌ）を−４０℃以下で滴下し１０分間撹拌した後、ジイソプロピルエチルアミン１０．１４ｇ（７８．５ｍｍｏｌ）を−２５℃以下で滴下し、そのままの温度で４時間撹拌した。反応終了後、反応液を分液ロートに移し、水洗後、有機層を脱溶媒し、残渣をシリカゲルカラムクロマトグラフィー（展開液：酢酸エチル／ヘキサン＝１／２）で処理した。更に酢酸エチル／ヘキサン混合溶媒で再結晶することによって目的物である中間体フェノール５．７１ｇ（収率３８．５％）を得た。

A reaction flask was charged with 4.50 g (37.5 mmol) of methanesulfonyl chloride and 30 g of (N, N′-dimethylformamide) DMF, cooled to −40 ° C. or lower, and then 10 g (35.7 mmol) of raw material benzoic acid, diisopropylethylamine 5 A mixed solution of .53 g (42.8 mmol) and DMF 30 g was added dropwise at −40 ° C. or lower and stirred as it was. Subsequently, 5.70 g (37.5 mmol) of 2,5-dihydroxyacetophenone dissolved in 60 g of DMF was dropped at −40 ° C. or lower and stirred for 10 minutes, and then 10.14 g (78.5 mmol) of diisopropylethylamine was −25 ° C. or lower. And stirred at the same temperature for 4 hours. After completion of the reaction, the reaction solution was transferred to a separatory funnel, washed with water, the organic layer was desolvated, and the residue was treated with silica gel column chromatography (developing solution: ethyl acetate / hexane = 1/2). Further, recrystallization from an ethyl acetate / hexane mixed solvent gave 5.71 g (yield: 38.5%) of the target intermediate phenol.

<Step 2>
According to the reaction formula shown in the following [Chemical Formula 11], compound No. 2 was synthesized.

メタンスルホニルクロリド１．３１ｇ（１１．５ｍｍｏｌ）、及びＴＨＦ１２ｇを反応フラスコに仕込み、−４０℃以下まで冷却、４−アクリロイルオキシ安息香酸２ｇ（１０．４ｍｍｏｌ）、トリエチルアミン１．２６ｇ（１２．５ｍｍｏｌ）、及びＴＨＦ２４ｇの混合液を−４０℃以下で滴下しそのまま１時間攪拌した。反応終了後、ＤＭＡＰ１ｍｇ（０．１０ｍｍｏｌ）、及びトリエチルアミン１．２６ｇ（１２．５ｍｍｏｌ）を追加し、ステップ１で得られた中間体フェノール４．５３ｇ（１０．９ｍｍｏｌ）のＴＨＦ１２ｇ溶液を−４５℃以下で滴下し、そのまま４時間攪拌した反応終了後、反応液を分液ロートに移し、水洗、有機層を脱溶媒し、残渣をシリカゲルカラムクロマトグラフィー（展開液：酢酸エチル／トルエン＝１／９）で処理した。更に残渣をアセトン／メタノール混合溶媒で再結晶することによって無色結晶２．６８ｇ（収率４３．７％）を得た。¹Ｈ−ＮＭＲ（重クロロホルム溶媒）測定を行い、目的の化合物Ｎｏ．２であることを確認した。また、得られた化合物Ｎｏ．２について、化合物Ｎｏ．１と同様にして、相転移挙動を観察した。結果を下記〔化１２〕に示す。

A reaction flask was charged with 1.31 g (11.5 mmol) of methanesulfonyl chloride and 12 g of THF, cooled to −40 ° C. or lower, 2 g (10.4 mmol) of 4-acryloyloxybenzoic acid, 1.26 g (12.5 mmol) of triethylamine, And THF 24g liquid mixture was dripped at -40 degrees C or less, and was stirred as it was for 1 hour. After completion of the reaction, 1 mg (0.10 mmol) of DMAP and 1.26 g (12.5 mmol) of triethylamine were added, and a THF 12 g solution of 4.53 g (10.9 mmol) of the intermediate phenol obtained in Step 1 was reduced to −45 ° C. or less. After completion of the reaction stirred for 4 hours, the reaction solution was transferred to a separatory funnel, washed with water, the organic layer was desolvated, and the residue was subjected to silica gel column chromatography (developing solution: ethyl acetate / toluene = 1/9). Was processed. Further, the residue was recrystallized with an acetone / methanol mixed solvent to obtain 2.68 g of colorless crystals (yield 43.7%). ¹ H-NMR (deuterated chloroform solvent) measurement was performed, and the target compound No. 2 was confirmed. In addition, the obtained compound No. No. 2, compound no. In the same manner as in Example 1, the phase transition behavior was observed. The results are shown in the following [Chemical Formula 12].

(Measurement result)
¹ H-NMR [CDCl ₃ ] (ppm)
2.6 (s; 3H), 3.8-4.0 (m; 4H), 4.2-4.4 (m; 4H), 5.9 (d; 1H), 6.1-6. 2 (m; 2H), 6.3-6.5 (m; 2H), 6.7 (d; 1H), 7.0 (d; 2H), 7.3 (m; 3H), 7.5 (D; 1H), 7.7 (d; 1H) 8.2-8.3 (q; 4H)
IR [ATR] (cm ^-1 )
421, 505, 532, 563, 616, 629, 660, 672, 689, 724, 757, 810, 843, 859, 958, 1017, 1070, 1137, 1159, 1171, 1193, 1248, 1271, 1300, 1404 1455, 1484, 1506, 1576, 1604, 1636, 1689, 1725, 2945, 3074

[Synthesis Example 3] Compound No. Synthesis of Compound No. 3 According to the procedure of Steps 1 and 2 shown below, Compound No. 3 was synthesized.

<Step 1>
According to the reaction formula shown in the following [Chemical Formula 13], an intermediate phenol was synthesized by the following procedure.

反応フラスコにメタンスルホニルクロリド４．５０ｇ（０．０３９３ｍｏｌ）、及びＤＭＦ１０ｇを仕込み、−３０℃まで冷却した。その反応溶液に安息香酸１０ｇ（０．０３５７ｍｏｌ）、及びジイソプロピルエチルアミン５．５３ｇ（０．０４２８ｍｏｌ）のＤＭＦ２０ｇ溶液を滴下し、１．５時間撹拌した。その後ジイソプロピルエチルアミン５．５３ｇ（０．０４２８ｍｏｌ）を加え、更に１−（２，５−ジヒドロキシフェニル）プロパン−１−オン５．９３ｇ（０．０３５７ｍｏｌ）のＤＭＦ５ｇ溶液を滴下し、そのまま３時間反応させた。室温に戻した後、酢酸エチルを加え、塩酸で酸性化した後、水洗し、有機層を脱溶媒した。残渣をシリカゲルカラムクロマトグラフィー（展開液：酢酸エチル／ヘキサン＝１／２）で精製し安息香誘導体酸（中間体フェノール）１．９ｇ（収率１２．４％）を得た。

A reaction flask was charged with 4.50 g (0.0393 mol) of methanesulfonyl chloride and 10 g of DMF, and cooled to −30 ° C. To the reaction solution, 10 g (0.0357 mol) of benzoic acid and 20 g of DMF in 5.53 g (0.0428 mol) of diisopropylethylamine were added dropwise and stirred for 1.5 hours. Thereafter, 5.53 g (0.0428 mol) of diisopropylethylamine was added, and a solution of 5.93 g (0.0357 mol) of 1- (2,5-dihydroxyphenyl) propan-1-one in 5 g of DMF was added dropwise and allowed to react for 3 hours. It was. After returning to room temperature, ethyl acetate was added, acidified with hydrochloric acid, washed with water, and the organic layer was desolvated. The residue was purified by silica gel column chromatography (developing solution: ethyl acetate / hexane = 1/2) to obtain 1.9 g (yield 12.4%) of benzoderivative acid (intermediate phenol).

<Step 2>
In accordance with the reaction formula shown in the following [Chemical Formula 14], Compound No. 3 was synthesized.

反応フラスコにメタンスルホニルクロリド０．６６ｇ（０．００５７６ｍｏｌ）、及びＴＨＦ６ｇを仕込み、−３０℃まで冷却した。４−アクリロイルオキシ安息香酸１ｇ（０．０５１６ｍｏｌ）、及びトリエチルアミン０．６５ｇ（０．００６３８ｍｏｌ）のＴＨＦ７ｇ溶液を滴下し、そのまま１．５時間攪拌した。トリエチルアミン０．６５ｇ（０．００６３８ｍｏｌ）を加えた後に、ステップ１で得られた中間体フェノール１．９ｇ（０．００４４３ｍｏｌ）のＴＨＦ１０ｇ溶液を滴下し、３時間反応させた。室温に戻した後、酢酸エチルを加え、塩酸で酸性化後、水洗し有機層を脱溶媒した。残渣をシリカゲルカラムクロマトグラフィー（展開液：酢酸エチル／ヘキサン＝１／２）で処理後、アセトン／メタノール混合溶媒で再結晶することによって無色結晶２．０ｇ（収率７４．９％）を得た。¹Ｈ−ＮＭＲ（重クロロホルム溶媒）測定を行い、目的の化合物Ｎｏ．３であることを確認した。また、得られた化合物Ｎｏ．３について、化合物Ｎｏ．１と同様にして、相転移挙動を観察した。結果を〔化１５〕に示す。

A reaction flask was charged with 0.66 g (0.00576 mol) of methanesulfonyl chloride and 6 g of THF, and cooled to −30 ° C. A solution of 4-acryloyloxybenzoic acid 1 g (0.0516 mol) and triethylamine 0.65 g (0.00638 mol) in THF 7 g was added dropwise, and the mixture was stirred as it was for 1.5 hours. After adding 0.65 g (0.00638 mol) of triethylamine, a 10 g THF solution of 1.9 g (0.00443 mol) of the intermediate phenol obtained in Step 1 was added dropwise and reacted for 3 hours. After returning to room temperature, ethyl acetate was added, acidified with hydrochloric acid, washed with water, and the organic layer was removed. The residue was treated with silica gel column chromatography (developing solution: ethyl acetate / hexane = 1/2) and recrystallized with a mixed solvent of acetone / methanol to obtain 2.0 g of colorless crystals (yield 74.9%). . ¹ H-NMR (deuterated chloroform solvent) measurement was performed, and the target compound No. 3 was confirmed. In addition, the obtained compound No. For compound 3, compound no. In the same manner as in Example 1, the phase transition behavior was observed. The results are shown in [Chemical 15].

(Measurement result)
_{^{1 H-NMR [CDCl 3]}} (ppm)
1.1 (t; 3H), 2.9 (q; 2H), 3.8-4.0 (m; 4H), 4.2-4.4 (m; 4H), 5.9 (d; 1H), 6.1-6.2 (m; 2H), 6.3-6.5 (m; 2H), 6.7 (d; 1H), 7.0 (d; 2H), 7.3 (M; 3H), 7.5 (d; 1H), 7.7 (d; 1H) 8.2-8.3 (q; 4H)
IR [ATR] (cm ^-1 )
417, 509, 599, 628, 655, 665, 692, 755, 761, 800, 852, 887, 905, 974, 986, 1019, 1075, 1123, 1162, 1184, 1196, 1123, 1251, 1294, 1346 1379, 1405, 1454, 1486, 1512, 1578, 1606, 1635, 1694, 1720, 2941, 3072

[Example 1]
<Preparation of polymerizable liquid crystal composition>
A 20% cyclopentanone solution of a polymerizable liquid crystal compound was prepared with the formulation shown in [Table 1] below. In addition, the compounds A and B shown in [Chemical Formula 16] and the comparative compounds 1 and 2 are the above-mentioned compound No. The synthesis was performed according to the method for 1 or a known method. The coating film liquid crystal phase stability of the obtained polymerizable liquid crystal composition was evaluated and measured by the following methods. In Table 1, the unit of the blending amount is mass%.

<Coating film liquid crystal phase stability evaluation>
The 20% cyclopentanone solution obtained above was rubbed with a spin coater (Opticaat MS-A-150, manufactured by Mikasa), and the film thickness after drying was 1.0 μm. It was coated so that After drying for 3 minutes on a 100 ° C. hot stage, the temperature was immediately returned to room temperature and left for 5 minutes. After confirming that uniaxially uniform orientation was obtained by observation with a polarizing microscope and the presence or absence of crystal precipitation, the sample was allowed to stand at room temperature. The first 8 hours were every 30 minutes, and then every 12 hours from the start. The optical structure was observed with a polarizing microscope and the presence or absence of a change was confirmed, and the first time when a change such as crystal precipitation was confirmed was compared.

From the above results, the following is clear. That is, the compound No. 1 which is a polymerizable liquid crystal compound represented by the above general formula (I). 1 and the polymerizable liquid crystal composition containing the compound A or the compound B which is the polymerizable liquid crystal compound represented by the general formula (II) have good stability of the liquid crystal phase at room temperature. In the polymerizable liquid crystal composition containing the compound A or B which is the polymerizable liquid crystal compound represented by II) and a comparative compound, the liquid crystal phase at room temperature is inferior in stability. In addition, this compound No. 1, a photopolymerization initiator N-1919 (manufactured by ADEKA) 3% added to the polymerizable liquid crystal compound was used for coating, irradiation with ultraviolet rays (high pressure mercury lamp 300 mJ) / Cm ² ) It was confirmed that none of the cured films prepared by the method had any tack and good curability.

[Example 2]
With the formulation shown in [Table 2] below, 20 parts of a polymerizable liquid crystal compound and 80 parts of propylene glycol monomethyl ether acetate were weighed and heated to 50 ° C. with stirring to confirm that they were completely dissolved. After returning to room temperature, the mixture was filtered with a 0.45 μm filter and allowed to stand at room temperature. The presence or absence of crystal precipitation was confirmed visually. It was allowed to stand at room temperature, and the presence or absence of change was checked every 10 minutes for the first 3 hours, thereafter every 30 minutes from the start to 12 hours, and thereafter every 12 hours. In Table 2, the unit of the blending amount is mass%.

  From the above results, the following is clear. That is, the compound No. 1 which is a polymerizable liquid crystal compound represented by the above general formula (I). 1 and the polymerizable liquid crystal composition containing the compound A which is the polymerizable liquid crystal compound represented by the general formula (II) can significantly improve the solvent solubility, but the general formula (II) In the polymerizable liquid crystal composition containing the compound A which is a polymerizable liquid crystal compound represented by formula (I) and a comparative compound, sufficient solvent solubility was not obtained.

化合物Ｎｏ．１／化合物Ａ／上記光学活性化合物＝４７．５／４７．５／５（質量比）の割合で重合性液晶化合物１．０ｇをシクロペンタノン４．０ｇに溶解させ、光重合開始剤Ｎ−１９１９（ＡＤＥＫＡ社製）を０．０３ｇ添加し、完全に溶解させた。スピンコーター（ミカサ社製ＯＰＴＩＣＯＡＴ ＭＳ−Ａ−１５０）を使用し、ラビング処理を施したポリイミド配向膜付ガラス基板に調製した重合性液晶組成物溶液を塗布した。１００℃で３分乾燥後、室温に戻し３分放置後、高圧水銀灯（１２０Ｗ／ｃｍ）で２０秒間照射し硬化させた（膜厚が約１．０ｍｍになるようスピンコーターの回転数および時間を調整した）。得られた硬化膜は、均一な黄緑色の選択反射を呈した光学異方性膜であった。更に、５°正反射付属装置を取り付けた分光光度計（日立ハイテクノロジーズ社製；Ｕ−３０１０形）を使用して、２５℃、波長８００〜４００ｎｍの範囲で反射率測定を実施し、選択反射中心波長（λ）を測定した。波長幅１２７ｎｍ、波長中心は５８６ｎｍであった。 [Example 3-1] Preparation of optically anisotropic film 1

Compound No. In a ratio of 1 / compound A / optically active compound = 47.5 / 47.5 / 5 (mass ratio), 1.0 g of a polymerizable liquid crystal compound was dissolved in 4.0 g of cyclopentanone, and a photopolymerization initiator N- 0.019 g of 1919 (manufactured by ADEKA) was added and completely dissolved. The prepared polymerizable liquid crystal composition solution was applied to a glass substrate with a polyimide alignment film subjected to rubbing treatment using a spin coater (OPTICOAT MS-A-150 manufactured by Mikasa). After drying at 100 ° C. for 3 minutes, returning to room temperature and allowing to stand for 3 minutes, it was cured by irradiation with a high-pressure mercury lamp (120 W / cm) for 20 seconds (the rotation speed and time of the spin coater were adjusted so that the film thickness was about 1.0 mm). It was adjusted). The obtained cured film was an optically anisotropic film exhibiting uniform yellow-green selective reflection. Furthermore, using a spectrophotometer (manufactured by Hitachi High-Technologies Corp .; U-3010 type) equipped with a 5 ° specular reflection accessory, the reflectance is measured in the range of 25 ° C. and wavelength of 800 to 400 nm, and selective reflection is performed. The central wavelength (λ) was measured. The wavelength width was 127 nm and the wavelength center was 586 nm.

[Example 3-1] Preparation of optically anisotropic film 2
Compound No. 1 / Compound No. 1 4 / The above-mentioned optically active compound = 45/45/10 (mass ratio) 1.0 g of a polymerizable liquid crystal compound was dissolved in 4.0 g of cyclopentanone, and a photopolymerization initiator N-1919 (manufactured by ADEKA) was added. 0.03 g was added and completely dissolved. The prepared polymerizable liquid crystal composition solution was applied to a glass substrate with a polyimide alignment film subjected to rubbing treatment using a spin coater (OPTICOAT MS-A-150 manufactured by Mikasa). After drying at 100 ° C. for 3 minutes, returning to room temperature and allowing to stand for 3 minutes, it was cured by irradiation with a high-pressure mercury lamp (120 W / cm) for 20 seconds (the rotation speed and time of the spin coater were adjusted so that the film thickness was about 1.0 mm). It was adjusted). The obtained cured film was transparent and reflected in the range of 25 ° C. and wavelength of 800 to 300 nm using a spectrophotometer (manufactured by Hitachi High-Technologies Corp .; U-3010 type) equipped with a 5 ° specular reflection accessory. When rate measurement was performed, selective reflection was not confirmed at 360 nm or more.
Moreover, the retardation measurement was performed by the Senarmon method with the monochromatic light of wavelength 546nm using the polarizing microscope OPTIPHOT2-POL by Nikon. In this case, the retardation at each inclination angle was measured by setting the substrate on a pedestal that can change the inclination angle and measuring the angle. The front retardation (angle 0 °) was 0 nm, and the tilt angles + 40 ° and −40 ° were both −20.3 nm. From this, it can be confirmed that a negative C plate which is a kind of optically anisotropic film is formed, and it is clear that it is useful as a retardation compensation material for liquid crystal displays.

[Example 4] Preparation of optically anisotropic film 3
Compound No. 1 / Compound A = 70/30 (mass ratio) The polymerizable liquid crystal compound 1.0g was dissolved in cyclopentanone 4.0g, and 0.03g of photoinitiator N-1919 (made by ADEKA) was added. And completely dissolved. The prepared polymerizable liquid crystal composition solution was applied to a glass substrate with a polyimide alignment film subjected to rubbing treatment using a spin coater (OPTICOAT MS-A-150 manufactured by Mikasa). After drying at 100 ° C. for 3 minutes, returning to room temperature and allowing to stand for 3 minutes, it was cured by irradiation with a high-pressure mercury lamp (120 W / cm) for 20 seconds. The obtained cured film was transparent, and homogeneity was evaluated by observation with a polarizing microscope. By rotating the stage on which the cured film sample was placed under crossed Nicols, the alignment state was observed and evaluated for homogeneity. As a result, alignment defects were not confirmed, and a uniform homogeneous alignment state could be confirmed. Moreover, the film thickness measured at 25 degreeC using the stylus type surface shape measuring device (DEKTAK6M; ULVAC company make) was 0.985 mm. Furthermore, using a Nikon polarizing microscope OPTIPHOT2-POL, retardation measurement was performed by the Senarmon method with monochromatic light having a wavelength of 546 nm. The front retardation was 203 nm, and it was confirmed that a uniform optically anisotropic film was formed.

  From the above, the following is clear. The polymerizable liquid crystal composition of the present invention has a wide process margin, that is, crystals do not precipitate even when left at room temperature, because the liquid crystal phase of the polymer film obtained by photopolymerization is stable and has good solvent solubility. Easy to handle. Furthermore, the polymer film exhibits a uniform orientation and maintains a uniform film state, and thus is useful as an optically anisotropic film.

Claims (12)

A polymerizable liquid crystal composition comprising at least one polymerizable liquid crystal compound represented by the following general formula (I) and at least one polymerizable liquid crystal compound represented by the following general formula (II).

(Wherein ring A ^1, A ² and A ³ each independently represent a benzene ring, a cyclohexane ring or a naphthalene ring,
S ¹ represents an alkylene group having 2 to 8 carbon atoms which may be substituted with a halogen atom and may have a branch, and the alkylene group is interrupted at least once by an oxygen atom;
X ¹ and X ² each independently represent a hydrogen atom or a methyl group,
Z ¹ and Z ² are independently a direct ^{bond, -L 1 -, - O-} CO -, - CO-O -, - L 1 O -, - OL 1 -, - L 1 O-CO-, ^{-L 1 CO-O -, -} L 1 O-CO-O -, - O-COL 1 -, - CO-OL 1 - or -O-CO-OL ¹ - represents,
L ¹ represents an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogen atom and may have a branch, and the alkylene group may be interrupted 1 to 3 times with an oxygen atom. ,
Y ¹ , Y ² and Y ³ are each independently an oxygen atom, a sulfur atom or an alkyl group having 1 to 6 carbon atoms which may be interrupted by —CO—, or a carbon atom which may be substituted with a halogen atom. An alkoxy group having 1 to 8 atoms, a halogen atom or a cyano group is represented, a, b and c are each independently 0 or 1, and a + b + c is 1 or more and 3 or less. )

(Wherein R ¹ and R ² each independently represents a hydrogen atom, a methyl group or a halogen atom,
Ring A ⁴ , Ring A ⁵ and Ring A ⁶ each independently represent a benzene ring, a cyclohexane ring, a cyclohexene ring, a naphthalene ring, a decahydronaphthalene ring, a tetrahydronaphthalene ring or a phenanthrene ring, and —CH in these rings = is a -N =, -CH ₂ - may be interrupted by -S- or -O-,
Y ⁴ , Y ⁵ and Y ⁶ each independently represents an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom or a cyano group, a halogen atom or a cyano group, and methylene in the alkyl group The group may be interrupted by —O—, —CO—, —O—CO— or —CO—O—,
L ² and L ³ are each independently a direct bond, —COO—, — (CE ₂ ) _p —, —CE═CE—, — (CE ₂ ) _p O—, —CE═CECE ₂ O—, — C≡C—, — (CE ₂ ) _p COO—, — (CE ₂ ) _p OCO—O— or — (CE ₂ ) _q O (CE ₂ ) _r O—
L ⁴ and L ⁵ are each independently a direct bond, —OCO—, — (CE ₂ ) _p —, —CE═CE—, —O (CE ₂ ) _p —, —OCE ₂ CE═CE—, — C≡C—, —OCO (CE ₂ ) _p —, —OCO—O (CE ₂ ) _p —, — (CE ₂ ) _q O (CE ₂ ) _r O— or —O (CE ₂ ) _q O (CE ₂ ) _r- represents, E in L ² and L ⁵ represents a hydrogen atom, a methyl group or an ethyl group, E in L ³ and L ⁴ represents a hydrogen atom, and a plurality of E may be the same or different. Well,
d, e, and f are the number of substituents in ring A ⁴ , ring A ^5, and ring A ⁶ , respectively, where t is the number of 6-membered rings included in each substituted monocyclic or condensed ring. , D, e and f are each independently an integer of 2t + 2 or less, and e represents an integer of 1 or more,
p represents each independently an integer of 1 to 8, and q and r each independently represents an integer of 1 to 3. ) The polymerizable liquid crystal composition according to claim ¹ , wherein, in the general formula (I), ring A ¹ , ring A ² and ring A ³ are 1,4-phenylene. The polymerizable liquid crystal composition according to claim 1 or 2, wherein, in the general formula (II), ring A ⁴ , ring A ⁵ and ring A ⁶ are 1,4-phenylene or 2,6-naphthylene. In the above general formula (II), L ² is — (CE ₂ ) _p OCO—O— or — (CE ₂ ) _p O—, and L ⁵ is —OCO—O (CE ₂ ) _p — or -O (CE _{2) p} - polymerizable liquid crystal composition according to any one of claims 1 to 3 is. In the general formula (II), L ² is — (CH ₂ ) _p OCO—O— or — (CH ₂ ) _p O—, and L ⁵ is —OCO—O (CH ₂ ) _p — or The polymerizable liquid crystal composition according to claim 1, which is —O (CH ₂ ) _p —. In the general formula (II), the polymerizable liquid crystal composition according to claim 1 or is a direct bond L ² and L ^5.   The mass ratio of the total amount of the polymerizable liquid crystal compound represented by the general formula (I) and the total amount of the polymerizable liquid crystal compound represented by the general formula (II) is 10/90 to 99.9 / 0. The polymerizable liquid crystal composition according to claim 1, which is 0.1 (the former / the latter).   The mass ratio of the total amount of the polymerizable liquid crystal compound represented by the general formula (I) and the total amount of the polymerizable liquid crystal compound represented by the general formula (II) is 25/75 to 90/10 (the former The latter is the polymerizable liquid crystal composition according to any one of claims 1 to 7.   The polymerizable liquid crystal composition according to claim 1, which exhibits a liquid crystal phase at 25 ° C. or lower.   The polymerizable liquid crystal composition according to claim 1, comprising an optically active compound and exhibiting a cholesteric liquid crystal phase.   The polymerizable liquid crystal composition according to claim 1, comprising a radical polymerization initiator.   An optically anisotropic film containing a polymer obtained by photopolymerizing the polymerizable liquid crystal composition according to claim 1.