JP2012211283A - Polymerizable liquid crystal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable liquid crystal composition provided as a material for an optically anisotropic body, wherein a material is provided which can obtain an excellent film having no crack when a patterned film is produced through a combination of polymerization by ultraviolet irradiation and polymerization by heating.SOLUTION: This invention relates to a polymerizable liquid crystal compound, a photopolymerization initiator, and the polymerizable liquid crystal composition that contains a thermal polymerization initiator. In the polymerizable liquid crystal composition, the thermal polymerization initiator has 10-hour half-life temperature of 70-93°C. The optically anisotropic body obtained by curing the polymerizable liquid crystal composition is also provided.

Description

  The present invention relates to a polymerizable liquid crystal composition used for producing an optical compensation film such as a liquid crystal display.

  An optical element in which a part having a phase difference and a part having no phase difference (isotropic part) are patterned in an arbitrary shape expected to be applied to a transflective liquid crystal display device or a liquid crystal display element capable of three-dimensional display A technique (Patent Document 1) for manufacturing simply and inexpensively is disclosed. This involves irradiating the polymerizable liquid crystal applied to the substrate with active energy rays through a photomask, curing the polymerizable liquid crystal only at the irradiated portion to form a portion having a phase difference, and further heating the substrate. Thus, the method includes a step of forming an isotropic portion by bringing the polymerizable liquid crystal in an uncured state into an isotropic phase state and performing thermal polymerization in that state. In addition, for the purpose of facilitating thermal polymerization, this document discloses the combined use of a thermal polymerization initiator. When this method is used, it is not necessary to remove the portion of the polymerizable liquid crystal having no phase difference with an organic solvent, so that there is an advantage that the environmental load can be reduced. However, this manufacturing method has a problem that cracks, steps, and white turbidity are likely to occur in the cured film of the polymerizable liquid crystal when the substrate is heated.

  In addition to the above production method, in the production of an optical element using a polymerizable liquid crystal, in addition to the irradiation with active energy rays, a combination of heat treatment is often used for the purpose of suppressing a change with time. This heat treatment may cause problems such as cracks and steps.

JP-T-2006-276697

  The purpose of the present invention is to irradiate the polymerizable liquid crystal applied to the substrate with active energy rays through a photomask, cure the polymerizable liquid crystal only at the irradiated portion, and further heat the substrate to bring the polymer liquid crystal into an uncured state. A process that combines irradiation with active energy rays and heat treatment for curing the polymerizable liquid crystal, such as a process in which a certain polymerizable liquid crystal is brought into an isotropic phase state and isotropically (thermally) polymerized to form an isotropic layer. It is an object of the present invention to provide a polymerizable liquid crystal material capable of realizing a high-quality state free from cracks, steps and white turbidity in an optical element manufactured using the same.

As a result of diligent studies to achieve the above-mentioned purpose, it is difficult to cause thermal polymerization during heating when cracks and steps occur, and clouding occurs before complete transfer of the polymerizable liquid crystal to the isotropic liquid phase during heating. It has been clarified that the polymerization is likely to proceed, and it has been found that a specific thermal polymerization initiator may be added to the polymerizable liquid crystal material, and the present invention has been completed.
The invention of the present application is characterized in that, in a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, a photopolymerization initiator, and a thermal polymerization initiator, the thermal polymerization initiator has a 10 hour half-life temperature of 70 to 93 ° C. A polymerizable liquid crystal composition is provided.

  When the polymerizable liquid crystal composition of the present invention is used, cracks, steps and white turbidity generated during thermal polymerization can be suppressed, and a high-quality optical element can be obtained.

  In the present invention, the “10 hour half-temperature” of the thermal polymerization initiator means a temperature at which half of the molecules are decomposed when the thermal polymerization initiator is kept at that temperature for 10 hours. The 10-hour half-life temperature of the thermal polymerization initiator used in the polymerizable liquid crystal composition of the present invention is 70 ° C to 93 ° C, preferably 80 ° C to 92 ° C, and particularly preferably 85 ° C to 91 ° C. When the temperature is lower than 70 ° C., the thermal polymerization initiator is likely to be cleaved (generates radicals) during heating, and the resulting optical film tends to become cloudy. When the initiator is cleaved at a temperature lower than the clearing point of the polymerizable liquid crystal composition, the cloudiness becomes extremely large. On the other hand, when the temperature is higher than 93 ° C., the timing at which the thermal polymerization initiator is cleaved is delayed even when heated, and an undesired flow occurs at that time, and there is a tendency that a step is generated in the film.

  Moreover, it is preferable to have a cyclohexane ring in the molecular skeleton of the thermal polymerization initiator. When it has a cyclohexane ring, compatibility with the polymerizable liquid crystal material can be ensured. Particularly preferred as such compounds are those of formula (a)

（式中、シクロヘキサン環中の炭素原子は、窒素原子、酸素原子で置換されていても良く、水素原子は炭素原子数1から18のアルキル基で置換されていても良い）で表される化合物である。
熱重合開始剤の重合性液晶組成物中の添加量は、0.1~3質量%が好ましく、0.5~2質量%が更に好ましく、0.7~1.2質量%が特に好ましい。添加量が少ないとひび割れや段差が発生しやすくなり、添加量が多いと重合性液晶組成物の液晶としての性質が損なわれやすくなる。更に、得られる硬化物において光散乱が大きくなってしまう。

(Wherein the carbon atom in the cyclohexane ring may be substituted with a nitrogen atom or an oxygen atom, and the hydrogen atom may be substituted with an alkyl group having 1 to 18 carbon atoms) It is.
The addition amount of the thermal polymerization initiator in the polymerizable liquid crystal composition is preferably 0.1 to 3% by mass, more preferably 0.5 to 2% by mass, and particularly preferably 0.7 to 1.2% by mass. If the addition amount is small, cracks and steps are likely to occur, and if the addition amount is large, the properties of the polymerizable liquid crystal composition as liquid crystals are likely to be impaired. Furthermore, light scattering will become large in the hardened | cured material obtained.

  Any photopolymerization initiator can be used without particular limitation as long as it is recognized as a photopolymerization initiator in this technical field. Examples of such photopolymerization initiators include Irgacure-651 (BASF Japan) which is a benzyldimethyl ketal compound, Irgacure-184 (BASF Japan) which is an α-hydroxyalkylphenone compound, and Irgacure which is an α-aminoalkylphenone compound. -907 (BASF Japan: Formula (B))

Irgacure-369（BASFジャパン：式（C））

Irgacure-369 (BASF Japan: Formula (C))

アシルフォスフィンオキシド化合物であるIrgacure-819（BASFジャパン：式（D））

Irgacure-819, an acylphosphine oxide compound (BASF Japan: Formula (D))

オキシムエステル化合物であるIrgacure OXE 01（BASFジャパン：式（E））

Irgacure OXE 01, an oxime ester compound (BASF Japan: Formula (E))

Can give. Among these, it is possible to ensure curability in the air when irradiated with active energy rays (no need to replace with an inert gas such as nitrogen when irradiated with active energy rays such as UV). From the viewpoint, it is preferable to select an α-aminoalkylphenone compound or an oxime ester compound. Irgacure-907 is preferably selected as the α-aminoalkylphenone compound, and Irgacure OXE 01 is preferably selected as the oxime ester compound. Although the addition amount of a photoinitiator changes with irradiation conditions of an active energy ray, 0.1-5 mass% is preferable in a polymeric liquid crystal composition, 1-4% is further more preferable, and 2-3% is especially preferable.
The polymerizable liquid crystal compound used in the polymerizable liquid crystal composition of the present invention is represented by the general formula (I)

（式中、Pは反応性官能基を表し、Spは炭素原子数１〜２０のスペーサー基を表し、mは０又は１を表し、MGはメソゲン基又はメソゲン性支持基を表し、R¹は、ハロゲン原子、シアノ基又は炭素原子数１〜２５のアルキル基を表すが、該アルキル基は１つ以上のハロゲン原子又はCNにより置換されていても良く、この基中に存在する１つのCH₂基又は隣接していない２つ以上のCH₂基はそれぞれ相互に独立して、酸素原子が相互に直接結合しない形で、-O-、-S-、-NH-、-N(CH₃)-、-CO-、-COO-、-OCO-、-OCOO-、-SCO-、-COS-又は-C≡C-により置き換えられていても良く、あるいはR¹は一般式（I-a）

(Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, m represents 0 or 1, MG represents a mesogenic group or a mesogenic support group, and R ¹ represents Represents a halogen atom, a cyano group or an alkyl group having 1 to 25 carbon atoms, and the alkyl group may be substituted by one or more halogen atoms or CN, and one CH ₂ present in the group. Group or two or more non-adjacent CH ₂ groups are each independently of each other such that —O—, —S—, —NH—, —N (CH ₃ ) -, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted, or R ¹ may be represented by the general formula (Ia)

（式中、Pは反応性官能基を表し、Spは炭素原子数１〜２０のスペーサー基を表し、mは０又は１を表す。）で表される構造を表す。）で表される化合物が好ましい。

(Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, and m represents 0 or 1). ) Is preferred.

In the general formula (I), Sp represents an alkylene group (the alkylene group may be substituted by one or more halogen atoms or CN, and is not adjacent to one CH ₂ group present in the group) Two or more CH ₂ groups are independently of each other, in a form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted.), MG is represented by the general formula (Ib)

（式中、A1、A2及びA3はそれぞれ独立的に、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基又はフルオレン2,7-ジイル基を表し、該1,4-フェニレン基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基及びフルオレン2,7-ジイル基は置換基として１個以上のF、Cl、CF₃、OCF₃、シアノ基、炭素原子数１〜８のアルキル基、アルコキシ基、アルカノイル基、アルカノイルオキシ基、炭素原子数２〜８のアルケニル基、アルケニルオキシ基、アルケノイル基又はアルケノイルオキシ基を有していても良く、Z0、Z1、Z2及びZ3はそれぞれ独立して、-COO-、-OCO-、-CH₂ CH₂-、-OCH₂-、-CH₂O-、-CH=CH-、-C≡C-、-CH=CHCOO-、-OCOCH=CH-、-CH₂CH₂COO-、-CH₂CH₂OCO-、-COO CH₂CH₂-、-OCOCH₂CH₂-、-CONH-、-NHCO-又は単結合を表し、nは０、１、２又は３を表す。）で表される構造を表し、Pが一般式（I-c）又は、一般式（I-d）

(In the formula, A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, Phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or fluorene 2, Represents a 7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9 , 10-Dihydrophenanthrene-2,7-diyl group 1,2,3,4,4a, 9,10a- octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group is 1 or more F as _{substituents, Cl, CF 3, OCF 3} , cyano Group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group or an alkenoyloxy group. , Z0, Z1, Z2 and Z3 are each independently -COO-, -OCO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -CH = CH-, -C≡C -, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COO CH ₂ CH _2- , -OCOCH ₂ CH _2- , -CONH-,- NHCO- or a single bond, n represents 0, 1, 2, or 3), and P represents a general formula (Ic) or general formula (Id)

(Wherein R ²¹ , R ²² , R ²³ , R ³¹ , R ³² and R ³³ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents 0 or 1) It is preferable to represent a substituent selected from the group consisting of substituents represented by:
Of the compounds represented by the general formula (I), specific examples of the compound having one polymerizable functional group include those represented by the general formula (II)

（式中、Z³は水素原子、ハロゲン原子、シアノ基又は炭素原子数１〜２０の炭化水素基を表し、Z⁴は水素原子又はメチル基を表し、W³は単結合、-O-、-COO-又は-OCO-を表し、vは０〜１８の整数を表し、uは０又は１を表し、D、E及びFはそれぞれ独立的に、1,4−フェニレン基、隣接しないCH基が窒素で置換された1,4−フェニレン基、1,4−シクロヘキシレン基、１つ又は隣接しない２つのCH₂基が酸素又は硫黄原子で置換された1,4−シクロヘキシレン基、1,4−シクロヘキセニレン基を表すが、式中に存在する1,4−フェニレン基は炭素原子数１〜７のアルキル基、アルコキシ基、アルカノイル基、シアノ基又はハロゲン原子で一つ以上置換されていても良く、Y⁶及びY⁷はそれぞれ独立的に単結合、-CH₂CH₂-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-C≡C-、-CH=CH-、-CF=CF-、-（CH₂）₄-、-CH₂CH₂CH₂O-、-OCH₂CH₂CH₂-、-CH=CHCH₂CH₂-、-CH₂CH₂CH=CH-、-CH=CHCOO-、-OCOCH=CH-、-CH₂CH₂COO-、-CH₂CH₂OCO-、-COO CH₂CH₂-又は-OCOCH₂CH₂-を表し、Y⁸は単結合、-O-、-COO-、-OCO-又は-CH=CHCOO-を表すが、W³が単結合を表す場合ｖは２〜１８の整数を表す。）で表される化合物を含有させることが好ましい。

(Wherein Z ³ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z ⁴ represents a hydrogen atom or a methyl group, W ³ represents a single bond, —O—, -COO- or -OCO-, v represents an integer of 0 to 18, u represents 0 or 1, D, E and F are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH ₂ groups are substituted with oxygen or sulfur atoms, 1, Represents a 4-cyclohexenylene group, but the 1,4-phenylene group present in the formula is substituted by one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms. Y ⁶ and Y ⁷ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, — CH = CH-, -CF = CF _{-, - (CH 2) 4} -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - CH 2 CH 2 CH = CH -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COO CH 2 CH 2 - or -OCOCH ₂ CH ₂ - represents, Y ⁸ represents a single bond, - O—, —COO—, —OCO— or —CH═CHCOO— is represented, but when W ³ represents a single bond, v represents an integer of 2 to 18). .

  The compound represented by the general formula (II) is useful because it has an effect of lowering the liquid crystal lower limit temperature, but the addition amount is preferably 0 to 60%, more preferably 0 to 50%, and more preferably 0 to 40%. Is particularly preferred. When the addition amount is large, the heat resistance of the obtained optical film tends to be impaired.

The compound represented by the general formula (II) includes a compound having a liquid crystalline skeleton and a compound having a spacer between polymerizable functional groups and a compound having no spacer. In the general formula (II), the case where W ³ represents a substituent other than a single bond and v represents an integer of 2 to 18 corresponds to a compound having a spacer. Specifically, the following general formula (II-1 To the compound represented by the general formula (II-9).

(Wherein, X ¹ represents a hydrogen atom or a methyl group, and R represents an alkyl group having 1 to 20 carbon atoms). X1 is preferably a hydrogen atom, and S is preferably 3, 4, or 6. Among such compounds, compounds of formula (IV-5), formula (IV-1), and formula (IV-6) are preferable. In the case of the compound of formula (IV-1), R is particularly preferably a methyl group.

On the other hand, in the general formula (II), the case where W ³ represents a single bond and v represents 0 corresponds to a compound having no spacer, and specifically the following structures are preferred.

(In the formula, a cyclohexane ring represents a transcyclohexane ring, a number represents a phase transition temperature, C represents a crystalline phase, N represents a nematic phase, S represents a smectic phase, and I represents an isotropic liquid phase.)
Of the compounds represented by the general formula (I), the compound having two polymerizable functional groups is represented by the general formula (III)

(In the formula, Z ⁵ and Z ⁶ represent a hydrogen atom and a methyl group, G, H and I are each independently 1,4-phenylene group and 1,4- A phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexylene group or a 1,4-cyclohexenylene group in which one or two non-adjacent CH2 groups are substituted with an oxygen or sulfur atom. The 1,4-phenylene group present therein may be substituted by one or more alkyl groups having 1 to 7 carbon atoms, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms, and m is an integer of 0 to 3 W ¹ and W ² each independently represent a single bond, —O—, —COO— or —OCO—, and Y ¹ and Y ² each independently represent a single bond, —COO—, —OCO— _{, -CH 2 CH 2 COO -,} - CH 2 CH 2 OCO -, - COOCH 2 CH2 -, - OCOCH 2 CH 2 - represents, r and s represent each independently 2 to 18 integer, formula Exist in The 1,4-phenylene group may be substituted with one or more alkyl groups having 1 to 7 carbon atoms, alkoxy groups, alkanoyl groups, cyano groups, or halogen atoms. More specifically, the following can be mentioned.

(Wherein j, k, l and m each independently represent an integer of 2 to 18)
Among the above compounds, a compound represented by (III-30) is preferable. (III-30) is effective as a component in the composition because of its excellent solubility and a liquid crystal lower limit temperature of about 50 to 70 ° C. The concentration in the composition is preferably 5% or more, more preferably 10% or more, and particularly preferably 15% or more. A compound represented by (III-9) is also preferred. The compound of (III-9) is also effective as a component in the composition because of its excellent solubility and orientation. The concentration in the composition is preferably 5% or more, more preferably 10% or more, and particularly preferably 15% or more. The sum of the concentration of the compound represented by (III-30) and the compound represented by (III-9) is preferably 10% or more, more preferably 20% or more, and 30% or more. Is particularly preferred. It is preferable to use a compound in which j and k are 3, 4, and 6 because the compound production cost and the liquid crystal temperature range can be appropriately set.

  Further, a discotic compound may be added to the polymerizable liquid crystal composition of the present invention. As such a discotic compound, a benzene derivative, a triphenylene derivative, a truxene derivative, a phthalocyanine derivative or a cyclohexane derivative is used as a mother nucleus at the center of the molecule, and a linear alkyl group, a linear alkoxy group, or a substituted benzoyloxy group is included. Preferably, the structure is a radially substituted structure as a side chain.

（式中、R⁵はそれぞれ独立して一般式（IV-a）で表される置換基を表す。）

(In the formula, each R ⁵ independently represents a substituent represented by the general formula (IV-a).)

（式中、R⁶及びR⁷はそれぞれ独立的に水素原子、ハロゲン原子又はメチル基を表し、R⁸は炭素原子数１〜２０アルコキシ基を表すが、該アルコキシ基中の水素原子は一般式（V-b）、一般式（IV-c）又は一般式（IV-d）で表される置換基によって置換されていても良い。）

(In the formula, R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom or a methyl group, and R ⁸ represents an alkoxy group having 1 to 20 carbon atoms, and the hydrogen atom in the alkoxy group represents a general formula. (It may be substituted by a substituent represented by (Vb), general formula (IV-c) or general formula (IV-d).)

（式中、R⁸¹、R⁸²、R⁸³、R⁸⁴、R⁸⁵、R⁸⁶はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数１〜５のアルキル基を表し、nは０又は１を表す。）で表される構造を有することがさらに好ましく、一般式（IV）においてR⁸の内少なくとも一つは一般式（IV-b）、一般式（IV-c）で表される置換基によって置換されたアルコキシ基を表すことが好ましく、R⁸の全てが一般式（IV-b）、一般式（IV-c）で表される置換基によって置換されたアルコキシ基を表すことが特に好ましい。

(Wherein R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents 0 or 1) It is more preferable that at least one of R ^{8 in} the general formula (IV) is a substituent represented by the general formula (IV-b) or (IV-c). It is preferable that all of R ⁸ represent an alkoxy group substituted by a substituent represented by the general formula (IV-b) or general formula (IV-c). .

  Further, the general formula (V-a) specifically represents the general formula (IV-e)

（式中ｎは２〜９の整数を表す）で表される構造を有することが特に好ましい。

It is particularly preferable to have a structure represented by the formula (wherein n represents an integer of 2 to 9).

  The polymerizable liquid crystal composition of the present invention has the general formula (V) for the purpose of quickly obtaining good planar alignment when applied.

（式中、R¹、R²、R³及びR⁴はそれぞれ独立的に水素原子、ハロゲン原子又は炭素原子数1〜２０の炭化水素基を表し、該炭化水素基中の水素原子は１つ以上のハロゲン原子で置換されていても良い。）で表される繰り返し単位を有する重量平均分子量が１００以上である化合物を含有させることが好ましい。

(In the formula, R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one hydrocarbon atom in the hydrocarbon group. It may be substituted with the above halogen atom.) It is preferable to contain a compound having a repeating unit represented by the following formula and having a weight average molecular weight of 100 or more.

Examples of the compound represented by the general formula (V) include polyethylene, polypropylene, polyisobutylene, paraffin, liquid paraffin, chlorinated polypropylene, chlorinated paraffin, and chlorinated liquid paraffin. In addition to this, a compound in which a fluorine atom is introduced is also effective from the viewpoint of suppressing unevenness.
Among the compounds having a repeating unit represented by the general formula (V), as a preferred structure, the formula (Va) to the formula (Vf)

The compound which has a repeating unit represented by these is mentioned. Among these, structures represented by the formulas (Va) to (Ve) are more preferable, and structures represented by the formulas (Va) and (Vc) are particularly preferable. A copolymer obtained by copolymerizing two or more compounds having a repeating unit represented by the formula (Va) to the formula (Vf) is also preferable. In this case, a copolymer having the formula (Va) and the formula (Vb), a copolymer having the formula (Va) and the formula (Vc), a copolymer having the formula (Va) and the formula (Vf), and More preferred are copolymers having formula (Va), (Vb) and formula (Vf), copolymers having formula (Va) and formula (Vb), and formulas (Va), (Vb) and formula (V A copolymer having Vf) is particularly preferred.

If the weight average molecular weight of the compound is too small, the effect of reducing the tilt angle is poor. Specifically, it is preferably 200 to 1000000, more preferably 300 to 100000, and particularly preferably 400 to 80000.
Moreover, it is preferable to contain 0.01-5 mass% of this compound in a polymeric liquid crystal composition, It is more preferable to contain 0.05-2 mass%, Containing 0.1-1 mass% Is particularly preferred.

The polymerizable liquid crystal composition of the present invention may contain a chiral compound for the purpose of obtaining a chiral nematic phase. Of the chiral compounds, compounds having a polymerizable functional group in the molecule are particularly preferred.
As the polymerizable functional group in the chiral compound, an acryloyloxy group is particularly preferable. The addition amount of the chiral compound needs to be appropriately adjusted depending on the helical induction force of the compound, but is preferably 12% or less.
Specific examples of the chiral compound include compounds of the formulas (ch-1) to (ch-8).

(Wherein n represents an integer of 2 to 12) Among these compounds, the compound of (ch-1) is preferable. In this case, n is most preferably 2 or 4 from the viewpoint of synthesis cost.

  A surfactant is preferably added to the polymerizable liquid crystal composition for the purpose of ensuring surface smoothness when it is applied. As the surfactant, there is no distinction between an ionic surfactant and a nonionic surfactant. Surfactants that can be included include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoro Examples thereof include alkylethylene oxide derivatives, polyethylene glycol derivatives, alkylammonium salts, fluoroalkylammonium salts, silicone derivatives and the like, and fluorine-containing surfactants and silicone derivatives are particularly preferable. More specifically, “MEGAFAC F-110”, “MEGAFACCF-113”, “MEGAFAC F-120”, “MEGAFAC F-812”, “MEGAFAC F-142D”, “MEGAFAC F-144D”, “MEGAFAC F-” 150 "," MEGAFAC F-171 "," MEGAFACCF-173 "," MEGAFAC F-177 "," MEGAFAC F-183 "," MEGAFAC F-195 "," MEGAFAC F-824 "," MEGAFAC F-833 " , “MEGAFAC F-114”, “MEGAFAC F-410”, “MEGAFAC F-493”, “MEGAFAC F-494”, “MEGAFAC F-443”, “MEGAFAC F-444”, “MEGAFAC F-445”, "ME GAFAC F-446, MEGAFAC F-470, MEGAFAC F-471, MEGAFAC F-474, MEGAFAC F-475, MEGAFAC F-477, MEGAFAC F-478, MEGAFAC F-479, MEGAFAC F-480SF, MEGAFAC F-482, MEGAFAC F-483, MEGAFAC F-484, MEGAFAC F-486, MEGAFAC F-487, MEGAFAC F -489 "," MEGAFAC F-172D "," MEGAFAC F-178K "," MEGAFAC F-178RM "," MEGAFAC R-08 "," MEGAFAC R-30 "," MEGAFAC F-472SF "," MEGAFAC " "BL-20", "MEGAFAC R-61", "MEGAFAC R-90", "MEGAFAC ESM-1", "MEGAFAC MCF-350SF" (above, manufactured by DIC Corporation),

“Furgent 100”, “Furgent 100C”, “Furgent 110”, “Furgent 150”, “Furgent 150CH”, “Furgent A”, “Furgent 100A-K”, “Furgent 501”, "Factent 300", "Factent 310", "Factent 320", "Factent 400SW", "FTX-400P", "Factent 251", "Factent 215M", "Factent 212MH", "Footer Gent 250, Fategent 222F, Fategent 212D, FTX-218, FTX-209F, FTX-213F, FTX-233F, Fate 245F, FTX-208G ”,“ FTX-240G ”,“ FT -206D "," FTX-220D "," FTX-230D "," FTX-240D "," FTX-207S "," FTX-211S "," FTX-220S "," FTX-230S "," FTX-750FM " ”,“ FTX-730FM ”,“ FTX-730FL ”,“ FTX-710FS ”,“ FTX-710FM ”,“ FTX-710FL ”,“ FTX-750LL ”,“ FTX-730LS ”,“ FTX-730LM ”, "FTX-730LL", "FTX-710LL" (above, manufactured by Neos),

“BYK-300”, “BYK-302”, “BYK-306”, “BYK-307”, “BYK-310”, “BYK-315”, “BYK-320”, “BYK-322”, “BYK” -323 "," BYK-325 "," BYK-330 "," BYK-331 "," BYK-333 "," BYK-337 "," BYK-340 "," BYK-344 "," BYK-370 " ”,“ BYK-375 ”,“ BYK-377 ”,“ BYK-350 ”,“ BYK-352 ”,“ BYK-354 ”,“ BYK-355 ”,“ BYK-356 ”,“ BYK-358N ”, “BYK-361N”, “BYK-357”, “BYK-390”, “BYK-392”, “BYK-UV3500”, “BYK-UV3510”, “BYK-UV3570”, “B K-Silclean3700 "(manufactured by BYK Japan KK),

Examples include “TEGO Rad2100”, “TEGO Rad2200N”, “TEGO Rad2250”, “TEGO Rad2300”, “TEGO Rad2500”, “TEGO Rad2600”, “TEGO Rad2700” (manufactured by TEGO). The preferred addition amount of the surfactant varies depending on components other than the surfactant contained in the polymerizable liquid crystal composition, the use temperature, etc., but is contained in the polymerizable liquid crystal composition in an amount of 0.01 to 1% by mass. The content is preferably 0.02 to 0.5 mass%, more preferably 0.03 to 0.1 mass%. When the content is lower than 0.01% by mass, it is difficult to obtain the effect of reducing film thickness unevenness. The total content of the surfactant and the content of the compound having a weight average molecular weight of 100 or more having the repeating unit represented by the general formula (VI) is preferably 0.02 to 0.5% by mass, It is more preferable to contain 0.05-0.4 mass%, and it is especially preferable to contain 0.1-0.2 mass%.

  The polymerizable liquid crystal composition of the present invention preferably contains 100 to 2000 ppm of a polymerizable inhibitor. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds and the like. More specific examples include methoxyphenol and 2,6-di-tert-butylphenol.

  The optical anisotropic body of the present invention can be obtained, for example, by supporting the polymerizable liquid crystal composition of the present invention on a substrate and aligning the material, followed by curing by irradiation with ultraviolet rays or electron beams. In the case where the polymerizable liquid crystal composition is carried, a method in which the polymerizable liquid crystal composition is dissolved in a solvent, applied onto a substrate, and the solvent is volatilized can be exemplified. It is also possible to apply the polymerizable liquid crystal directly onto the substrate without dissolving it in the solvent. Suitable organic solvents include, for example, alkyl-substituted benzenes such as toluene, xylene, cumene, propylene glycol monomethyl ether acetate, butyl acetate, cyclohexanone, cyclopentanone and the like. Further, dimethylformamide, γ-butyrolactone, N-methylpyrrolidinone, methyl ethyl ketone, ethyl acetate and the like may be added to these solvents. Examples of the method for volatilizing the solvent include a method in which heating at 60 to 150 ° C., more preferably 80 to 120 ° C. is performed for 15 to 120 seconds, more preferably 30 to 90 seconds. In addition to this heating, vacuum drying can be combined. Examples of the application method include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spray coating, dipping, and printing. As the substrate, either an inorganic material such as glass or an organic material such as a plastic film may be used. These substrates are preferably subjected to an alignment treatment. Alignment treatment includes rubbing treatment that rubs the substrate with a cloth, rubbing treatment after an organic thin film such as polyimide is formed on the substrate, or light that is irradiated with polarized ultraviolet light after the photo-alignment film is formed on the substrate. An alignment process etc. can be mentioned.

As the active energy ray, an electron beam or UV light can be used. As the UV light, light having a wavelength of 280 to 360 nm can be used. The intensity is preferably 1 to 100 mW / cm ^2, more preferably ^{2~50mW / cm 2, 5~30mW / cm} 2 is particularly preferred. Preferably 5 to 200 mJ / cm ² as irradiation energy, more preferably ^{10~150mJ / cm 2, 20~120mJ / cm} 2 is particularly preferred.

When irradiating an active energy ray through a pattern mask, the distance between the pattern mask and the polymerizable liquid crystal composition layer is preferably 10 to 300 μm, more preferably 50 to 200 μm, and particularly preferably 100 to 150 μm. As the distance is smaller, the resolution of the pattern is improved. However, if the distance is smaller, the polymerizable liquid crystal composition layer may be attached to the mask.
The heat treatment temperature after irradiation with active energy rays is preferably from 100 to 240 ° C, more preferably from 150 to 235 ° C, particularly preferably from 180 to 230 ° C. The heating time is preferably 10 to 80 minutes, more preferably 20 to 70 minutes, and particularly preferably 30 to 60 minutes. If the heating time is short, thermal polymerization does not proceed sufficiently and the reliability tends to deteriorate, and if the heating time is long, thermal degradation tends to proceed.

EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. In addition,% represents mass%. The front phase difference Re was measured with RETS-100 manufactured by Otsuka Electronics (wavelength 589 nm).
(Reference Example 1) Liquid crystalline acrylate compound of the formula (III-8-a) for preparation of polymerizable liquid crystal composition 10.00%

式（III-9-a）の液晶性アクリレート化合物40.00%

Liquid crystalline acrylate compound of formula (III-9-a) 40.00%

式（III-30-a）の液晶性アクリレート化合物25.00%

Liquid crystalline acrylate compound of formula (III-30-a) 25.00%

式（II-30-b）の液晶性アクリレート化合物25.00％

Liquid crystalline acrylate compound of formula (II-30-b) 25.00%

からなる重合性液晶組成物（A-0）を調製した。さらに、重合性液晶組成物（A-0）が97．54％、流動パラフィンが0.3％、レベリング剤FTX-218（株式会社ネオス社製）が0.05％、レベリング剤BYK-333（ビックケミー・ジャパン社製）が0.01％、光重合開始剤Irgacure OXE 01（BASFジャパン社製）が2.00％、重合禁止剤p-メトキシフェノールが0.10％からなる重合性液晶組成物（A-1）を調製した。
（実施例１）
参考例１で調製した重合性液晶組成物（A-1）が99.00%、式（a）の熱重合開始剤1,1'-Azobis(cyclohexane-1-carbonitrile)が1．00％からなる重合性液晶組成物（A-2）を調製した。式（a）の熱重合開始剤の10時間半減温度は、88℃である。

A polymerizable liquid crystal composition (A-0) comprising: Furthermore, the polymerizable liquid crystal composition (A-0) is 97.54%, the liquid paraffin is 0.3%, the leveling agent FTX-218 (manufactured by Neos Co., Ltd.) is 0.05%, the leveling agent BYK-333 (BIC Chemie Japan) A polymerizable liquid crystal composition (A-1) comprising 0.01%, photopolymerization initiator Irgacure OXE 01 (manufactured by BASF Japan) 2.00%, and polymerization inhibitor p-methoxyphenol 0.10% was prepared.
Example 1
Polymerization comprising 99.00% of the polymerizable liquid crystal composition (A-1) prepared in Reference Example 1 and 1.00% of the thermal polymerization initiator 1,1′-Azobis (cyclohexane-1-carbonitrile) of the formula (a) Liquid crystal composition (A-2) was prepared. The 10-hour half-life temperature of the thermal polymerization initiator of formula (a) is 88 ° C.

Further, a polymerizable liquid crystal solution (A-3) comprising 35% of the polymerizable liquid crystal composition (A-2) and 65% of cyclopentanone was prepared. This was spin coated (800 rpm) for 15 seconds on a glass substrate with a polyimide alignment film that had been rubbed. The spin-coated substrate was heated at 80 ° C. for 2 minutes to volatilize the solvent, and then allowed to stand at room temperature for 2 minutes. When the polymerizable liquid crystal composition layer was observed in this state, it was confirmed that horizontal uniaxial alignment was achieved. The polymerizable liquid crystal composition layer thus obtained was irradiated with ultraviolet light generated from a high-pressure mercury lamp (passed through a band-pass filter. Intensity 20 mW / cm ^{2 at a} wavelength of 365 nm) in a mask pattern (in part). With a line pattern of 1 mm pitch) for 0.31 seconds. The distance between the mask pattern and the polymerizable liquid crystal composition layer was kept at 150 μm. In this way, a portion where the ultraviolet rays were partially irradiated with a width of 1 mm and a portion where the ultraviolet rays were not irradiated with a width of 1 mm were repeated. This was allowed to stand in an oven at 230 ° C. for 1 hour, and the portion that had not been irradiated with ultraviolet rays was thermally polymerized. When the optically anisotropic body thus obtained was observed after cooling to room temperature, the polymerizable liquid crystal material was cured over the entire area. It was confirmed that there was no phase difference due to the thermal polymerization in the state. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 338 nm.

(Example 2)
The experiment was performed in the same manner as in Example 1 except that the UV irradiation time was 0.63 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 353 nm.

(Example 3)
The experiment was performed in the same manner as in Example 1 except that the UV irradiation time was 1.25 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 377 nm.

Example 4
In Example 1, the experiment was performed in the same manner except that the UV irradiation time was 2.5 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 394 nm.

(Comparative Example 1)
A polymerizable liquid crystal solution (B-3) comprising 35% of the polymerizable liquid crystal composition (A-1) prepared in Reference Example 1 and 65% of cyclopentanone was prepared. This was spin coated (800 rpm) for 15 seconds on a glass substrate with a polyimide alignment film that had been rubbed. The spin-coated substrate was heated at 80 ° C. for 2 minutes to volatilize the solvent, and then allowed to stand at room temperature for 2 minutes. When the polymerizable liquid crystal composition layer was observed in this state, it was confirmed that horizontal uniaxial alignment was achieved. The polymerizable liquid crystal composition layer thus obtained was irradiated with ultraviolet light generated from a high-pressure mercury lamp (passed through a band-pass filter. Intensity 20 mW / cm ^{2 at a} wavelength of 365 nm) in a mask pattern (in part). With a line pattern of 1 mm pitch) for 0.31 seconds. The distance between the mask pattern and the polymerizable liquid crystal composition layer was kept at 150 μm. In this way, a portion where the ultraviolet rays were partially irradiated with a width of 1 mm and a portion where the ultraviolet rays were not irradiated with a width of 1 mm were repeated. This was allowed to stand in an oven at 230 ° C. for 1 hour, and the portion that had not been irradiated with ultraviolet rays was thermally polymerized. When the optically anisotropic body thus obtained was observed after cooling to room temperature, the polymerizable liquid crystal material was cured over the entire area. It was confirmed that there was no phase difference due to the thermal polymerization in the state. However, many cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 293 nm.

(Comparative Example 2)
In Comparative Example 1, the experiment was performed in the same manner except that the UV irradiation time was set to 0.63 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. Cracks were observed in the pattern area. The UV irradiated part had optical anisotropy and the phase difference was 309 nm.

(Comparative Example 3)
An experiment was conducted in the same manner as in Comparative Example 1 except that the UV irradiation time was changed to 1.25 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 325 nm.

(Comparative Example 4)
An experiment was conducted in the same manner as in Comparative Example 1 except that the UV irradiation time was 2.5 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 333 nm.

(Comparative Example 5)
Polymerizable liquid crystal composition comprising 99.00% of the polymerizable liquid crystal composition (A-1) prepared in Reference Example 1 and 1.00% of the thermal polymerization initiator 2,2′-Azobis (isobutyronitrile) of the formula (r1). (C-2) was prepared. The 10-hour half-life temperature of the thermal polymerization initiator of the formula (r1) is 60 ° C.

更に重合性液晶組成物（C-2）35%、シクロペンタノン65%からなる重合性液晶溶液（C-3）を調製した。これをラビング処理を施したポリイミド配向膜付きのガラス基板にスピンコート（800回転/分、15秒）した。スピンコートした基板を80℃で2分間加熱して溶媒を揮発させた後、2分間室温で放置した。この状態で重合性液晶組成物層を観察したところ、水平１軸配向していることが確かめられた。このようにして得られた重合性液晶組成物層に、高圧水銀ランプから発生する紫外線（バンドパスフィルターを通したもの。波長365nmにおいて強度20mW/cm²）を空気中でマスクパターン（一部に1mmピッチのラインパターンを持つ）と通して0.31秒照射した。マスクパターンと重合性液晶組成物層の間の距離は150μmに保った。このようにして、一部に1mmの幅で紫外線が照射されたところと、1mmの幅で紫外線が未照射のところが繰り返された状態にした。これを230℃のオーブンに1時間静置して、紫外線が未照射だった部分を熱重合させた。このようにして得られた光学異方体を室温まで冷却したのちに観察したところ、重合性液晶材料は面積全体にわたって硬化していること、紫外線が未照射だった部分は、等方性液体相の状態で熱重合したために、位相差を持っていないことが確かめられた。しかし、パターン部にひび割れが多数観察された。UV照射した部分は光学異方性を持っており、位相差は278nmであった。

Furthermore, a polymerizable liquid crystal solution (C-3) comprising 35% of a polymerizable liquid crystal composition (C-2) and 65% of cyclopentanone was prepared. This was spin coated (800 rpm) for 15 seconds on a glass substrate with a polyimide alignment film that had been rubbed. The spin-coated substrate was heated at 80 ° C. for 2 minutes to volatilize the solvent, and then allowed to stand at room temperature for 2 minutes. When the polymerizable liquid crystal composition layer was observed in this state, it was confirmed that horizontal uniaxial alignment was achieved. The polymerizable liquid crystal composition layer thus obtained was irradiated with ultraviolet light generated from a high-pressure mercury lamp (passed through a band-pass filter. Intensity 20 mW / cm ^{2 at a} wavelength of 365 nm) in a mask pattern (in part). With a line pattern of 1 mm pitch) for 0.31 seconds. The distance between the mask pattern and the polymerizable liquid crystal composition layer was kept at 150 μm. In this way, a portion where the ultraviolet rays were partially irradiated with a width of 1 mm and a portion where the ultraviolet rays were not irradiated with a width of 1 mm were repeated. This was allowed to stand in an oven at 230 ° C. for 1 hour, and the portion that had not been irradiated with ultraviolet rays was thermally polymerized. When the optically anisotropic body thus obtained was observed after cooling to room temperature, the polymerizable liquid crystal material was cured over the entire area. It was confirmed that there was no phase difference due to the thermal polymerization in the state. However, many cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 278 nm.

(Comparative Example 6)
In Comparative Example 5, the experiment was performed in the same manner except that the UV irradiation time was set to 0.63 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. Some cracks were observed in the pattern area. The UV irradiated part had optical anisotropy and the phase difference was 308 nm.

(Comparative Example 7)
In Comparative Example 5, the experiment was performed in the same manner except that the UV irradiation time was 1.25 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 332 nm.

(Comparative Example 8)
In Comparative Example 5, the experiment was performed in the same manner except that the UV irradiation time was 2.5 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 354 nm.

(Comparative Example 9)
Polymerizable liquid crystal composition comprising 99.00% of the polymerizable liquid crystal composition (A-1) prepared in Reference Example 1 and 1.00% of the thermal polymerization initiator 2,2′-Azobis (isobutylate) of the formula (r2). (D-2) was prepared. The 10-hour half-life temperature of the thermal polymerization initiator of the formula (r2) is 66 ° C.

更に重合性液晶組成物（D-2）35%、シクロペンタノン65%からなる重合性液晶溶液（D-3）を調製した。これをラビング処理を施したポリイミド配向膜付きのガラス基板にスピンコート（800回転/分、15秒）した。スピンコートした基板を80℃で2分間加熱して溶媒を揮発させた後、2分間室温で放置した。この状態で重合性液晶組成物層を観察したところ、水平１軸配向していることが確かめられた。このようにして得られた重合性液晶組成物層に、高圧水銀ランプから発生する紫外線（バンドパスフィルターを通したもの。波長365nmにおいて強度20mW/cm²）を空気中でマスクパターン（一部に1mmピッチのラインパターンを持つ）と通して0.31秒照射した。マスクパターンと重合性液晶組成物層の間の距離は150μmに保った。このようにして、一部に1mmの幅で紫外線が照射されたところと、1mmの幅で紫外線が未照射のところが繰り返された状態にした。これを230℃のオーブンに1時間静置して、紫外線が未照射だった部分を熱重合させた。このようにして得られた光学異方体を室温まで冷却したのちに観察したところ、重合性液晶材料は面積全体にわたって硬化していること、紫外線が未照射だった部分は、等方性液体相の状態で熱重合したために、位相差を持っていないことが確かめられた。しかし、パターン部にひび割れが多数観察された。UV照射した部分は光学異方性を持っており、位相差は343nmであった。

Further, a polymerizable liquid crystal solution (D-3) comprising 35% of a polymerizable liquid crystal composition (D-2) and 65% of cyclopentanone was prepared. This was spin coated (800 rpm) for 15 seconds on a glass substrate with a polyimide alignment film that had been rubbed. The spin-coated substrate was heated at 80 ° C. for 2 minutes to volatilize the solvent, and then allowed to stand at room temperature for 2 minutes. When the polymerizable liquid crystal composition layer was observed in this state, it was confirmed that horizontal uniaxial alignment was achieved. The polymerizable liquid crystal composition layer thus obtained was irradiated with ultraviolet light generated from a high-pressure mercury lamp (passed through a band-pass filter. Intensity 20 mW / cm ^{2 at a} wavelength of 365 nm) in a mask pattern (in part). With a line pattern of 1 mm pitch) for 0.31 seconds. The distance between the mask pattern and the polymerizable liquid crystal composition layer was kept at 150 μm. In this way, a portion where the ultraviolet rays were partially irradiated with a width of 1 mm and a portion where the ultraviolet rays were not irradiated with a width of 1 mm were repeated. This was allowed to stand in an oven at 230 ° C. for 1 hour, and the portion that had not been irradiated with ultraviolet rays was thermally polymerized. When the optically anisotropic body thus obtained was observed after cooling to room temperature, the polymerizable liquid crystal material was cured over the entire area. It was confirmed that there was no phase difference due to the thermal polymerization in the state. However, many cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 343 nm.

(Comparative Example 10)
In Comparative Example 9, the experiment was performed in the same manner except that the UV irradiation time was set to 0.63 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. Cracks were observed in the pattern area. The UV irradiated part had optical anisotropy and the phase difference was 376 nm.

(Comparative Example 11)
In Comparative Example 9, the experiment was performed in the same manner except that the UV irradiation time was set to 1.25 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. Further, some cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 392 nm.

(Comparative Example 12)
The experiment was performed in the same manner as in Example 9 except that the UV irradiation time was 2.5 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 419 nm.

(Comparative Example 13)
The polymerizable liquid crystal composition (A-1) prepared in Reference Example 1 was 99.00%, and the thermal polymerization initiator 2,2′-Azobis [N- (2-propenyl) -2-methylpropionamide] of the formula (r3) was 1 A polymerizable liquid crystal composition (E-2) consisting of 0.00% was prepared. The 10-hour half-life temperature of the thermal polymerization initiator of the formula (r3) is 96 ° C.

更に重合性液晶組成物（D-2）35%、シクロペンタノン65%からなる重合性液晶溶液（D-3）を調製した。これをラビング処理を施したポリイミド配向膜付きのガラス基板にスピンコート（800回転/分、15秒）した。スピンコートした基板を80℃で2分間加熱して溶媒を揮発させた後、2分間室温で放置した。この状態で重合性液晶組成物層を観察したところ、水平１軸配向していることが確かめられた。このようにして得られた重合性液晶組成物層に、高圧水銀ランプから発生する紫外線（バンドパスフィルターを通したもの。波長365nmにおいて強度20mW/cm²）を空気中でマスクパターン（一部に1mmピッチのラインパターンを持つ）と通して0.31秒照射した。マスクパターンと重合性液晶組成物層の間の距離は150μmに保った。このようにして、一部に1mmの幅で紫外線が照射されたところと、1mmの幅で紫外線が未照射のところが繰り返された状態にした。これを230℃のオーブンに1時間静置して、紫外線が未照射だった部分を熱重合させた。このようにして得られた光学異方体を室温まで冷却したのちに観察したところ、重合性液晶材料は面積全体にわたって硬化していること、紫外線が未照射だった部分は、等方性液体相の状態で熱重合したために、位相差を持っていないことが確かめられた。しかし、パターン部にひび割れが観察された。UV照射した部分は光学異方性を持っており、位相差は335nmであった。

Further, a polymerizable liquid crystal solution (D-3) comprising 35% of a polymerizable liquid crystal composition (D-2) and 65% of cyclopentanone was prepared. This was spin coated (800 rpm) for 15 seconds on a glass substrate with a polyimide alignment film that had been rubbed. The spin-coated substrate was heated at 80 ° C. for 2 minutes to volatilize the solvent, and then allowed to stand at room temperature for 2 minutes. When the polymerizable liquid crystal composition layer was observed in this state, it was confirmed that horizontal uniaxial alignment was achieved. The polymerizable liquid crystal composition layer thus obtained was irradiated with ultraviolet light generated from a high-pressure mercury lamp (passed through a band-pass filter. Intensity 20 mW / cm ^{2 at a} wavelength of 365 nm) in a mask pattern (in part). With a line pattern of 1 mm pitch) for 0.31 seconds. The distance between the mask pattern and the polymerizable liquid crystal composition layer was kept at 150 μm. In this way, a portion where the ultraviolet rays were partially irradiated with a width of 1 mm and a portion where the ultraviolet rays were not irradiated with a width of 1 mm were repeated. This was allowed to stand in an oven at 230 ° C. for 1 hour, and the portion that had not been irradiated with ultraviolet rays was thermally polymerized. When the optically anisotropic body thus obtained was observed after cooling to room temperature, the polymerizable liquid crystal material was cured over the entire area. It was confirmed that there was no phase difference due to the thermal polymerization in the state. However, cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 335 nm.

(Comparative Example 14)
In Comparative Example 13, the experiment was performed in the same manner except that the UV irradiation time was set to 0.63 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. Some cracks were observed in the pattern area. The UV irradiated part had optical anisotropy and the phase difference was 359 nm.

(Comparative Example 15)
In Comparative Example 13, the experiment was performed in the same manner except that the UV irradiation time was changed to 1.25 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 396 nm.

(Comparative Example 16)
The experiment was performed in the same manner as in Example 13 except that the UV irradiation time was 2.5 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 408 nm.

(Comparative Example 17)
The polymerizable liquid crystal composition (A-1) prepared in Reference Example 1 is 99.00%, and the thermal polymerization initiator 2,2′-Azobis (N-butyl-2-methylpropionamide) of the formula (r4) is from 1.00%. A polymerizable liquid crystal composition (F-2) was prepared. The 10-hour half-life temperature of the thermal polymerization initiator of the formula (r4) is 110 ° C.

更に重合性液晶組成物（F-2）35%、シクロペンタノン65%からなる重合性液晶溶液（F-3）を調製した。これをラビング処理を施したポリイミド配向膜付きのガラス基板にスピンコート（800回転/分、15秒）した。スピンコートした基板を80℃で2分間加熱して溶媒を揮発させた後、2分間室温で放置した。この状態で重合性液晶組成物層を観察したところ、水平１軸配向していることが確かめられた。このようにして得られた重合性液晶組成物層に、高圧水銀ランプから発生する紫外線（バンドパスフィルターを通したもの。波長365nmにおいて強度20mW/cm²）を空気中でマスクパターン（一部に1mmピッチのラインパターンを持つ）と通して0.31秒照射した。マスクパターンと重合性液晶組成物層の間の距離は150μmに保った。このようにして、一部に1mmの幅で紫外線が照射されたところと、1mmの幅で紫外線が未照射のところが繰り返された状態にした。これを230℃のオーブンに1時間静置して、紫外線が未照射だった部分を熱重合させた。このようにして得られた光学異方体を室温まで冷却したのちに観察したところ、重合性液晶材料は面積全体にわたって硬化していること、紫外線が未照射だった部分は、等方性液体相の状態で熱重合したために、位相差を持っていないことが確かめられた。しかし、パターン部にひび割れが観察された。UV照射した部分は光学異方性を持っており、位相差は264nmであった。

Furthermore, a polymerizable liquid crystal solution (F-3) comprising 35% of a polymerizable liquid crystal composition (F-2) and 65% of cyclopentanone was prepared. This was spin coated (800 rpm) for 15 seconds on a glass substrate with a polyimide alignment film that had been rubbed. The spin-coated substrate was heated at 80 ° C. for 2 minutes to volatilize the solvent, and then allowed to stand at room temperature for 2 minutes. When the polymerizable liquid crystal composition layer was observed in this state, it was confirmed that horizontal uniaxial alignment was achieved. The polymerizable liquid crystal composition layer thus obtained was irradiated with ultraviolet light generated from a high-pressure mercury lamp (passed through a band-pass filter. Intensity 20 mW / cm ^{2 at a} wavelength of 365 nm) in a mask pattern (in part). With a line pattern of 1 mm pitch) for 0.31 seconds. The distance between the mask pattern and the polymerizable liquid crystal composition layer was kept at 150 μm. In this way, a portion where the ultraviolet rays were partially irradiated with a width of 1 mm and a portion where the ultraviolet rays were not irradiated with a width of 1 mm were repeated. This was allowed to stand in an oven at 230 ° C. for 1 hour, and the portion that had not been irradiated with ultraviolet rays was thermally polymerized. When the optically anisotropic body thus obtained was observed after cooling to room temperature, the polymerizable liquid crystal material was cured over the entire area. It was confirmed that there was no phase difference due to the thermal polymerization in the state. However, cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 264 nm.

(Comparative Example 18)
In Comparative Example 17, the experiment was performed in the same manner except that the UV irradiation time was set to 0.63 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. Cracks were observed in the pattern area. The UV irradiated part had optical anisotropy and the phase difference was 278 nm.

(Comparative Example 19)
In Comparative Example 17, the experiment was performed in the same manner except that the UV irradiation time was set to 1.25 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 295 nm.

(Comparative Example 20)
The experiment was performed in the same manner as in Example 17 except that the UV irradiation time was 2.5 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 313 nm.

(Example 5)
Polymerizable liquid crystal comprising 99.50% of the polymerizable liquid crystal composition (A-1) prepared in Reference Example 1 and 0.50% of the thermal polymerization initiator 1,1′-Azobis (cyclohexane-1-carbonitrile) of the formula (a) A composition (G-2) was prepared.
Further, a polymerizable liquid crystal solution (G-3) comprising 35% of a polymerizable liquid crystal composition (G-2) and 65% of cyclopentanone was prepared. This was spin coated (800 rpm) for 15 seconds on a glass substrate with a polyimide alignment film that had been rubbed. The spin-coated substrate was heated at 80 ° C. for 2 minutes to volatilize the solvent, and then allowed to stand at room temperature for 2 minutes. When the polymerizable liquid crystal composition layer was observed in this state, it was confirmed that horizontal uniaxial alignment was achieved. The polymerizable liquid crystal composition layer thus obtained was irradiated with ultraviolet rays generated from a high-pressure mercury lamp (passed through a bandpass filter. The intensity was 20 mW / cm ^{2 at a} wavelength of 360 nm) in air in a mask pattern (partially With a line pattern of 1 mm pitch) for 0.31 seconds. The distance between the mask pattern and the polymerizable liquid crystal composition layer was kept at 150 μm. In this way, a portion where the ultraviolet rays were partially irradiated with a width of 1 mm and a portion where the ultraviolet rays were not irradiated with a width of 1 mm were repeated. This was allowed to stand in an oven at 230 ° C. for 1 hour, and the portion that had not been irradiated with ultraviolet rays was thermally polymerized. When the optically anisotropic body thus obtained was observed after cooling to room temperature, the polymerizable liquid crystal material was cured over the entire area. It was confirmed that there was no phase difference due to the thermal polymerization in the state. Moreover, some cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 337 nm.

(Example 6)
In Example 5, an experiment was performed in the same manner except that the UV irradiation time was set to 0.63 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. Further, some cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 357 nm.

(Example 7)
In Example 5, an experiment was performed in the same manner except that the UV irradiation time was set to 1.25 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 384 nm.

(Example 8)
In Example 5, the experiment was performed in the same manner except that the UV irradiation time was 2.5 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 400 nm.

Example 9
Polymerizable liquid crystal comprising 99.50% of the polymerizable liquid crystal composition (A-1) prepared in Reference Example 1 and 2.00% of the thermal polymerization initiator 1,1′-Azobis (cyclohexane-1-carbonitrile) of the formula (a) A composition (H-2) was prepared.
Furthermore, a polymerizable liquid crystal solution (H-3) comprising 35% of a polymerizable liquid crystal composition (H-2) and 65% of cyclopentanone was prepared. This was spin coated (800 rpm) for 15 seconds on a glass substrate with a polyimide alignment film that had been rubbed. The spin-coated substrate was heated at 80 ° C. for 2 minutes to volatilize the solvent, and then allowed to stand at room temperature for 2 minutes. When the polymerizable liquid crystal composition layer was observed in this state, it was confirmed that horizontal uniaxial alignment was achieved. The polymerizable liquid crystal composition layer thus obtained was irradiated with ultraviolet rays generated from a high-pressure mercury lamp (passed through a bandpass filter. The intensity was 20 mW / cm ^{2 at a} wavelength of 360 nm) in air in a mask pattern (partially With a line pattern of 1 mm pitch) for 0.31 seconds. The distance between the mask pattern and the polymerizable liquid crystal composition layer was kept at 150 μm. In this way, a portion where the ultraviolet rays were partially irradiated with a width of 1 mm and a portion where the ultraviolet rays were not irradiated with a width of 1 mm were repeated. This was allowed to stand in an oven at 230 ° C. for 1 hour, and the portion that had not been irradiated with ultraviolet rays was thermally polymerized. When the optically anisotropic body thus obtained was observed after cooling to room temperature, the polymerizable liquid crystal material was cured over the entire area. It was confirmed that there was no phase difference due to the thermal polymerization in the state, but there was some cloudiness. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 322 nm.

(Example 6)
In Example 9, the experiment was performed in the same manner except that the UV irradiation time was set to 0.63 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference, but there was some cloudiness. It was. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 353 nm.

(Example 7)
In Example 9, the experiment was performed in the same manner except that the UV irradiation time was 1.25 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference, but there was some cloudiness. It was. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 377 nm.

(Example 8)
In Example 5, the experiment was performed in the same manner except that the UV irradiation time was 2.5 seconds. In the obtained optical anisotropic body, it was confirmed that the polymerizable liquid crystal material was cured over the entire area, and the portion that had not been irradiated with ultraviolet rays had no phase difference, but there was some cloudiness. It was. In addition, no cracks were observed in the pattern portion. The UV irradiated part had optical anisotropy and the phase difference was 387 nm.
The above results are summarized in Table 1. From these results, it can be seen that when the UV irradiation amount is small, cracks are likely to be induced, but the polymerizable liquid crystal composition of the present invention is unlikely to crack and a good quality cured film can be obtained.

ひび割れの基準（○：無、△：若干有、×：有、××：多数有）

Crack standard (○: None, △: Slightly, ×: Yes, XX: Many)

Claims (10)

A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound, a photopolymerization initiator, and a thermal polymerization initiator, wherein the 10-hour half-life temperature of the thermal polymerization initiator is from 70 ° C to 93 ° C Liquid crystal composition. The polymerizable liquid crystal composition according to claim 1, wherein the thermal polymerization initiator has a cyclohexane ring. The thermal polymerization initiator is represented by the general formula (a)

(Wherein the carbon atom in the cyclohexane ring may be substituted with a nitrogen atom or an oxygen atom, and the hydrogen atom may be substituted with an alkyl group having 1 to 18 carbon atoms) The polymerizable liquid crystal composition according to claim 2. The polymerizable liquid crystal composition according to any one of claims 1 to 3, wherein a monofunctional polymerizable liquid crystal compound or a bifunctional polymerizable liquid crystal compound is used as the polymerizable liquid crystal compound. The polymerizable liquid crystal composition has the general formula (I)

(Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, m represents 0 or 1, MG represents a mesogenic group or a mesogenic support group, and R ¹ represents Represents a halogen atom, a cyano group or an alkyl group having 1 to 25 carbon atoms, and the alkyl group may be substituted by one or more halogen atoms or CN, and one CH ₂ present in the group. Group or two or more non-adjacent CH ₂ groups are each independently of each other such that —O—, —S—, —NH—, —N (CH ₃ ) -, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted, or R ¹ may be represented by the general formula (Ia)

(Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, and m represents 0 or 1). And Sp represents an alkylene group (the alkylene group may be substituted by one or more halogen atoms or CN, one CH ₂ group present in the group or two or more not adjacent to each other) The CH ₂ groups of the present invention are independent of each other, and in the form in which oxygen atoms are not directly bonded to each other, —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, —COO— , -OCO-, -OCOO-, -SCO-, -COS- or -C≡C-), MG is represented by the general formula (Ib)

(In the formula, A1, A2 and A3 are each independently 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1, 3-dioxane-2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine- 2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, Phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene 2,7-diyl group or fluorene 2, Represents a 7-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9 , 10-Dihydrophenanthrene-2,7-diyl group 1,2,3,4,4a, 9,10a- octahydrophenanthrene 2,7-diyl group and fluorene 2,7-diyl group is 1 or more F as _{substituents, Cl, CF 3, OCF 3} , cyano Group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkanoyl group, an alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group, an alkenoyl group or an alkenoyloxy group. , Z0, Z1, Z2 and Z3 are each independently -COO-, -OCO-, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -CH = CH-, -C≡C -, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COO CH ₂ CH _2- , -OCOCH ₂ CH _2- , -CONH-,- NHCO- or a single bond, n represents 0, 1, 2, or 3), and P represents a general formula (Ic) or general formula (Id)

(Wherein R ²¹ , R ²² , R ²³ , R ³¹ , R ³² and R ³³ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents 0 or 1) The polymerizable liquid crystal composition according to claim 4, wherein the polymerizable liquid crystal composition is a compound representing a substituent selected from the group consisting of substituents represented by: Monofunctional polymerizable compounds are represented by the general formula (II)

(Wherein Z ³ represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, Z ⁴ represents a hydrogen atom or a methyl group, W ³ represents a single bond, —O—, -COO- or -OCO-, v represents an integer of 0 to 18, u represents 0 or 1, D, E and F are each independently a 1,4-phenylene group or a non-adjacent CH group. 1,4-phenylene group substituted with nitrogen, 1,4-cyclohexylene group, 1,4-cyclohexylene group in which one or two non-adjacent CH ₂ groups are substituted with oxygen or sulfur atoms, 1, Represents a 4-cyclohexenylene group, but the 1,4-phenylene group present in the formula is substituted by one or more alkyl groups, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms having 1 to 7 carbon atoms. Y ⁶ and Y ⁷ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, — CH = CH-, -CF = CF _{-, - (CH 2) 4} -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, - CH 2 CH 2 CH = CH -, - CH = CHCOO -, - OCOCH = CH -, - CH 2 CH 2 COO -, - CH 2 CH 2 OCO -, - COO CH 2 CH 2 - or -OCOCH ₂ CH ₂ - represents, Y ⁸ represents a single bond, - O-, -COO-, -OCO- or -CH = CHCOO-, but when W ³ represents a single bond, v represents an integer of 2 to 18.) 5. The polymerizable liquid crystal composition according to claim 4, wherein Bifunctional polymerizable compounds are represented by the general formula (III)

(In the formula, Z ⁵ and Z ⁶ represent a hydrogen atom and a methyl group, G, H and I are each independently 1,4-phenylene group and 1,4- A phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexylene group or a 1,4-cyclohexenylene group in which one or two non-adjacent CH2 groups are substituted with an oxygen or sulfur atom. The 1,4-phenylene group present therein may be substituted by one or more alkyl groups having 1 to 7 carbon atoms, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms, and m is an integer of 0 to 3 W ¹ and W ² each independently represent a single bond, —O—, —COO— or —OCO—, and Y ¹ and Y ² each independently represent a single bond, —COO—, —OCO— _{, -CH 2 CH 2 COO -,} - CH 2 CH 2 OCO -, - COOCH 2 CH2 -, - OCOCH 2 CH 2 - represents, r and s represent each independently 2 to 18 integer, formula Exist in The 1,4-phenylene group may be an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom. The polymerizable liquid crystal composition according to claim 4. As a polymerizable liquid crystal compound, a benzene derivative, a triphenylene derivative, a truxene derivative, a phthalocyanine derivative or a cyclohexane derivative is used as a mother nucleus at the center of the molecule, and a linear alkyl group, a linear alkoxy group or a substituted benzoyloxy group is used as its side chain. The polymerizable liquid crystal composition according to any one of claims 1 to 3, comprising a discotic polymerizable liquid crystal compound having a radially substituted structure. Discotic polymerizable liquid crystal compounds are represented by the general formula (IV)

(In the formula, each R ⁵ independently represents a substituent represented by the general formula (IV-a).)

(In the formula, R ⁶ and R ⁷ each independently represent a hydrogen atom, a halogen atom or a methyl group, and R ⁸ represents an alkoxy group having 1 to 20 carbon atoms, and the hydrogen atom in the alkoxy group represents a general formula. (It may be substituted by a substituent represented by (Vb), general formula (IV-c) or general formula (IV-d).)

(Wherein R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents 0 or 1) It is more preferable that at least one of R ^{8 in} the general formula (IV) is a substituent represented by the general formula (IV-b) or (IV-c). And all of R ⁸ are represented by the general formula (IV-b) and the alkoxy group substituted by the substituent represented by the general formula (IV-c)). The polymerizable liquid crystal composition according to claim 8. An optical anisotropic body obtained by curing the polymerizable liquid crystal composition according to any one of claims 1 to 9.