JP5776920B2 - Method for producing biaxial retardation film - Google Patents

Description

  The present invention relates to a method for producing a biaxial retardation film useful as an optical compensation film for liquid crystal displays and the like.

  As a technique useful for improving the performance of a liquid crystal display, particularly a VA liquid crystal display, use of a biaxial retardation film using a polymerizable cholesteric material has been proposed (see Patent Documents 1 to 3). This biaxial film can be produced by applying a polymerizable cholesteric liquid crystal to a substrate and then polymerizing with polarized ultraviolet light.

  In the biaxial retardation film, the front retardation (Re) and thickness direction retardation (Rth) defined as follows are important physical properties, the front retardation (Re) is 40 nm or more, and the thickness direction retardation. Rth is preferably 180 nm or more.

（式中、ｎｘ、ｎｙはそれぞれフィルム平面方向の屈折率を表し、nｚは厚み方向の屈折率を表し、ｄは厚みをを表す。）

(In the formula, nx and ny represent the refractive index in the film plane direction, nz represents the refractive index in the thickness direction, and d represents the thickness.)

（式中、ｎｘ、ｎｙはそれぞれフィルム平面方向の屈折率を表し、nｚは厚み方向の屈折率を表し、ｄは厚みをを表す。）
二軸性位相差フィルムの製造において、非偏光紫外線を照射した場合には正面位相差は0となるが、偏光紫外線を照射して偏光紫外光の振動方向に対して異方的な重合を引き起こすことによって、螺旋構造を歪ませて正面位相差を生じさせている。このような二軸フィルム作製において、正面位相差を40nm以上にするのが技術上重要な課題となっている。

(In the formula, nx and ny represent the refractive index in the film plane direction, nz represents the refractive index in the thickness direction, and d represents the thickness.)
In the production of a biaxial retardation film, the front phase difference is 0 when irradiated with non-polarized ultraviolet light, but irradiation with polarized ultraviolet light causes anisotropic polymerization with respect to the vibration direction of polarized ultraviolet light. As a result, the spiral structure is distorted to produce a front phase difference. In producing such a biaxial film, it is an important technical issue to set the front phase difference to 40 nm or more.

In order to increase the front phase difference, a slower polymerization rate is advantageous. For this purpose, for example, it is necessary to reduce the intensity of polarized ultraviolet light to about 20 mW / cm ² or less. However, if the intensity of polarized ultraviolet light is weakened, it is necessary to lengthen the ultraviolet irradiation time in order to ensure a certain degree of curing. When the polarized light irradiation time is long, there is a problem that productivity is lowered. In order to extend the irradiation time of polarized ultraviolet rays while maintaining a constant production amount, it is necessary to install many polarized ultraviolet ray irradiation devices. In reality, it was difficult to cope with the increase. On the other hand, the obtained film is required to have a small retardation change rate even when heated to about 200 ° C. If the polarized light irradiation time is not lengthened, there is a problem that the degree of curing is lowered and the reliability of the obtained film is deteriorated.

  As described above, it is difficult to produce a biaxial retardation film having a large front phase difference and high heat resistance with high production efficiency, which hinders the application of a biaxial retardation film using a polymerizable cholesteric material. It was.

JP 2005-513241 A Special table 2008-505369 Special table 2008-512504 gazette

  An object of the present invention is to provide an efficient method for producing a biaxial retardation film having a large front phase difference and high heat resistance.

  As a result of diligent examination of various manufacturing conditions to achieve the above object, the exposure process of the polymerizable liquid crystal composition includes a polarized UV irradiation process for securing a front phase difference and a non-polarized UV light for ensuring heat resistance. We examined a manufacturing method with two stages of the irradiation process, and found that the irradiation time of polarized ultraviolet rays can be shortened even if the intensity of polarized ultraviolet rays is reduced for the purpose of increasing the front phase difference, and the present invention has been completed. It was.

The present invention relates to a first exposure in which a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, an optically active compound and a photopolymerization initiator and exhibiting a chiral nematic phase is irradiated with polarized ultraviolet rays having a light absorption wavelength of the photopolymerization initiator. A process for producing a biaxial retardation film comprising a second exposure step of irradiating a non-polarized ultraviolet ray having a wavelength of 200 to 400 nm is provided. However, when there are a plurality of photopolymerization initiators, the light absorption wavelength irradiated in the first exposure step is the light absorption wavelength of the one photopolymerization initiator contained.
Moreover, this invention provides the liquid crystal display element using the biaxial retardation film manufactured by the said manufacturing method.

  By the production method of the present invention, a biaxial retardation film having a large front phase difference and high heat resistance can be produced with high production efficiency. The biaxial retardation film produced by the production method of the present invention is useful as an optical compensation film for liquid crystal displays and the like.

It is a figure which shows the emission spectrum of non-polarization UV of the high pressure mercury lamp used in Example 1. FIG.

The first exposure step of the production method of the present invention includes a step of irradiating polarized ultraviolet rays having a light absorption wavelength of the photopolymerization initiator. Although compounds having various light absorption wavelengths are known as photopolymerization initiators, specifically, irradiation with polarized light having a wavelength of either 280 to 320 nm or wavelengths of 320 to 380 nm as a main component It is preferable to use polarized ultraviolet rays having a wavelength of 320 to 380 nm.
In this case, when a plurality of photopolymerization initiators are contained, the light absorption wavelength for irradiating polarized ultraviolet rays is the light absorption wavelength of one photopolymerization initiator contained.
The main component preferably has an integrated intensity of at least 80%, more preferably 90% or more in at least a selected wavelength region.

Exposure intensity in the first exposure step, since the very strong and front retardation intensity of polarized UV is reduced, preferably 20 mW / cm ² or less strength, more preferably 15 mW / cm ² or less, 10 mW / cm ² The following is particularly preferred, but preferably not less than 5 mW / cm ² .
The irradiation time of polarized ultraviolet rays in the first exposure step is preferably 60 seconds or less, more preferably 30 seconds or less, and particularly preferably 15 seconds or less, from the viewpoint of shortening the tact time and improving productivity. Preferably no less than 1 second.
Although there is no restriction | limiting in particular about the temperature at the time of irradiation, It is necessary to maintain the polymerizable liquid crystal composition at the temperature which exhibits a chiral nematic phase.

In the second exposure step, non-polarized ultraviolet rays having a wavelength of 200 to 400 nm are irradiated, but it is preferable to irradiate non-polarized ultraviolet rays containing wavelengths other than those selected in the first exposure step. At this time, the wavelengths other than the wavelength selected in the first exposure step preferably have an intensity of at least 20% or more, more preferably 40% or more, and particularly preferably 60% or more.
The exposure dose in the second exposure step is preferably 50 mW / cm ² or more, more preferably 100 mW / cm ² or more, particularly preferably 400 mW / cm ² or more, but preferably does not exceed 2000 mJ / cm ² . If it exceeds 2000 mJ / cm ² , the resulting film tends to yellow.
Exposure in the second exposure step is preferably 200 mJ / cm ² or more, more preferably 400 mJ / cm ² or more, 600 mJ / cm ² or more is particularly preferred, preferably does not exceed 2000 mJ / cm ^2. If it exceeds 2000 mJ / cm ² , the resulting film tends to yellow.

  The atmosphere at the time of exposure is preferably performed in the air without replacement with an inert gas such as nitrogen or argon in both the first and second exposure steps. Replacement with an inert gas increases the takt time and is disadvantageous in terms of manufacturing cost.

The photopolymerization initiator used in the present invention is preferably a photoradical initiator. In particular,
Examples of the main absorption wavelength at a wavelength of 280 to 320 nm include `` Irgacure-184 '', `` Irgacure-184D '', `` Irgacure-907 '', `` Irgacure-369 '',
The main absorption wavelengths at 320 to 380 nm include “Irgacure-651”, “Lucirin TPO” (manufactured by BASF), and the oxime esters “Irgacure OXE 01” and “Irgacure OXE 02” (above, Ciba Specialty) Chemicals).
The polymerization initiator generates a radical at the light absorption wavelength and has the highest sensitivity. From this viewpoint, “Irgacure OXE 01” having a high sensitivity around 360 nm is particularly preferable.

  Two or more photopolymerization initiators are preferably used in combination. In this case, the two polymerization initiators preferably have different light absorption wavelengths, and those having a main absorption wavelength of 280 to 320 nm, 320 It is more preferable to use at least one of those having a main absorption wavelength at ˜380 nm.

The total addition amount of the polymerization initiator in the polymerizable liquid crystal composition is preferably 1 to 6%, more preferably 1 to 5%, and particularly preferably 3 to 5%. When the addition amount is small, the curability is deteriorated, and when the addition amount is large, the properties of the polymerizable liquid crystal composition as a liquid crystal are easily impaired.
In particular, when using “Irgacure OXE 01”, it is preferable to contain 1% or more.

  In the production method of the present invention, the polymerizable liquid crystal composition exhibiting a chiral nematic phase is subjected to the first exposure step after forming a layer by a method such as coating on a glass or plastic substrate. In the case of coating, a method in which the polymerizable liquid crystal composition is dissolved in a solvent, coated on 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. The substrate may not be subjected to orientation treatment, but is preferably subjected to orientation treatment. In the case of a glass substrate, it is preferable to form a polyimide alignment film or a photo-alignment film and perform horizontal uniaxial alignment at the substrate interface.

  The lower limit temperature of the chiral nematic phase of the polymerizable liquid crystal composition used in the production method of the present invention is preferably lower than 40 ° C, more preferably lower than 30 ° C, and particularly preferably lower than 20 ° C. The upper limit temperature of the chiral nematic phase is preferably higher than 60 ° C, more preferably higher than 80 ° C, and particularly preferably higher than 100 ° C.

  The helical pitch of the chiral nematic phase is preferably designed so that the selective reflection of the chiral nematic phase is not in the visible light range. That is, it is preferable to design in the infrared region or the ultraviolet region, and it is particularly preferable to design in the ultraviolet region.

(Polymerizable liquid crystal compound)
The polymerizable liquid crystal composition used in the production method of the present invention contains a polymerizable liquid crystal compound as an essential component, but the content thereof is 40 to 97%, more preferably 60 to 95% in the polymerizable liquid crystal composition. In particular, the content is preferably 80 to 90%.
Specifically, the polymerizable liquid crystal compound is represented by the general formula (II)

(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 have the general formula (II-a)

（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 (II), 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 (II-b)

（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（II-c）又は、一般式（II-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 (II-c) or a general formula (II-d)

(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 (II), the compound having one polymerizable functional group is specifically represented by the general formula (III)

（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 (III) is useful because it has an effect of lowering the liquid crystal lower limit temperature, but the addition amount is preferably 5 to 60%, more preferably 10 to 50%, and more preferably 15 to 40%. Is particularly preferred. If the amount added is large, the heat resistance of the obtained biaxial film tends to be impaired.

The compound represented by the general formula (III) includes a compound having a liquid crystalline skeleton and a compound having a spacer between polymerizable functional groups. In the general formula (III), 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 (IV-1 ) To the compound represented by the general formula (IV-9) is preferable.

(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 (III), 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.)
Among the compounds represented by the general formula (II), the compound having two polymerizable functional groups is represented by the general formula (IV)

(Wherein Z ⁵ and Z ⁶ represent a hydrogen atom and a methyl group, G, H and I are each independently 1,4-phenylene group, 1,4- A phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexylene group in which one or two non-adjacent CH ₂ groups are substituted with an oxygen or sulfur atom, and a 1,4-cyclohexenylene group, The 1,4-phenylene group present in the formula may be substituted with one or more alkyl groups having 1 to 7 carbon atoms, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms, and m is from 0 to 3 W ¹ and W ² each independently represent a single bond, —O—, —COO— or —OCO—, Y ¹ and Y ² each independently represent a single bond, —COO—, —OCO -, -CH ₂ CH ₂ COO-, -CH ₂ CH ₂ OCO-, -COO CH ₂ CH _2- , -OCOCH ₂ CH _2- , and r and s each independently represent an integer of 2 to 18 Is present in the formula The 1,4-phenylene group is preferably an alkyl group having 1 to 7 carbon atoms, an alkoxy group, an alkanoyl group, a cyano group, or a halogen atom.

The compound represented by the general formula (IV) is effective for obtaining high heat resistance when formed into a film, but the addition amount is preferably 30 to 85%, more preferably 40 to 80%, ˜75% or less is particularly preferable.
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, compounds represented by (II-8) and (II-9) are preferable. 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.

  A discotic compound may be used in the polymerizable liquid crystal composition. 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 side chain, and is represented by the general formula (V)

（式中、R⁵はそれぞれ独立して一般式（V-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 (Va).)

（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（V-c）又は一般式（V-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 (Vc) or general formula (Vd).)

（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（V）においてR⁸の内少なくとも一つは一般式（V-b）、一般式（V-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（V-b）、一般式（V-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。
さらに、一般式(V-a)は具体的には一般式(V-e)

(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 (V) is substituted with a substituent represented by the general formula (Vb) or the general formula (Vc). It is preferable to represent an alkoxy group, and it is particularly preferable that all of R ⁸ represent an alkoxy group substituted by a substituent represented by the general formula (Vb) or the general formula (Vc).
Further, the general formula (Va) specifically represents the general formula (Ve).

（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。
（キラル化合物）
本発明の製造方法で用いる重合性液晶組成物にはキラルネマチック相を得ることを目的としてキラル化合物を含有させる。キラル化合物のなかでも、分子中に重合性官能基を有する化合物が特に好ましい。重合性官能基としては、アクリロイルオキシ基が特に好ましい。キラル化合物の添加量は、化合物の螺旋誘起力によって適宜調整することが必要であるが、15%以下が好ましい。キラル化合物の具体的例としては、式（a）〜（g）の化合物を挙げることができる。

It is particularly preferable to have a structure represented by the formula (wherein n represents an integer of 2 to 9).
(Chiral compound)
The polymerizable liquid crystal composition used in the production method of the present invention contains 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, 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 15% or less. Specific examples of the chiral compound include compounds of the formulas (a) to (g).

（式中、ｎは2〜12の整数を表す）これらの化合物のなかでも（a）の化合物が好ましい。この場合、ｎは2もしくは4が合成コストの観点からもっとも好ましい。

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

(Various additives)
It is preferable to add a light absorber to the polymerizable liquid crystal composition used in the production method of the present invention. The light absorber has an absorption band at a wavelength of 280 to 400 nm, more preferably an absorption band at a wavelength of 300 to 390 nm, and particularly preferably an absorption band at 320 to 380 nm. As a specific structure, it is preferable to have a double bond in the molecule. As the double bond, a carbon-carbon double bond and a carbon-nitrogen double bond are preferable. Further, a molecule having good linearity is preferable. This light absorber may or may not exhibit liquid crystallinity.
Specifically, the general formula (I)

（式中、Ｘ¹からＸ⁴はそれぞれ独立してフッ素原子、炭素原子数1〜18のアルキル基、アルコキシ基、アシル基、アルコキシカルボキシ基、炭素原子数2〜18のアルケニル基、又はアルケニルオキシ基を表し、ｌ及びｏはそれぞれ独立して１から５の整数を表し、ｍ及びｎはそれぞれ独立して１から４の整数を表し、Ｌ¹からＬ³はそれぞれ独立して単結合又は−CH＝CH−を表すが、Ｌ¹からＬ³の少なくとも二つは−CH＝CH−を表す。）で表される化合物が好ましく、一般式（Ia）

Wherein X ¹ to X ⁴ are each independently a fluorine atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group, an acyl group, an alkoxycarboxy group, an alkenyl group having 2 to 18 carbon atoms, or alkenyloxy. And l and o each independently represents an integer of 1 to 5, m and n each independently represents an integer of 1 to 4, and L ¹ to L ³ each independently represents a single bond or- CH = CH—, wherein at least two of L ¹ to L ³ represent —CH═CH—.

Wherein X ¹ to X ⁴ are each independently a fluorine atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group, an acyl group, an alkoxycarboxy group, an alkenyl group having 2 to 18 carbon atoms, or alkenyloxy. Wherein l and o each independently represents an integer of 1 to 5, and m and n each independently represents an integer of 1 to 4).
Formula (I-1)

で表される化合物が特に好ましい。本化合物は360nm付近に吸収帯を有する。光吸収剤の添加量は0.1~4%以下が好ましく、0.2~3%が更に好ましく、0.3~2%が特に好ましい。
光吸収剤の吸収帯は、波長320〜380nmの中にあることが好ましい。

Is particularly preferred. This compound has an absorption band around 360 nm. The addition amount of the light absorber is preferably 0.1 to 4% or less, more preferably 0.2 to 3%, and particularly preferably 0.3 to 2%.
The absorption band of the light absorber is preferably in the wavelength range of 320 to 380 nm.

The polymerizable liquid crystal composition used in the production method of the present invention preferably contains 1000 to 15000 ppm of a polymerization 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 polymerizable liquid crystal composition has a general formula (VI) for the purpose of quickly obtaining good planar alignment when applied.

(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 (VI) 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 (VI), as a preferred structure, the formula (VI-a) to the formula (VI-f)

The compound which has a repeating unit represented by these is mentioned. Among these, structures represented by formulas (VI-a) to (VI-e) are more preferable, and structures represented by formulas (VI-a) and (VI-c) are particularly preferable. A copolymer obtained by copolymerizing two or more compounds having a repeating unit represented by formula (VI-a) to formula (VI-f) is also preferable. In this case, a copolymer having the formula (VI-a) and the formula (VI-b), a copolymer having the formula (VI-a) and the formula (VI-c), the formula (VI-a) and the formula ( More preferred are copolymers having VI-f) and copolymers having formulas (VI-a), (VI-b) and formula (VI-f), wherein formula (VI-a) and formula (VI Particularly preferred are copolymers having -b) and copolymers having the formulas (VI-a), (VI-b) and (VI-f).

  If the weight average molecular weight of the compound is too small, the effect of reducing the tilt angle is poor. If the weight average molecular weight is too large, the orientation is not stable for a long time, so there is an optimum range. 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.

  A surfactant is preferably added to the polymerizable liquid crystal composition used in the production method of the present invention for the purpose of ensuring the smoothness of the surface when 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 "(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” (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%.

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). The phase difference in the thickness direction was determined by measuring the angle dependency of the phase difference with RETS-100 manufactured by Otsuka Electronics, and fitting with computer simulation software LCD-Master (manufactured by Shintech Co., Ltd.).
Reference Example 1 36.47% Liquid Crystalline Acrylate Compound of Preparation Formula (II-9-a) for Polymerizable Liquid Crystal Composition

式（II-9-b）の液晶性アクリレート化合物15.63%

Liquid crystalline acrylate compound of formula (II-9-b) 15.63%

式（II-8-a）の液晶性アクリレート化合物13.03%

Liquid crystalline acrylate compound of formula (II-8-a) 13.03%

式（IV-5-a）の液晶性アクリレート化合物21.71%

21.71% liquid crystalline acrylate compound of formula (IV-5-a)

式（a-1）のキラルアクリレート化合物9.12%

9.12% of chiral acrylate compound of formula (a-1)

式（e-1）のキラルアクリレート化合物3.04%

3.04% chiral acrylate compound of formula (e-1)

光吸収剤（I-1）0.74%

Light absorber (I-1) 0.74%

流動パラフィン0.26%、p-メトキシフェノール0.09%からなる重合性液晶組成物（A）を調整した。光吸収剤（I−１）は360nm付近に吸収帯を有する。

A polymerizable liquid crystal composition (A) comprising 0.26% liquid paraffin and 0.09% p-methoxyphenol was prepared. The light absorber (I-1) has an absorption band around 360 nm.

Example 1
Polymeric liquid crystal composition (A) prepared in Reference Example 1 is composed of 95.84% and 4.16% of photopolymerization initiator Irgacure OXE-01 (manufactured by Ciba Specialty Chemicals) having an absorption band near 360 nm ( B) was adjusted.
Further, a polymerizable liquid crystal solution (B) was prepared from 40% of the polymerizable liquid crystal composition (B) and 60% of cyclohexanone. This was spin-coated (1000 rotations / min, 30 seconds) on a glass substrate with a polyimide alignment film that had been rubbed. The spin-coated substrate was dried at 60 ° C. for 2 minutes and then allowed to stand at room temperature for 3 minutes to align the polymerizable liquid crystal in the planar orientation. The polymerizable liquid crystal composition layer thus obtained is irradiated with ultraviolet rays generated from a high-pressure mercury lamp through a polarizing filter and a bandpass filter for 30 seconds with polarized UV light (intensity 10 mW / cm ² ) for 30 seconds. The liquid crystal composition was cured (first exposure step). Furthermore, the non-polarized UV (intensity 30 mW / cm ² ) was irradiated for 27 seconds without passing through the bandpass filter and the polarizing filter with the ultraviolet rays generated from the same high-pressure mercury lamp (second exposure step). FIG. 1 shows an emission spectrum of non-polarized UV in a high-pressure mercury lamp. The thickness of the obtained film was 3 μm. The resulting film was optically biaxial. The front phase difference Re was 43 nm, and the thickness direction retardation Rth was 152 nm. When this was heated at 230 ° C. for 4 hours, the front phase difference Re was 27 nm and the thickness direction retardation Rth was 124 nm. Assuming that the phase difference before heating was 100%, the front phase difference Re was 63%, and the phase difference in the thickness direction was 70%.

(Example 2)
Polymeric liquid crystal composition (A) prepared in Reference Example 1 is 95.84%, photopolymerization initiator Irgacure OXE-01 (manufactured by Ciba Specialty Chemicals) having an absorption band near 360 nm, 2.50%, having an absorption band near 310 nm A polymerizable liquid crystal composition (C) comprising 1.66% of a photopolymerization initiator Irgacure OXE-01 (manufactured by Ciba Specialty Chemicals) was prepared. A biaxial film was produced in the same manner as in Example 1 except that the polymerizable liquid crystal composition (C) was used instead of the polymerizable liquid crystal composition (A). The front phase difference Re was 39 nm, and the thickness direction retardation Rth was 138 nm. When this was heated at 230 ° C. for 4 hours, the front phase difference Re was 27 nm and the thickness direction retardation Rth was 97 nm. Assuming that the phase difference before heating was 100%, the front phase difference Re was 69%, and the phase difference in the thickness direction was 70%.

(Comparative Example 1)
The polymerizable liquid crystal solution (B) prepared in Example 1 was spin-coated (1000 rotations / minute, 30 seconds) on a glass substrate with a polyimide alignment film subjected to rubbing treatment. The spin-coated substrate was dried at 60 ° C. for 2 minutes and then allowed to stand at room temperature for 3 minutes to align the polymerizable liquid crystal in the planar orientation. The polymerizable liquid crystal composition layer thus obtained is irradiated with 300 seconds of polarized UV light (intensity 10 mW / cm ² ) with a wavelength of 360 nm through a polarizing filter and a bandpass filter. The liquid crystal composition was cured (first exposure step). The thickness of the obtained film was 3 μm. The resulting film was optically biaxial. The front phase difference Re was 45 nm, and the thickness direction retardation Rth was 200 nm. When this was heated at 230 ° C. for 4 hours, the front phase difference Re was 27 nm and the thickness direction retardation Rth was 124 nm. Assuming that the phase difference before heating was 100%, the front phase difference Re was 60%, and the phase difference in the thickness direction was 62%.

(Comparative Example 2)
The polymerizable liquid crystal solution (B) prepared in Example 1 was spin-coated (1000 rotations / minute, 30 seconds) on a glass substrate with a polyimide alignment film subjected to rubbing treatment. The spin-coated substrate was dried at 60 ° C. for 2 minutes and then allowed to stand at room temperature for 3 minutes to align the polymerizable liquid crystal in the planar orientation. The polymerizable liquid crystal composition layer thus obtained is irradiated with ultraviolet rays generated from a high-pressure mercury lamp through a polarizing filter and a bandpass filter for 30 seconds with polarized UV light (intensity 10 mW / cm ² ) for 30 seconds. The liquid crystal composition was cured (first exposure step). The thickness of the obtained film was 3 μm. The resulting film was optically biaxial. The front phase difference Re was 43 nm, and the thickness direction retardation Rth was 152 nm. When this was heated at 230 ° C. for 4 hours, the front phase difference Re was 25 nm and the thickness direction retardation Rth was 90 nm. Assuming that the phase difference before heating is 100%, the front phase difference Re is 58%, and the thickness direction retardation is 59%.

  The above results are summarized in Table 1. From Comparative Example 1 and Comparative Example 2, it can be seen that as the exposure time decreases, the remaining ratio of Re and Rth decreases, that is, the rate of change in phase difference due to heating increases. From the comparison with Example 1, Example 2 and Comparative Example 2, it is possible to increase the residual ratio of Re and Rth by performing the second exposure even under the same first exposure conditions, that is, the rate of change of the phase difference due to heating. You can see that it can be made smaller.

Claims (17)

Polymerizable liquid crystal compound, chiral compound, photoradical polymerization initiator containing oxime ester, and general formula (I)

(Wherein X ¹ to X ⁴ are each independently a fluorine atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group, an acyl group, an alkoxycarboxy group, an alkenyl group having 2 to 18 carbon atoms, or an alkenyloxy group) And l and o each independently represents an integer of 1 to 5, m and n each independently represents an integer of 1 to 4, and L ¹ to L ³ each independently represents a single bond or- A polymerizable liquid crystal composition containing a light absorber represented by CH═CH—, wherein at least two of L ¹ to L ³ represent —CH═CH—, and exhibiting a chiral nematic phase, Biaxial position characterized by including a first exposure step of irradiating polarized ultraviolet rays having a light absorption wavelength of a photopolymerization initiator in the air, and a second exposure step of irradiating non-polarized ultraviolet rays having a wavelength of 200 to 400 nm in the air. Production of phase difference film Law, however, if the photopolymerization initiator is a plurality of light absorption wavelength to be irradiated in the first exposure step is a light absorption wavelength of the first photo-polymerization initiator containing. The method according to claim 1, wherein the photopolymerization initiator has a light absorption wavelength of 280 to 320 nm or a wavelength of 320 to 380 nm. The manufacturing method according to claim 1 or 2, wherein an exposure intensity in the first exposure step is 20 mW / cm ² or less. The manufacturing method according to claim 1, wherein the exposure time in the first exposure step is 60 seconds or less. The manufacturing method according to claim 1, wherein an exposure intensity in the second exposure step is 10 mW / cm ² or more. The manufacturing method according to claim 1, wherein an exposure amount in the second exposure step is 200 mJ / cm ² or more. The production method according to claim 1, wherein the polymerizable liquid crystal composition contains at least two kinds of polymerization initiators. The production method according to claim 7, wherein one of the two polymerization initiators is an oxime compound. The production method according to claim 1, wherein the polymerizable liquid crystal composition contains a light absorber. The general formula (I) is represented by the general formula (Ia)

(Wherein X ¹ to X ⁴ are each independently a fluorine atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group, an acyl group, an alkoxycarboxy group, an alkenyl group having 2 to 18 carbon atoms, or an alkenyloxy group) represents a group, l and o represents an integer from 1 to 5 independently, prepared according to claim 9, wherein m and n are each independently compounds represented by the representative.) an integer from 1 to 4 Method. The polymerizable liquid crystal compound has the general formula (II)

(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. A group or two or more non-adjacent CH ₂ groups are independently of each other such that —O—, —S—, —NH—, —N (CH ₃ ), in which oxygen atoms are not directly bonded to each other. -, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted, or R ¹ may have the general formula (II-a)

(Wherein P represents a reactive functional group, Sp represents a spacer group having 1 to 20 carbon atoms, and m represents 0 or 1). The manufacturing method in any one of Claim 1 to 10 containing the compound represented by this. In the general formula (II), 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 this 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 (II-b)

(Wherein 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 2,7-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 as substituents 1 or more _{F, Cl, CF 3, OCF} 3, cyano group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, alkanoyl group, alkanoyloxy group, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group , An alkenoyl group or an alkenoyloxy group, and Z 0, Z 1, Z 2 and Z 3 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, and n represents 0, 1, 2 or 3. P is the general formula (II-c) or the general formula (II-d)

(Wherein R ²¹ , R ²² , R ²³ , R ³¹ , R ³² , 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 production method according to claim 11, which represents a substituent selected from the group consisting of substituents represented by: Among the compounds represented by the general formula (II), the compound having one polymerizable functional group is specifically represented by the general formula (III)

(In the formula, 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, and 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. At best, ^{Y 6} and ^{Y 7} are each Standing 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 represents a -CH = CHCOO-, manufacture of claim 12, wherein if v is a compound represented by the representative) an integer of 2 to 18 ^{in which W 3} represents a single bond. Method. The compound represented by the general formula (II) is represented by the general formula (VI)

(Wherein 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-phenylene group in which adjacent CH groups are substituted with nitrogen. A phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexylene group in which one or two non-adjacent CH ₂ groups are substituted with an oxygen or sulfur atom, a 1,4-cyclohexenylene group, The 1,4-phenylene group present in the formula may be substituted with one or more alkyl groups having 1 to 7 carbon atoms, alkoxy groups, alkanoyl groups, cyano groups or halogen atoms, and m is from 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} -, - C H ₂ CH ₂ OCO—, —COO CH ₂ CH ₂ —, —OCOCH ₂ CH ₂ —, and r and s each independently represent an integer of 2 to 18; phenylene group is an alkyl group having 1 to 7 carbon atoms, an alkoxy group, alkanoyl group, cyano group, or a manufacturing method of claim 11, wherein a halogen atom is optionally substituted one or more.). The polymerizable liquid crystal composition has a benzene derivative, a triphenylene derivative, a truxene derivative, a phthalocyanine derivative or a cyclohexane derivative as a mother nucleus at the center of the molecule, and a linear alkyl group, a linear alkoxy group, or a substituted benzoyloxy group as its side chain. The manufacturing method according to any one of claims 1 to 10 , comprising a discotic liquid crystal compound having a radially substituted structure. The manufacturing method according to claim 15 , wherein the discotic liquid crystal compound contains a polymerizable liquid crystal composition represented by the general formula (V).

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

(In the formula, R ⁶ and R ⁷ each independently represents 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 (Vc) or general formula (Vd)).

(Wherein R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents 0 or 1 Represents.) The liquid crystal display device using a biaxial retardation film obtained in any of the manufacturing method of claims 1 16, wherein.

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