JP2013035938A - Polymerizable cholesteric liquid crystal composition and cholesteric reflective film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable cholesteric liquid crystal composition suitable for production of a cholesteric reflective film scarcely exhibiting light scattering.SOLUTION: In the polymerizable cholesteric liquid crystal composition which contains a polymerizable liquid crystal material, a chiral material, a photo-polymerization initiator, and an additive for horizontally aligning a cholesteric liquid crystal material (hereafter designated as a horizontal alignment additive), the horizontal alignment additive is a polypropylene having the mass average molecular weight of 1,300-2,800.

Description

  The present invention relates to a polymerizable liquid crystal composition useful as a liquid crystal device, a display, an optical component, a colorant, a security marking, and a member for laser emission, and a cholesteric polarizing film obtained from the polymerized liquid crystal composition, and a reflective polarizing plate About.

  Reflective polarizing plates using the circularly polarized reflection characteristics of cholesteric liquid crystals have been developed. Since this reflective polarizing plate can be used for the purpose of efficiently extracting polarized light from the backlight of a liquid crystal display, it is extremely effective from the viewpoint of energy saving. In order to put this cholesteric liquid crystal into a circularly polarizing plate into practical use, a thin film of a polymerizable cholesteric liquid crystal material is formed by means such as coating on a substrate, brought into a planar alignment state, then polymerized and solidified into a polymer film. Much has been studied.

  The polarization extraction efficiency from the backlight of a reflective polarizing plate produced using such a polymerizable cholesteric liquid crystal is affected by light scattering of the reflective polarizing plate. When light scattering increases, depolarization occurs, and the polarization extraction efficiency decreases.

  One of the causes of this light scattering is a discontinuous change in the refractive index at the alignment defect portion generated in the thin film of the polymerizable cholesteric liquid crystal material formed by means such as coating on the substrate. This alignment defect is considered to occur because the liquid crystal material is not uniformly aligned on the air interface side of the thin film formed on the substrate.

  When forming an optically anisotropic body having homogeneous alignment using a polymerizable nematic liquid crystal composition, an additive for horizontally aligning the liquid crystal material on the air interface side (hereinafter referred to as horizontal alignment additive) is a hydrocarbon. A technique using a system compound has already been disclosed (see Patent Documents 1 to 4), and as an example, a technique using polypropylene having a weight average molecular weight of 12000 is also disclosed. However, nematic liquid crystals having homogeneous alignment and cholesteric liquid crystals have different liquid crystal alignment properties, and the use of the horizontal alignment additives described therein cannot sufficiently reduce light scattering.

JP 2000-105315 A JP 2007-246896 A JP 2009-62513 A JP 2009-242563 A

  The problem to be solved by the present invention is to provide a polymerizable cholesteric liquid crystal composition capable of reducing light scattering of a film obtained by curing the polymerizable cholesteric liquid crystal composition.

As a result of intensive studies, it was found that light scattering can be effectively reduced by using a specific compound as a horizontal alignment additive, and the present invention has been achieved.
That is, the present invention relates to a polymerizable liquid crystal material, a chiral material, a photopolymerization initiator, and a general formula (I)

（式中、R¹、R²、R³及びR⁴はそれぞれ独立的に水素原子又は炭素原子数1〜２０の炭化水素基を表す。）で表される繰り返し単位を有する質量平均分子量が１３００以上２１８０以下の化合物を含有することを特徴とする重合性コレステリック液晶組成物を提供する。

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) and a mass average molecular weight having a repeating unit represented by 1300 There is provided a polymerizable cholesteric liquid crystal composition characterized by containing a compound of 2180 or less.

  The polymerizable cholesteric liquid crystal composition of the present invention can obtain a good horizontal alignment state with few alignment defects when a thin film is formed by means such as coating. For this reason, the light scattering of the film which hardened | cured polymeric cholesteric liquid crystal composition becomes small, and the reflective polarizing plate which is excellent in polarized light extraction efficiency can be produced.

  The polymerizable liquid crystal composition of the present invention contains a compound represented by the general formula (I) as a horizontal alignment additive, but polymers such as polyethylene and polypropylene are preferable, and polypropylene is more preferable. The compound represented by the general formula (I) has a mass average molecular weight of 1300 to 2180, more preferably 1400 to 2160, and particularly preferably 1500 to 2140. There is a tendency that light scattering can be reduced as the mass average molecular weight increases. Therefore, when a film is formed by coating or the like without adding a solvent to the polymerizable cholesteric liquid crystal composition, a solvent is added to the polymerizable cholesteric liquid crystal composition as long as solubility can be secured in the polymerizable cholesteric liquid crystal composition. In the case of forming a film by coating or the like, it is preferable to use a compound having a large mass average molecular weight as long as solubility can be secured in the solution of the polymerizable cholesteric liquid crystal composition. If a compound having a mass average molecular weight that does not dissolve in a solvent is used as a horizontal alignment additive, unevenness and an increase in light scattering may be caused.

  Since the compound represented by the general formula (I) is a compound having a low polarity, it dissolves well in a solvent having a low polarity, whereas it tends to hardly dissolve in a solvent having a high polarity. From this, for example, when using an aromatic hydrocarbon having no polar group such as toluene, xylene, cumene, mesitylene, etc. as a solvent, the weight average molecular weight of the horizontal alignment additive is 1600-2180. 1700 to 2160 is more preferable, and 1800 to 2140 is particularly preferable. On the other hand, when a highly polar ketone compound such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or cyclopentanone is used as a solvent, the weight average molecular weight of the horizontal alignment additive is preferably 1300 to 1900, and 1400 to 1800. More preferably, it is particularly preferably 1500-1700. When using an ester compound such as propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, γ-butyrolactone as a solvent, the mass average molecular weight of the horizontal alignment additive is preferably 1400-2180, and 1500-2080 More preferably, it is particularly preferably 1600 to 1980. When a mixed solvent is used as the solvent, it is preferable to use a horizontal alignment additive having a weight average molecular weight that is arithmetically calculated based on the above preferred weight average molecular weight, depending on the polarity and ratio of the solvent used. For example, when using a mixed solvent comprising 60% by mass of toluene and 40% by mass of cyclopentanone, the weight average molecular weight of the horizontal alignment additive is preferably 1480 to 2068, and more preferably 1580 to 2016. 1680 to 1964 is particularly preferable.

  The concentration of the horizontal alignment additive in the polymerizable liquid crystal composition is preferably 0.05 to 1.0%, more preferably 0.08 to 0.5%, and still more preferably 0.10 to 0.3%.

  The polymerizable liquid crystal compound contained in the polymerizable cholesteric liquid crystal composition of the present invention can be used without particular limitation as long as it is recognized as a polymerizable liquid crystal compound in this technical field. Among these, a compound having only one polymerizable functional group in the molecule is preferable because it is easy to produce a compound containing a low temperature around room temperature as the liquid crystal temperature range of the composition. Such compounds include, for example, Handbook of Liquid Crystals (D. Demus, JW Goodby, GW Gray, WW Spies, V. Vill, published by Wiley-VCH, 1998). , Quarterly Chemical Review No. 22, Liquid Crystal Chemistry (edited by the Chemical Society of Japan, 1994), or JP-A-7-294735, JP-A-8-3111, JP-A-8-29618, JP-A-11-80090, A rigid part called a mesogen in which a plurality of structures such as 1,4-phenylene group and 1,4-cyclohexylene group are connected as described in Kaihei 11-116538, JP-A-11-148079, etc. A rod-like polymerizable liquid crystal compound having a polymerizable functional group such as a vinyl group, an acryloyl group, or a (meth) acryloyl group, or a maleimide as described in JP-A Nos. 2004-2373 and 2004-99446 Examples thereof include a rod-like polymerizable liquid crystal compound having a group.

Examples of the polymerizable functional group include a vinyl group, an acryloyl group, a (meth) acryloyl group, and a maleimide group. From the viewpoint of productivity, an acryloyl group, a (meth) acryloyl group, and a maleimide group are preferable. Is the general formula (II)

（式中、Pは反応性官能基を表し、Spはそれぞれ独立的にスペーサー基を表し、i、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、Rは末端基、もしくは‐（Sp）i-P基と同じ意味を表す）で表される化合物が好ましい。一般式（II）において、Spが炭素原子数１から２０のアルキレン基を表し、該アルキレン基は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、MGが一般式（II-b）

(In the formula, P represents a reactive functional group, Sp represents a spacer group independently, i, represents 0 or 1, MG represents a mesogenic group or a mesogenic support group, R represents a terminal group, Or a compound represented by the same meaning as the-(Sp) iP group). In the general formula (II), Sp represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be substituted by one or more halogen atoms or CN, and one CH present in the group _Two groups or two or more non-adjacent CH ₂ groups are each independently independent 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-, and 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を表し、R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、該炭化水素基は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-、‐C＝C−又は-C≡C-により置き換えられていても良い）で表される構造を表し、Pが一般式（II-c）、（II-ｄ）又は、一般式（II-e）

(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, R represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is 1 May be substituted by one or more halogen atoms or CN, The two or more CH ₂ groups not one CH ₂ group or adjacent present in groups independently of one another each in the form of oxygen atoms are not directly bonded to each other, -O -, - S-, Replaced by -NH-, -N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS-, -C = C- or -C≡C- And P represents a general formula (II-c), (II-d), or a general formula (II-e)

(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 k is 0 or 1) Represents a substituent represented by the formula (1).
Among such liquid crystal compounds, the liquid crystal compounds having only one polymerizable functional group are specifically exemplified by the following liquid crystal compounds, but are not limited thereto.

(In the formula, l, m and n each independently represent an integer of 1 to 10, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, or a carbamoyl group. , A cyano group, a nitro group, and a halogen atom, and when these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they are all unsubstituted, or one or When these groups are a carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. May be.)
In these formulas, R preferably represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group.
These liquid crystal compounds can be used alone or in combination of two or more.

As a polymerizable liquid crystal compound contained in the polymerizable cholesteric liquid crystal composition of the present invention, a liquid crystal compound having two polymerizable functional groups is useful from the viewpoint of securing the mechanical strength of a film obtained by curing. Examples of such a compound having two polymerizable functional groups include, for example, Handbook of Liquid Crystals (D. Demus, JW Goodby, GW Gray, H. W. Spiss, V. Vill, edited by Wiley. -Published by VCH, 1998), Quarterly Chemical Review No. 22, Liquid Crystal Chemistry (Edited by Chemical Society of Japan, 1994), or Japanese Patent Laid-Open Nos. 4-227684, 11-80090, 11-116538, 11-148079, 1,4-phenylene group 1,4-cyclohexane as described in JP-A-2000-178233, JP-A-2002-308831, JP-A-2002-145830, JP-A-2004-125842, and the like. A rod-like polymerizable liquid crystal compound having a rigid site called mesogen in which a plurality of structures such as a len group are connected, and a polymerizable functional group such as a vinyl group, an acryloyl group, and a (meth) acryloyl group, or JP-A-2004-2373, A rod-like polymerizable liquid crystal compound having a maleimide group as described in JP-A-2004-99446 And the like.
Specific examples of the liquid crystal compound having two polymerizable functional groups among the compounds represented by the general formula (II) include the following liquid crystal compounds.

(In the formula, m and n each independently represent an integer of 1 to 10, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, cyano. Represents a group, a nitro group or a halogen atom, but when these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they are all unsubstituted or one or two When these groups are a carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. Good.)
R is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a cyano group.
These liquid crystal compounds can be used alone or in combination of two or more.

  The chiral compound contained in the polymerizable cholesteric liquid crystal composition of the present invention preferably has one or more polymerizable functional groups. Examples of such compounds include JP-A-11-193287, JP-A-2001-158788, JP-T 2006-52669, JP-A-2007-269639, JP-A-2007-269640, 2009. -84178 and the like, including a chiral saccharide such as isosorbide, isomannite, glucoside, etc., and a rigid site such as a 1,4-phenylene group and a 1,4-cyclohexylene group, and a vinyl group A polymerizable chiral compound having a polymerizable functional group such as an acryloyl group, a (meth) acryloyl group or a maleimide group, a polymerizable chiral compound comprising a terpenoid derivative as described in JP-A-8-239666, NATURE VOL35 467-469 pages (November 30, 1995) Published), NATURE VOL 392, pages 476 to 479 (issued on April 2, 1998), or the like, or a polymerizable chiral compound comprising a mesogenic group and a spacer having a chiral moiety, or JP-T-2004-504285. And a polymerizable chiral compound containing a binaphthyl group as described in JP-A-2007-248945. Among them, a chiral compound having a large helical twisting power (HTP) is preferable because the polymerizable liquid crystal composition of the present invention can be easily produced.

  Among such chiral compounds, compounds containing chiral saccharides are particularly preferred. like this

As such a compound, the general formula (III)

(In the general formula (III), Sp represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be substituted by one or more halogen atoms or CN. A CH ₂ group or two or more non-adjacent CH ₂ groups are each independently independent of each other in a form in which oxygen atoms are not directly bonded to each other, such as —O—, —S—, —NH—, —N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted, A4 is a 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-tetrahydronaphtha 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 are one or more F, Cl, CF ₃ , OCF ₃ , cyano group, C 1-8 alkyl group, alkoxy group, alkanoyl group, alkanoyloxy group as substituents , an alkenyl group having 2 to 8 carbon atoms, alkenyloxy group which may have a alkenoyl group or alkenoyloxy group, Z4 is, -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, m represents 0, 1, 2 or 3, and P1 represents the general formula (III-a), (III -b) or general formula (III-e)

で表される化合物が好ましい。更に具体的には以下に示されるような液晶化合物が例示される。

The compound represented by these is preferable. More specifically, liquid crystal compounds as shown below are exemplified.

In addition to the chiral compound as described above, the polymerizable cholesteric liquid crystal composition of the present invention may contain the following chiral compound.

(In the formula, m and n each independently represent an integer of 1 to 10, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxyl group, a carbamoyl group, cyano. A group, a nitro group, or a halogen atom, and when these groups are alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms, they are all unsubstituted or one or two When these groups are a carboxyl group or a carbamoyl group, the terminal hydrogen atom may be unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. Good.)
These chiral compounds can be used alone or in combination of two or more.

  As the polymerization initiator used in the polymerizable cholesteric liquid crystal composition of the present invention, known photopolymerization initiators used when polymerization is carried out by light irradiation can be used. For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one (“Darocur 1173” manufactured by Merck), 1-hydroxycyclohexyl phenyl ketone (“Irgacure 184” manufactured by Ciba Specialty Chemicals), 1- ( 4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one ("Darocur 1116" manufactured by Merck & Co.), 2-methyl-1-[(methylthio) phenyl] -2-morpholinopropane-1 ( “Irgacure 907” manufactured by Ciba Specialty Chemicals). Benzylmethylketal ("Irgacure 651" manufactured by Ciba Specialty Chemicals) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone ("Irgacure 369" manufactured by Ciba Specialty Chemicals) ), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (“Irgacure 379” manufactured by Ciba Specialty Chemicals), 2 , 2-dimethoxy-1,2-diphenylethane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Darocur TPO), 2,4,6-trimethylbenzoyl-diphenyl-phosphine Oxide ("Irgaku" manufactured by Ciba Specialty Chemicals) 819 "), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone (" Irgacure OXE01 "manufactured by Ciba Specialty Chemicals), 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) ("Irgacure OXE02" manufactured by Ciba Specialty Chemicals). A mixture of 2,4-diethylthioxanthone (“Kayacure DETX” manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate (“Kayacure EPA” manufactured by Nippon Kayaku Co., Ltd.) -ITX ") and a mixture of ethyl p-dimethylaminobenzoate, acylphosphine oxide (" Lucirin TPO "manufactured by BASF), and the like. The content of the photopolymerization initiator is preferably 1 to 10 mass%, particularly preferably 2 to 7 mass%. These can be used alone or in combination of two or more.

  A thermal polymerization initiator used for thermal polymerization may be added to the polymerizable cholesteric liquid crystal composition of the present invention. Examples of the thermal polymerization initiator include methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxybenzoate, and methyl ethyl ketone peroxide. Oxide, 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydroperoxide, dicumylperoxide, isobutylperoxide, di (3- Methyl peroxides such as methyl-3-methoxybutyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-Dimethylvaleronitrile ), Azonitrile compounds such as 2,2′-azobis (2-methyl-N-phenylpropion-amidin) dihydrochloride, 2,2′azobis {2-methyl-N- [1,1-bis An azoamide compound such as (hydroxymethyl) -2-hydroxyethyl] propionamide}, an alkylazo compound such as 2,2′azobis (2,4,4-trimethylpentane), or the like can be used. The content of the thermal polymerization initiator is preferably 1 to 10 mass%, particularly preferably 2 to 6 mass%. These can be used alone or in combination of two or more.

  It is preferable to add a polymerization inhibitor to the polymerizable cholesteric liquid crystal composition of the present invention. Examples of the polymerization inhibitor include phenol compounds, quinone compounds, amine compounds, thioether compounds, nitroso compounds, and the like.

Examples of phenolic compounds include p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis (4-methyl-6-t-butylphenol) 2.2′-methylenebis (4-ethyl-6-tert-butylphenol), 4.4′-thiobis (3-methyl-6-tert-butylphenol), 4-methoxy-1-naphthol, 4,4′- Dialkoxy-2,2′-bi-1-naphthol, and the like.
As quinone compounds, hydroquinone, methylhydroquinone, tert-butylhydroquinone, p-benzoquinone, methyl-p-benzoquinone, tert-butyl-p-benzoquinone, 2,5-diphenylbenzoquinone, 2-hydroxy-1,4-naphthoquinone 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone and the like.
Examples of amine compounds include p-phenylenediamine, 4-aminodiphenylamine, N.I. N'-diphenyl-p-phenylenediamine, Ni-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N.I. N′-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4.4′-dicumyl-diphenylamine, 4.4′-dioctyl-diphenylamine and the like.
Examples of thioether compounds include phenothiazine and distearyl thiodipropionate.

Examples of nitroso compounds include N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol, and N, N-dimethyl. p-nitrosoaniline, p-nitrosodiphenylamine, p-nitronedimethylamine, p-nitrone-N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso-N-n-butyl- 4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholine, N-nitroso-N-phenylhydroxylamine Ammonium salt, ditrosobenzene, 2,4.6-tri-tert-butylnitronebenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N-nitroso-N- n-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso 1-naphthol, sodium 1-nitroso-2-naphthol-3,6-sulfonate, sodium 2-nitroso-1-naphthol-4-sulfonate, Examples include 2-nitroso-5-methylaminophenol hydrochloride and 2-nitroso-5-methylaminophenol hydrochloride.

  A surfactant is preferably added to the polymerizable cholesteric liquid crystal composition of the present invention for the purpose of ensuring leveling properties of the coating film. 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 the components other than the surfactant contained in the polymerizable liquid crystal composition, the use temperature, etc., but 0.01 to 1% by mass in the polymerizable cholesteric liquid crystal composition It is preferable to contain 0.02-0.5 mass%, and it is especially preferable to contain 0.03-0.1 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 horizontal alignment additive having the repeating unit represented by the general formula (I) and the content of the surfactant is preferably 0.02 to 0.5% by mass, 0.05 to 0 It is more preferable to contain 4 mass%, and it is especially preferable to contain 0.1-0.2 mass%.
In the polymerizable cholesteric liquid crystal composition of the present invention, general-purpose additives can be used depending on the purpose. For example, additives such as thixotropic agents, surfactants, ultraviolet absorbers, infrared absorbers, antioxidants, and surface treatment agents can be added to such an extent that the liquid crystal alignment ability is not significantly reduced.

(Cholesteric reflective film)
The cholesteric reflective film of the present invention can be produced by forming the polymerizable cholesteric liquid crystal composition of the present invention on a substrate by a method such as coating and then curing. The cholesteric reflective film of the present invention is particularly preferably a cholesteric reflective film having a polarization reflection band of 250 nm or more.

  The substrate used for the cholesteric reflective film of the present invention is a substrate usually used for liquid crystal devices, displays, optical components and optical films, and when dried after application of the polymerizable liquid crystal composition of the present invention, or If it is the material which has heat resistance which can endure the heating at the time of liquid crystal device manufacture, there will be no restriction | limiting in particular. Examples of such a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a plastic substrate. In particular, when the substrate is an organic material, cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyether sulfones, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons, polystyrenes, and the like can be given. Of these, plastic substrates such as polyester, polystyrene, polyolefin, cellulose derivatives, polyarylate, and polycarbonate are preferable.

  In order to improve the applicability and adhesion of the polymerizable cholesteric liquid crystal composition of the present invention, surface treatment of these substrates may be performed. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, silane coupling treatment, and the like. In addition, in order to adjust the light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the substrate by a method such as vapor deposition, or in order to add optical added value. The material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusion film, a color filter, or the like. Among these, a pickup lens, a retardation film, a light diffusion film, and a color filter that have higher added value are preferable.

  Further, the substrate is usually subjected to an alignment treatment or an alignment film so that the polymerizable liquid crystal composition is aligned when the polymerizable liquid crystal composition of the present invention is applied and dried. It is preferable. Examples of the alignment treatment include stretching treatment, rubbing treatment, polarized ultraviolet visible light irradiation treatment, ion beam treatment, and the like. When the alignment film is used, a known and conventional alignment film is used. Such alignment films include polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyether sulfone, epoxy resin, epoxy acrylate resin, acrylic resin, coumarin compound, chalcone. Examples of the compound include compounds, cinnamate compounds, fulgide compounds, anthraquinone compounds, azo compounds, and arylethene compounds. The compound subjected to the alignment treatment by rubbing is preferably an alignment treatment or a compound in which crystallization of the material is promoted by inserting a heating step after the alignment treatment. Among the compounds that perform alignment treatment other than rubbing, it is preferable to use a photo-alignment material.

  The method for applying the polymerizable cholesteric liquid crystal composition of the present invention to a substrate includes applicator method, bar coating method, spin coating method, gravure printing method, flexographic printing method, ink jet method, die coating method, cap coating method. , Dipping and the like can be carried out by known methods. It is preferable to apply a polymerizable liquid crystal composition diluted with a solvent. The solvent to be used may be any solvent that does not dissolve the substrate or the alignment film formed on the substrate when applied on the substrate. Moreover, as a solvent to be used, a solvent that favorably dissolves the polymerizable cholesteric liquid crystal composition of the present invention is preferable. Examples of solvents that can be used include aromatic hydrocarbons such as toluene, xylene, cumene, and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketone solvents such as tetrahydrofuran, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane, anisole, amide solvents such as N, N-dimethylformamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, diethylene glycol Examples include monomethyl ether acetate, γ-butyrolactone, and chlorobenzene. These can be used alone or in combination of two or more.

The ratio of the solvent is not particularly limited as long as the polymerizable liquid crystal composition used in the present invention is usually applied by coating, so long as the applied state is not significantly impaired, but the solid content of the polymerizable liquid crystal composition and the solvent The ratio is preferably 0.1: 99.9 to 80:20, and more preferably 1:99 to 60:40 in view of coating properties. When a solvent is used, 60 to 100 ° C., more preferably 80 to 90 ° C. It is preferable to evaporate the solvent by heating at The heating time is preferably 5 seconds to 3 minutes.

The polymerization operation of the polymerizable liquid crystal composition of the present invention is generally preferably performed by light irradiation such as ultraviolet rays in a planar alignment state after removing the solvent in the polymerizable liquid crystal composition by drying or the like. When the polymerization is performed by light irradiation, specifically, it is preferable to irradiate ultraviolet light having a wavelength of 390 nm or less, and it is most preferable to irradiate light having a wavelength of 250 to 370 nm. However, when the polymerizable liquid crystal composition causes decomposition or the like due to ultraviolet light of 390 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and unpolarized light. The intensity of the ultraviolet light 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.

  In order to improve the solvent resistance and heat resistance of the obtained cholesteric reflective film, the cholesteric reflective film can be heat-treated. The heating temperature is preferably within a range not exceeding the glass transition point of the base material when an organic material is used as the base material.

Hereinafter, the present invention will be described with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” is based on mass. Moreover, the measurement of haze was performed using NDH-2000 by Nippon Denshoku Industries Co., Ltd.
Reference Example 1 Preparation of polymerizable liquid crystal cholesteric liquid crystal composition 15.18% polymerizable liquid crystal compound represented by formula (A-1), 6.50% polymerizable liquid crystal compound represented by formula (A-2), B-1) polymerizable liquid crystal compound represented by 23.85%, polymerizable liquid crystal compound represented by formula (B-2) 32.52%, polymerizable chiral compound represented by formula (C-1) 7.01%, formula 8.67% of the polymerizable liquid crystal compound represented by (D-1), 3.25% of the liquid crystal compound represented by formula (E-1), 2.17% of the photopolymerization initiator represented by formula (F-1), A polymerizable liquid crystal cholesteric liquid crystal composition (1) was obtained by mixing 0.44 parts of a photopolymerization initiator represented by F-2) and 0.44 parts of p-methoxyphenol (E-1).

Example 1
The polymerizable cholesteric liquid crystal composition (1 ′) of the present invention was prepared by adding 0.10% of polypropylene having a weight average molecular weight of 1650 as a horizontal alignment additive to the polymerizable cholesteric liquid crystal composition (1) prepared in Reference Example 1. . To this polymerizable cholesteric liquid crystal composition (1 ′), 30% toluene and 30% cyclohexanone were added to prepare a solution of the polymerizable liquid crystal composition (1 ′).

  Next, the polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. . The obtained coating film was rubbed to obtain a cholesteric reflective film substrate of the present invention. The rubbing treatment was performed using a commercially available rubbing apparatus.

Next, a solution of the polymerizable liquid crystal composition (A) was applied to the rubbed substrate by a spin coating method and dried at 65 ° C. for 3 minutes. The obtained coating film was placed on a hot plate at 60 ° C., and a 15 mW / cm ² high-pressure mercury lamp adjusted so that ultraviolet light (UV light) of only around 365 nm was obtained with a band-pass filter. Irradiated with UV light for 10 seconds at intensity. Next, the bandpass filter was removed, and UV light was irradiated for 20 seconds at an intensity of 70 mW / cm ² to obtain a cholesteric reflective film of the present invention.
The film thickness of the obtained cholesteric reflective film was 5.5 μm. When this cholesteric reflective film was observed with a polarizing microscope, alignment defects were hardly observed. Moreover, when the haze of the film was measured with a haze meter NDH2000, the haze was 8.8%.

(Example 2)
A cholesteric reflective film was obtained in the same manner except that 0.20% of polypropylene was added in Example 1.
The film thickness of the obtained cholesteric reflective film was 5.5 μm. When this cholesteric reflective film was observed with a polarizing microscope, alignment defects were hardly observed. Moreover, when the haze of the film was measured, the haze was 4.8%.

(Example 3)
A cholesteric reflective film was obtained in the same manner as in Example 1, except that 0.1% of polypropylene having a mass average molecular weight of 2119 was added. The film thickness of the obtained cholesteric reflective film was 5.5 μm. When this cholesteric reflective film was observed with a polarizing microscope, alignment defects were hardly observed. Moreover, when the haze of the film was measured, the haze was 5.6%.

(Comparative Example 1)
To the polymerizable cholesteric liquid crystal composition (1) prepared in Reference Example 1, 30% toluene and 30% cyclohexanone were added to prepare a polymerizable liquid crystal composition (1) solution.
Next, the polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm using a spin coating method, dried at 100 ° C. for 10 minutes, and then baked at 200 ° C. for 60 minutes to obtain a coating film. . The obtained coating film was rubbed to obtain a cholesteric reflective film substrate of the present invention. The rubbing treatment was performed using a commercially available rubbing apparatus.

Next, a solution of the polymerizable liquid crystal composition (1 ′) was applied to the rubbed substrate by a spin coating method and dried at 65 ° C. for 3 minutes. The obtained coating film was placed on a hot plate at 60 ° C., and a 15 mW / cm ² high-pressure mercury lamp adjusted so that ultraviolet light (UV light) of only around 365 nm was obtained with a band-pass filter. Irradiated with UV light for 10 seconds at intensity. Next, the bandpass filter was removed, and UV light was irradiated for 20 seconds at an intensity of 70 mW / cm ² to obtain a cholesteric reflective film of the present invention.
The film thickness of the obtained cholesteric reflective film was 5.5 μm. When this cholesteric reflective film was observed with a polarizing microscope, it was found that a large number of orientation defects were observed and almost no horizontal orientation was observed. Moreover, when the haze of the film was measured with a haze meter NDH2000, the haze was 83.1%.

(Comparative Example 2)
A cholesteric reflective film was obtained in the same manner as in Example 1 except that 0.1% of polypropylene having a mass average molecular weight of 878 was added. The film thickness of the obtained cholesteric reflective film was 5.5 μm. When this cholesteric reflective film was observed with a polarizing microscope, many alignment defects were observed. Moreover, when the haze of the film was measured, the haze was 21.8%.

(Comparative Example 3)
A cholesteric reflective film was obtained in the same manner as in Example 1 except that 0.2% of polypropylene having a weight average molecular weight of 878 was added. The film thickness of the obtained cholesteric reflective film was 5.5 μm. When this cholesteric reflective film was observed with a polarizing microscope, alignment defects were observed. Moreover, when the haze of the film was measured, the haze was 10.2%.

(Comparative Example 4)
A cholesteric reflective film was obtained in the same manner as in Example 1, except that 0.1% of polyethylene having a mass average molecular weight of 1660 was added instead of polypropylene. The film thickness of the obtained cholesteric reflective film was 5.5 μm. When this cholesteric reflective film was observed with a polarizing microscope, many alignment defects were observed. Moreover, when the haze of the film was measured, the haze was 38.6%.

(Comparative Example 5)
A cholesteric reflective film was obtained in the same manner as in Example 1, except that 0.2% of polyethylene having a mass average molecular weight of 1660 was added instead of polypropylene. The film thickness of the obtained cholesteric reflective film was 5.5 μm. When this cholesteric reflective film was observed with a polarizing microscope, it was found that a large number of orientation defects were observed and almost no horizontal orientation was observed. Moreover, when the haze of the film was measured, the haze was 60.4%.

  The above results are summarized in Table 1. From these results, it can be seen that when the polymerizable cholesteric liquid crystal composition of the present invention is used, a high-quality cholesteric reflective film with small light scattering (haze) can be produced.

  Alignment defect criteria (○: almost none, Δ: some, ×: many, ×: very many)

Claims (7)

Polymerizable liquid crystal material, chiral material, photopolymerization initiator, and general formula (I)

(Wherein R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms) and a mass average molecular weight having a repeating unit represented by 1300 A polymerizable cholesteric liquid crystal composition comprising a compound of 2180 or less. The polymerizable cholesteric liquid crystal composition according to claim 1, wherein the concentration of the compound represented by the general formula (I) is 0.05 to 1.0% by mass. Formula (II)

(In the formula, P represents a reactive functional group, Sp represents a spacer group independently, i, represents 0 or 1, MG represents a mesogenic group or a mesogenic support group, R represents a terminal group, Or a polymerizable cholesteric liquid crystal composition according to claim 1, which contains a compound represented by the same meaning as — (Sp) iP group ”. In the general formula (II), Sp represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be substituted by one or more halogen atoms or CN, and one CH present in the group _Two groups or two or more non-adjacent CH ₂ groups are each independently independent 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-, and MG is represented by the general formula (II-b)

(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, R represents a hydrogen atom, a halogen atom, a cyano group or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group is 1 May be substituted by one or more halogen atoms or CN, The two or more CH ₂ groups not one CH ₂ group or adjacent present in groups independently of one another each in the form of oxygen atoms are not directly bonded to each other, -O -, - S-, Replaced by -NH-, -N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS-, -C = C- or -C≡C- And P represents a general formula (II-c), (II-d), or a general formula (II-e)

(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 k is 0 or 1) The polymerizable cholesteric liquid crystal composition according to claim 3, which represents a substituent represented by: Chiral materials are represented by the general formula (III)

(In the general formula (III), Sp represents an alkylene group having 1 to 20 carbon atoms, and the alkylene group may be substituted by one or more halogen atoms or CN. A CH ₂ group or two or more non-adjacent CH ₂ groups are each independently independent of each other in a form in which oxygen atoms are not directly bonded to each other, such as —O—, —S—, —NH—, —N (CH ₃ )-, -CO-, -COO-, -OCO-, -OCOO-, -SCO-, -COS- or -C≡C- may be substituted, A4 is a 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-tetrahydronaphtha 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 are one or more F, Cl, CF ₃ , OCF ₃ , cyano group, C 1-8 alkyl group, alkoxy group, alkanoyl group, alkanoyloxy group as substituents , an alkenyl group having 2 to 8 carbon atoms, alkenyloxy group which may have a alkenoyl group or alkenoyloxy group, Z4 is, -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, m represents 0, 1, 2 or 3, and P1 represents the general formula (III-a), (III -b) or general formula (III-e)

The polymerizable cholesteric liquid crystal composition according to claim 1, wherein The photopolymerization initiator is 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[(methylthio) phenyl] -2-morpholinopropane, Benzylmethylketal, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinline-4 -Yl-phenyl) butan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6 -A compound selected from the group consisting of trimethylbenzoyl-diphenyl-phosphine oxide and 1,2-octanedione Claim 1 polymerizable cholesteric liquid crystal composition. A cholesteric reflective film, which is a cured product of the polymerizable cholesteric liquid crystal composition according to claim 1.