JP2013166883A - Polymerizable cholesteric liquid crystal composition and thin film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable cholesteric liquid crystal composition that has good adhesion to a substrate, can realize a thin film having low haze and no unevenness, and has an excellent appearance using the polymerizable cholesteric liquid crystal composition Provide a thin film.
SOLUTION: A compound having two specific polymerizable functional groups as a first component, a polymerizable liquid crystal compound having one specific polymerizable functional group as a second component, a chiral compound as a third component, A polymerizable cholesteric liquid crystal composition containing a photopolymerization initiator as the fourth component, a specific chain transfer agent as the fifth component, and an additive for reducing the tilt angle of the liquid crystal compound at the air interface as the sixth component, and A thin film comprising a composition as a constituent member.
[Selection figure] None

Description

The present invention relates to a polymerizable cholesteric liquid crystal composition and a thin film using the same.

In recent years, development of polarizing plates, retardation plates and the like using a polymerizable liquid crystal material has been actively conducted. These can be obtained by applying a solution containing a polymerizable liquid crystal material to a rubbing-treated substrate, drying the solvent, and then polymerizing with ultraviolet rays or heat. In addition, it is also known that when a chiral compound is added to a polymerizable liquid crystal material to obtain a polymerizable cholesteric liquid crystal material, a circularly polarized light separating element can be obtained by the same method. Has been.
When applying a polymerizable cholesteric liquid crystal material to a brightness enhancement film, etc., it is required to have high-band reflection wavelength characteristics and high reflection brightness, as well as uniformity in brightness, low haze, and good adhesion to a substrate. . High reflection luminance can be realized with a material having a large Δn, and high-band reflection wavelength characteristics can be realized by using a method of combining compounds having different reactivities as seen in Patent Document 1.

  However, it has been difficult to achieve both brightness uniformity, low haze, and good adhesion. Regarding adhesion, Patent Document 2 discloses a method using an oxime ester photopolymerization initiator, Patent Document 3 includes a method containing a polymerizable phosphorus compound, and Patent Document 4 includes a silane coupling agent containing an amino group. However, the methods of Patent Document 2 and Patent Document 3 are still insufficient in adhesion, and the method of Patent Document 4 does not provide a non-liquid crystalline compound. There was a problem that the transition point (Tni) of the liquid crystal was lowered due to the addition amount being too large. The temperature for drying the solvent is not higher than Tni of the polymerizable liquid crystal composition, but it is essential for uniformity of brightness, low haze, and avoiding uneven phenomenon, but it is sufficiently high when Tni is low. Since the drying temperature condition cannot be set, the volatilization rate of the solvent becomes slow and unevenness tends to occur. As a technique for increasing the adhesion of the polymerization composition to the substrate, a technique using thiol is known as in Patent Document 5. This technique is effective to some extent as long as it is a uniaxially oriented polymerizable composition that does not require orientation control or a polymerizable liquid crystal composition that requires orientation control, but it is difficult for a polymerizable cholesteric liquid crystal composition. there were. Uniaxial orientation can maintain the orientation of the entire film if a certain degree of orientation is obtained. However, in the case of a cholesteric liquid crystal composition, slight misalignment causes haze and luminance nonuniformity. This is because it will increase.

  As described above, in a thin film using a polymerizable cholesteric liquid crystal composition, it has been difficult to achieve both low haze and no unevenness and good adhesion.

JP-A-6-281814 JP 2010-152217 A JP 2008-250108 A JP 2007-332270 A JP 2008-163094 A

  The problem to be solved by the present invention is to provide a polymerizable cholesteric liquid crystal composition capable of realizing a thin film having good adhesion to a substrate, low haze and no unevenness, and also the polymerizable cholesteric liquid crystal composition. An object of the present invention is to provide a thin film having an excellent external appearance.

As a result of studying combinations of various compounds in order to solve the above problems, the present invention has solved the problems.
That is, it contains at least one compound represented by the general formula (1) as the first component,

(Wherein P ¹ and P ² each independently represent an acrylate group or a methacrylate group,
E ¹ and E ² each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or two or more methylene groups present in the alkylene group have an oxygen atom mutually As those not directly bonded, they may be substituted with an oxygen atom, —CO—, —OCO—, —COO—, or —CH═CH—, and A ¹ , A ² and A ³ are each independently 1 , 4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, decahydronaphthalene -2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2,5-diyl group or 1,3-dioxane- Represents a 2,5-diyl group These groups may be unsubstituted, fluorine atom, chlorine atom, cyano group, nitro group, alkyl group having 1 to 7 carbon atoms, alkoxy group having 1 to 7 carbon atoms, or 1 to carbon atoms. 7 alkyl groups, alkoxy groups or alkanoyl groups, one or more hydrogen atoms may be replaced by fluorine atoms or chlorine atoms,
Z ¹ and Z ² are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—S—, —S—CO—, —CO—NH—, —NH _{-CO -, - SCH 2 -,} - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH 2 CF 2 - _{, -CF 2 CH 2 -, -} CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO- _{CH 2 CH 2 -, - OCO} -CH 2 CH 2 -, - CH 2 CH 2 -OCO -, - CH 2 CH 2 -COO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 It represents —OCO—, —CH ₂ —COO—, —CH═CH—, —C≡C—, or a single bond. )
Containing at least one compound of the general formula (2) as the second component,

(Wherein P ³ represents an acrylate group or a methacrylate group,
E ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more methylene groups present in the alkylene group are oxygen atoms on the assumption that oxygen atoms are not directly bonded to each other. Optionally substituted with an atom, -CO-, -OCO-, -COO-, or -CH = CH-,
A ⁴ , A ⁵ and A ⁶ are each independently 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4 -Bicyclo [2.2.2] octylene group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, It represents a pyrimidine-2,5-diyl group or a 1,3-dioxane-2,5-diyl group, but these groups may be unsubstituted, fluorine atom, chlorine atom, cyano group, nitro group, carbon It may be substituted by an alkyl group having 1 to 7 atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkanoyl group having 1 to 7 carbon atoms. One or more of these alkyl groups, alkoxy groups or alkanoyl groups may be substituted May be replaced by a fluorine atom or a chlorine atom,
Z ³ and Z ⁴ are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—S—, —S—CO—, —CO—NH—, —NH. _{-CO -, - SCH 2 -,} - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH 2 CF 2 - _{, -CF 2 CH 2 -, -} CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO- _{CH 2 CH 2 -, - OCO} -CH 2 CH 2 -, - CH 2 CH 2 -OCO -, - CH 2 CH 2 -COO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 _{-OCO -, - CH 2 -COO -} , - CH = CH -, - C≡C-, or a single bond,
R ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group or an alkyl group having 1 to 15 carbon atoms, one methylene group in the alkyl group, or two or more methylene groups not adjacent to each other Each independently represents an oxygen atom, a sulfur atom, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-,- May be replaced by NH—CO—, —CH═CH—, —CH═CF—, —CF═CH— or —C≡C—,
n represents 0 or 1. )
As a third component, at least one kind of chiral compound is contained,
As the fourth component, at least one polymerization initiator is contained,
As a 5th component, at least 1 type of chain transfer agents represented by General formula (5) is contained, The content is 0.1-5.0 mass%,

(In the formula, A ⁷ represents a 1,4-phenylene group or a naphthalene-2,6-diyl group, and A ⁸ represents a phenyl group or a naphthyl group (the phenyl group or naphthyl group may be unsubstituted). , A fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkanoyl group having 1 to 7 carbon atoms, These alkyl groups, alkoxy groups or alkanoyl groups represent one or more hydrogen atoms may be replaced by fluorine atoms or chlorine atoms),
A ⁹ represents 1,4-phenylene group, 1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl 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 or naphthalene- Represents a 2,6-diyl group, and the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or naphthalene-2,6-diyl group is unsubstituted or Can have one or more fluorine atoms, chlorine atoms, methyl groups, methoxy groups, CF ₃ groups, or OCF ₃ groups as substituents;
G ¹ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and one or more hydrogen atoms in the alkylene group may be substituted with a methyl group, a methoxy group, an ethyl group, or an ethoxy group, One or more methylene groups in the alkylene group may be substituted with an oxygen atom, -CO-, -COO- or -OCO-,
Z ⁵ is —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—S—, —S—CO—, —CO—NH—, —NH—CO—, —SCH _{2. -, - CH 2 S -,} - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 - , —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, — OCO—CH ₂ CH ₂ —, —CH ₂ CH ₂ —OCO—, —CH ₂ CH ₂ —COO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —OCO—, —CH ₂ -COO-, -CH = CH-, -C≡C-, or a single bond,
m represents 0, 1, or 2;
R ² represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, a halogen atom, a cyano group, or an NCS group, and the alkyl group or alkenyl group is unsubstituted or 1 or 2 or more fluorine atoms, chlorine atoms, cyano groups, methyl groups, methoxy groups or CF ₃ groups can be present as substituents, and one or more groups present in the alkyl group or alkenyl group These methylene groups may be substituted with an oxygen atom, —CO—, or —COO— as those in which oxygen atoms are not directly bonded to each other. )
As a sixth component, a surfactant or a polymerizable cholesteric liquid crystal composition containing a compound having a repeating unit represented by the general formula (6) and having a weight average molecular weight of 100 or more, and the composition as a constituent member A thin film is provided.

  By using the polymerizable cholesteric liquid crystal composition of the present invention, a thin film having good adhesion to the substrate, low haze and no unevenness can be obtained.

  The polymerizable liquid crystal composition of the present invention comprises (1) a compound having two polymerizable functional groups as a first component, and (2) a polymerizable liquid crystal compound having one polymerizable functional group as a second component. 3) A chiral compound as the third component, (4) a photopolymerization initiator as the fourth component, (5) a chain transfer agent as the fifth component, and (6) a tilt of the liquid crystal compound at the air interface as the sixth component. Additives for reducing corners (7) Other additives are included as required.

(First component)
The compound having two polymerizable functional groups as the first component is a material necessary for obtaining the heat resistance, solvent resistance, etc. of the thin film because it takes a crosslinked structure after polymerization. The compound having two polymerizable functional groups is represented by the general formula (1).

(Wherein P ¹ and P ² each independently represent an acrylate group or a methacrylate group,
E ¹ and E ² each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or two or more methylene groups present in the alkylene group have an oxygen atom mutually As those not directly bonded, they may be substituted with an oxygen atom, —CO—, —OCO—, —COO—, or —CH═CH—, and A ¹ , A ² and A ³ are each independently 1 , 4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, decahydronaphthalene -2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2,5-diyl group or 1,3-dioxane- Represents a 2,5-diyl group These groups may be unsubstituted, fluorine atom, chlorine atom, cyano group, nitro group, alkyl group having 1 to 7 carbon atoms, alkoxy group having 1 to 7 carbon atoms, or 1 to carbon atoms. 7 alkyl groups, alkoxy groups or alkanoyl groups in which one or more hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, and Z ¹ and Z ² are each independently substituted. _{to, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - CO-S -, - S-CO -, - CO-NH -, - NH-CO -, - SCH 2 - _{, -CH 2 S -, - CF} 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, _{-CF 2 CF 2 -, - CH} = C -COO -, - CH = CH- OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH _{2 -OCO -, - CH 2 CH} 2 -COO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -OCO -, - CH 2 -COO -, - CH = CH -, - C ≡C— or a single bond. )
As A ¹ , A ² and A ³ , 1,4-phenylene group or naphthalene-2,6-diyl group (these groups may be unsubstituted, fluorine atom, chlorine atom, from 1 carbon atom) 3 alkyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkanoyl group having 1 to 3 carbon atoms), and any one of A ¹ , A ² and A ³ More preferably, one or two are 1,4-phenylene groups or naphthalene-2,6-diyl groups in which one hydrogen atom is substituted with a fluorine atom, a chlorine atom, a methyl group, or a methoxy group.

The Z ¹ and _{^{Z 2, -COO -, - OCO}} -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -OCO -, - CH 2 CH 2 -COO —, —CH ₂ —CH ₂ —, —CH═CH—, —C≡C—, or a single bond is preferable, and —COO— or —OCO— is more preferable.

E ¹ and E ² are each an alkylene group having 1 to 8 carbon atoms (one or two or more methylene groups present in the alkylene group are oxygen atoms, Or may be substituted with -C = C-), and an alkylene group having 3 to 6 carbon atoms (one or two or more methylene groups present in the alkylene group have oxygen atoms attached to each other). It is preferable that it is not directly bonded, and may be substituted with an oxygen atom.

Furthermore, the general formula (1-1)

(In the formula, Y ¹¹ and Y ¹² each independently represent a hydrogen atom or a methyl group; E ¹¹ and E ¹² each independently represent an alkylene group having 1 to 8 carbon atoms; One or more methylene groups present in the group are substituted with oxygen atoms, —CO—, —OCO—, —COO—, or —CH═CH—, as oxygen atoms are not directly bonded to each other. However, an alkylene group having 1 to 8 carbon atoms is preferable, an alkylene group having 3 to 6 carbon atoms is more preferable, and X ^{1 to} X ¹² are each independently a hydrogen atom, a fluorine atom, chlorine Represents an atom, a methyl group, or a methoxy group, and one of X ^{1 to} X ⁴ is a fluorine atom, a chlorine atom, a methyl group, or a methoxy group, or one of X ^{5 to} X ⁸ is a fluorine atom. , Chlorine atom, methyl group, Is preferably a methoxy group, and Z ¹¹ and Z ¹² each independently represent —COO—, —OCO—, or a single bond.

  The content of the compound having two polymerizable functional groups is preferably 5 to 30% by mass, more preferably 8 to 24% by mass, and 10 to 19% by mass. Even more preferred is 10-15% by weight.

(Second component)
The compound having one polymerizable functional group as the second component is used for adjusting various physical property values such as refractive index anisotropy, transition point, and viscosity. The compound having one polymerizable functional group is represented by the general formula (2).

(Wherein P ³ represents an acrylate group or a methacrylate group,
E ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more methylene groups present in the alkylene group are oxygen atoms on the assumption that oxygen atoms are not directly bonded to each other. ^May be substituted with an atom, —CO—, —OCO—, —COO—, or —CH═CH—, and A ⁴ , A ⁵ and A ⁶ are each independently a 1,4-phenylene group or naphthalene; -2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, decahydronaphthalene-2,6-diyl group 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group. These groups are unsubstituted Substituted by a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkanoyl group having 1 to 7 carbon atoms. In these alkyl groups, alkoxy groups or alkanoyl groups, one or more hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, and Z ³ and Z ⁴ are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—S—, —S—CO—, —CO—NH—, —NH—CO—, —SCH ₂ —, —CH ₂ S—, — _{CF 2 O -, - OCF 2} -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO-, -CH = C -OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -OCO -, - CH 2 CH ₂ —COO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —OCO—, —CH ₂ —COO—, —CH═CH—, —C≡C—, or a single bond R ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms, one methylene group in the alkyl group, or two or more non-adjacent ones Each methylene group is independently an oxygen atom, a sulfur atom, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, —O—CO—O—, —CO—NH—. , -NH-CO-, -CH = CH-, -CH = CF-, -CF = CH- or- It may be replaced by ≡C-, n represents 0 or 1. )

As A ⁴ , A ⁵ and A ⁶ , 1,4-phenylene group or naphthalene-2,6-diyl group (these groups may be unsubstituted, fluorine atom, chlorine atom, from 1 carbon atom) 3 alkyl group, an alkoxy group having 1 to 3 carbon atoms, or an alkanoyl group having 1 to 3 carbon atoms), and any one of A ⁴ , A ⁵ and A ⁶ More preferably, one or two is a 1,4-phenylene group or a naphthalene-2,6-diyl group in which one hydrogen atom is substituted with a fluorine atom, a chlorine atom, a methyl group or a methoxy group.

Z ³ and Z ⁴ include —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—, —C≡. C— or a single bond is preferable, and —COO—, —OCO—, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, or a single bond is more preferable.

E ³ represents an alkylene group having 1 to 8 carbon atoms (one or two or more methylene groups present in the alkylene group are oxygen atoms or —C ═C— may be substituted, and an alkylene group having 3 to 6 carbon atoms (one or two or more methylene groups present in the alkylene group are not directly bonded to each other by oxygen atoms). Preferred is that it may be substituted with an oxygen atom.

R ¹ represents an alkyl group having 1 to 8 carbon atoms (one methylene group in the alkyl group or two or more methylene groups not adjacent to each other independently represents an oxygen atom, —COO—, — It may be substituted with OCO-).

  n is preferably 1.

  The content of the second component is preferably 50 to 90% by mass, more preferably 60 to 85% by mass, still more preferably 65 to 83% by mass, and 70 to 80% by mass. Most preferably.

(Third component)
By adding the third component chiral compound, the liquid crystal composition has a helical structure and exhibits a function as a circularly polarized light separating element.
The chiral compound preferably has a polymerizable functional group, and the polymerizable functional group is more preferably an acrylic group or a methacryl group.
The HTP (helical twist power) is preferably 20 or more, more preferably 30 or more, and even more preferably 45 or more with respect to the composition system to be added.
Specifically, compounds of general formulas (3-1) to (3-4) are preferable.

(Wherein Y ^{71 to} Y ⁷⁷ each independently represents a hydrogen atom or a methyl group, and A ^{71 to} A ⁷⁷ each independently represents a 1,4-phenylene group, a 1,4-cyclohexylene group or 2, Represents a 6-naphthylene group, and the 1,4-phenylene group and the 2,6-naphthylene group are unsubstituted or have one or more fluorine atoms, chlorine atoms, methyl groups, methoxy groups as substituents, CF ₃ group or OCF ₃ group can be included, and Z ^{71 to} Z ⁷⁷ are each independently —COO—, —OCO—, —CH ₂ CH ₂ —, —COO—CH ₂ CH ₂ —, —OCO. _{-CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO-, or a single ^bond, E 71 ^{to E 77} are each independently a single bond, or a number of carbon atoms 1 15 alkylene groups, One or more methylene groups present in the alkylene group are oxygen atoms, —CO—, —OCO—, —COO—, or —CH═CH—, assuming that the oxygen atoms are not directly bonded to each other. may be substituted one or more hydrogen atoms present in the alkylene group may be substituted with a methyl group, n ⁷¹ ~n ⁷⁷ are each independently 0, 1, or 2 In addition, the arrangement of binaphthyl may be either R or S.)
As chiral content, 3-10 mass% is preferable, and 3-7 mass% is more preferable.

  The presence of the third component increases the viscoelasticity of the composition, and the effect of the fifth component chain transfer agent can be exhibited.

(4th component)
The polymerization initiator of the fourth component is a compound necessary for polymerizing the polymerizable liquid crystal composition of the present invention. As the polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used, but a photopolymerization initiator is preferable, and specifically, the following are preferable.
BASF Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 127, Irgacure 369, Irgacure 379, Irgacure 819, Irgacure OXE01, Irgacure OXE02, Lucyrin TPO, Darocur 1173. LAMBSON Esacure 1001M, Esacure KIP150, Speed Cure BEM, Speed Cure BMS, Speed Cure PBZ, Benzophenone.

  One kind of these polymerization initiators may be used, but two or more kinds may be used, and a sensitizer or the like may be added.

  As content of a polymerization initiator, 2-10 mass% is preferable, and 3-7 mass% is more preferable.

(5th component)
The fifth component chain transfer agent is a compound necessary for further improving the adhesion to the substrate. This chain transfer agent is represented by the general formula (5).

(In the formula, A ⁷ represents a 1,4-phenylene group or a naphthalene-2,6-diyl group,
A ⁸ is a phenyl group or a naphthyl group (the phenyl group or naphthyl group may be unsubstituted, fluorine atom, chlorine atom, cyano group, nitro group, alkyl group having 1 to 7 carbon atoms, carbon atom It may be substituted by an alkoxy group having 1 to 7 carbon atoms or an alkanoyl group having 1 to 7 carbon atoms. In these alkyl groups, alkoxy groups or alkanoyl groups, one or more hydrogen atoms are replaced by fluorine atoms or chlorine atoms. is represents also good) by, ^{a 9} is a 1,4-phenylene group, 1,4-cyclohexylene group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl 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 Represents a tetrahydronaphthalene-2,6-diyl group or naphthalene-2,6-diyl group, the 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or naphthalene-2 , 6-diyl groups can be unsubstituted or have one or more fluorine, chlorine, methyl, methoxy, CF ₃ or OCF ₃ groups as substituents, G ¹ Represents a single bond or an alkylene group having 1 to 5 carbon atoms, and one or more hydrogen atoms in the alkylene group may be substituted with a methyl group, a methoxy group, an ethyl group or an ethoxy group. One or more methylene groups therein may be substituted with an oxygen atom, —CO—, —COO— or —OCO—, and Z ⁵ represents —OCH ₂ —, —CH ₂ O—, —COO—, -OCO-,- O-S -, - S- CO -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S- _{, -SCF 2 -, - CH 2} CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO-, _{-COO-CH = CH -, -} OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -OCO -, - CH 2 CH 2 -COO _{-, - COO-CH 2 -} , - OCO-CH 2 -, - CH 2 -OCO -, - CH 2 -COO -, - CH = CH -, - C≡C-, or a single bond, m is Represents 0, 1, or 2, and R ² represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, or 2 to 15 carbon atoms. An alkenyl group, a halogen atom, a cyano group or an NCS group, wherein the alkyl group or alkenyl group is unsubstituted or has one or more fluorine atoms, chlorine atoms, cyano groups, methyl groups as substituents, it can have a methoxy group or a CF ₃ group, or two or more methylene groups present in the alkyl or alkenyl group, as the oxygen atoms are not directly bonded to each other, an oxygen atom, -CO- Or may be substituted with -COO-. )
A ⁷ is preferably a 1,4-phenylene group.

The A ^8, a phenyl group, a naphthyl group are preferred, the phenyl group is preferred. A ⁹ is a 1,4-phenylene group or a 1,4-cyclohexylene group (the 1,4-phenylene group is one or more fluorine atoms, chlorine atoms, methyl groups, methoxy groups as substituents) , CF ₃ group, or OCF ₃ group) may be preferable, and a 1,4-phenylene group is more preferable.

Z ⁵ includes a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, —CH═CH—, —C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O. - or -OCF ₂ -, more preferably a single bond, -COO- or -OCO- are more preferred.

R ² is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.

G ¹ represents a single bond or an alkylene group having 1 to 3 carbon atoms, and one or more hydrogen atoms in the alkylene group may be substituted with a methyl group, a methoxy group, an ethyl group, or an ethoxy group. Are preferably a single bond or a 1,1 dimethyl-1,2-ethylene group, more preferably a 1,1 dimethyl-1,2-ethylene group.
As m, 0 or 1 is preferable, and 0 is more preferable.

  More specifically, the compound (5-1) and / or (5-2) is preferable, and (5-2) is more preferable.

  The addition amount of the fifth component is preferably 10 to 30% by mass with respect to the initiator amount. In the polymerizable cholesteric composition, 0.2 to 3.0% by mass is preferable, and 0.3 to 2.0% by mass is more preferable.

  Since the compound of the general formula (5) has a ring structure such as a benzene ring in the molecular structure, it has an advantage of being excellent in compatibility with liquid crystal and difficult to lower liquid crystallinity. Moreover, when it wants to implement | achieve at low cost, the compound of (5-1) and (5-2) is useful.

(Sixth component)
The sixth component is a compound necessary for reducing the tilt angle of the liquid crystal compound at the air interface, and is a surfactant or a compound having a weight average molecular weight of 100 or more having a repeating unit represented by the general formula (6) Is used.

(In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one hydrogen atom in the hydrocarbon group. It may be substituted with the above halogen atoms.)
The weight average molecular weight of the compound represented by the general formula (6) is preferably 200 to 100,000, more preferably 300 to 10,000, and even more preferably 500 to 5,000.

  In addition, the surfactant and the compound having a repeating unit represented by the general formula (6) and having a weight average molecular weight of 100 or more may be used singly or in combination, or in combination.

  The addition amount of the surfactant and the compound having a repeating unit represented by formula (6) and having a weight average molecular weight of 100 or more is preferably 0.01 to 1% by mass, and 0.02 to 0. More preferably, it is 2% by mass.

(Other ingredients)
In order to improve the storage stability, it is also preferable to add a polymerization inhibitor, an antioxidant or the like. Examples of such compounds include hydroquinone derivatives, hindered phenol antioxidants, and more specifically, p-methoxyphenol, IRSF NOOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1098, IRGANOX 1135, IRGANOX 1330, IRGANOX 1425, and IRGANOX 1520 from BASF. IRGANOX 1726, IRGANOX 245, IRGANOX 259, IRGANOX 3114, IRGANOX 3790, IRGANOX 5057, IRGANOX 565, and the like.

  As addition amount of a polymerization inhibitor and antioxidant, it is preferable that it is 0.01-1.0 mass%, and it is more preferable that it is 0.05-0.2 mass%.

  Furthermore, in order to adjust the physical properties, it is also possible to add a non-polymerizable liquid crystal compound or a non-liquid crystalline polymerizable compound as necessary. The addition amount of these compounds is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

  The polymerizable liquid crystal composition of the present invention is usually used in a form dissolved in a solvent. Although there is no limitation in particular as a solvent used, The solvent in which a polymeric liquid crystal compound shows favorable solubility is preferable, and it is preferable that it is a solvent which can be dried at the temperature of 100 degrees C or less. Examples of such solvents 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, cyclohexanone, cyclohexane, and the like. Ketone solvents such as pentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate , Diethylene glycol monomethyl ether acetate, γ-butyrolactone, chlorobenzene and the like. 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, as long as the applied state is not significantly impaired, but the solid content of the polymerizable liquid crystal composition is 10 to 10. It is preferably 60% by mass, and more preferably 20-50% by mass.

(Preparation of thin film)
Next, a method for producing a thin film using the polymerizable liquid crystal composition of the present invention will be described. Usually, the polymerizable liquid crystal composition of the present invention is used in the form of a solution dissolved in a solvent. The thin film of the present invention is obtained by applying the solution to a substrate or the like and then drying and polymerizing with ultraviolet rays or the like. .
The substrate on which the solution containing the polymerizable liquid crystal composition of the present invention is applied is a substrate that is usually used for liquid crystal devices, displays, optical components and optical films, and after the application of the polymerizable liquid crystal composition of the present invention. There is no particular limitation as long as it is a material having heat resistance that can withstand heating during the drying of the liquid crystal or during the manufacture of the liquid crystal device. 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, polyolefin, polyester, polyethylene terephthalate, polycarbonate, polyacrylate, polyarylate, polyethersulfone, polyimide, polyphenylene sulfide, polyphenylene ether, nylon, polystyrene, or the like can be given. Further, in order to add an optical added value, the base 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. Further, the substrate may be subjected to an alignment treatment so that the polymerizable liquid crystal composition is easily aligned when the polymerizable liquid crystal composition of the present invention is applied and dried.
Examples of the coating method for obtaining the thin film of the present invention include an applicator method, a bar coating method, a spin coating method, a gravure printing method, a flexographic printing method, an ink jet method, a die coating method, a cap coating method, and a dipping method. It can be performed. Further, after the application, a drying process is performed to remove the solvent. The drying treatment temperature is preferably a temperature not higher than the transition point of the polymerizable liquid crystal composition and, if the substrate is an organic material, not higher than the glass transition temperature of the substrate.

  The dried thin film is usually polymerized by ultraviolet rays, whereby the orientation state is fixed. In order to obtain a high-band reflection wavelength characteristic, an appropriate heat treatment and an appropriate ultraviolet irradiation amount may be selected in the ultraviolet polymerization process, or a plurality of conditions may be appropriately combined.

  Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, “part” and “%” are based on mass.

The polymerizable liquid crystal compositions shown in Examples and Comparative Examples were charged into sample bottles at the ratios shown in the examples, and 1.5 times the amount of cyclohexanone by mass relative to the solid content of the polymerizable cholesteric liquid crystal composition. And heated and stirred with a hot stirrer at 80 to 100 ° C. for 15 minutes to obtain a transparent and uniform solution. Next, an appropriate amount of a polymerizable liquid crystal composition solution was applied to an A4 size PET film subjected to rubbing treatment, and applied onto the PET film with a bar coater (No. 9). The PET film coated with the solution is allowed to stand in a constant temperature layer at 100 ° C. for 3 minutes, and after removing the solvent by drying, the UV irradiation of the conveyor type UV irradiation is performed with the PET film set to 450 mJ / cm ^2. The thin film having a selective reflection wavelength in the visible light region was obtained by putting it into the apparatus and curing the polymerizable liquid crystal composition.

For haze, the obtained thin film was measured at three points using a haze meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd., and the average value was evaluated. Unevenness was observed visually. The transition point was measured using a temperature control system FP-80 and hot stage FP82 manufactured by METTLER TOLEDO, using the polymerizable composition before UV curing. The cross cut test was performed by a method according to the old JIS standard K5400.
The compounds used are represented by the following abbreviations.

The following compounds were used as additives.
Examples of the chain transfer agent include 1,1-diphenylethylene manufactured by Tokyo Chemical Industry Co., Ltd. represented by the formula (5-1), and alphamethylstyrene dimer (AMSD) manufactured by Goi Kasei Co., Ltd. represented by the formula (5-2). ), SC Organic Chemical Co., Ltd. 3-mercaptopropionate (TMMP), a compound represented by formula (5-3) was used. As a photopolymerization initiator, Irgacure 907 (Irg. 907) manufactured by BASF was used. As the polymerization inhibitor, p-methoxyphenol (MEHQ) manufactured by Wako Pure Chemical Industries, Ltd. was used. As the compound for reducing the tilt angle of the liquid crystal compound at the air interface, polypropylene (PP) having a weight average molecular weight of 2000 was used.

Example 1
9.0% of the polymerizable liquid crystal compound (A) as the first component, 4.0% of (B), 62.0% of the polymerizable liquid crystal compound (C) as the second component, and 14 of (D). 0.0%, chiral compound (J) as the third component 4.8%, polymerization initiator Irgacure 907 as the fourth component 5.0%, chain transfer agent AMSD as the fifth component 1.0% Then, 0.1% of PP as the sixth component and 0.1% of MEHQ as the other components were mixed, and a thin film was obtained by the method described above. The haze of this thin film was as low as 1.8%, there was no unevenness, and all 100 squares remained in the cross cut test.

(Example 2)
9.0% of the polymerizable liquid crystal compound (A) as the first component, 4.0% of (B), 62.5% of the polymerizable liquid crystal compound (C) as the second component, and 14 of (D). 0.0%, chiral compound (K) as the third component 4.3%, polymerization initiator Irgacure 907 as the fourth component 5.0%, chain transfer agent AMSD as the fifth component 1.0% Then, 0.1% of PP as the sixth component and 0.1% of MEHQ as the other components were mixed, and a thin film was obtained by the method described above. The haze of this thin film was as low as 1.8%, there was no unevenness, and all 100 squares remained in the cross cut test.

(Example 3)
The polymerizable liquid crystal compound (A) as the first component is 9.0%, (B) is 4.0%, the polymerizable liquid crystal compound (C) as the second component is 62.8%, and (D) is 14%. 0.0%, chiral compound (L), the third component, 4.0%, polymerization initiator Irgacure 907, the fourth component, 5.0%, chain transfer agent AMSD, the fifth component, 1.0% Then, 0.1% of PP as the sixth component and 0.1% of MEHQ as the other components were mixed, and a thin film was obtained by the method described above. The haze of this thin film was as low as 2.1%, there was no unevenness, and all 100 squares remained in the cross cut test.

Example 4
The first component polymerizable liquid crystal compound (A) is 8.0%, (B) is 3.5%, the second component polymerizable liquid crystal compound (D) is 24.0%, and (E) is 26%. 0.0%, (F) 27.0%, third component chiral compound (J) 5.3%, fourth component polymerization initiator Irgacure 907 5.0%, fifth component The chain transfer agent AMSD was mixed at 1.0%, PP as the sixth component was mixed at 0.1%, and MEHQ was mixed at 0.1% as the other components, and a thin film was obtained by the method described above. The haze of this thin film was as low as 1.9%, there was no unevenness, and 100 squares remained even in the cross cut test.

(Example 5)
The first component polymerizable liquid crystal compound (A) is 8.0%, (B) is 3.5%, the second component polymerizable liquid crystal compound (E) is 26.0%, and (F) is 27%. 0.0%, (G) 24.0%, third compound chiral compound (J) 5.3%, fourth component polymerization initiator Irgacure 907 5.0%, fifth component The chain transfer agent AMSD was mixed at 1.0%, PP as the sixth component was mixed at 0.1%, and MEHQ was mixed at 0.1% as the other components, and a thin film was obtained by the method described above. The haze of this thin film was as low as 1.8%, there was no unevenness, and all 100 squares remained in the cross cut test.

(Example 6)
The first component polymerizable liquid crystal compound (A) is 8.0%, (B) is 3.5%, the second component polymerizable liquid crystal compound (D) is 24.0%, and (E) is 26%. 0.0%, (H) 27.0%, third component chiral compound (J) 5.3%, fourth component polymerization initiator Irgacure 907 5.0%, fifth component The chain transfer agent AMSD was mixed at 1.0%, PP as the sixth component was mixed at 0.1%, and MEHQ was mixed at 0.1% as the other components, and a thin film was obtained by the method described above. The haze of this thin film was as low as 2.1%, there was no unevenness, and all 100 squares remained in the cross cut test.

(Example 7)
The first component polymerizable liquid crystal compound (A) is 8.0%, (B) is 3.5%, the second component polymerizable liquid crystal compound (D) is 33.0%, and (E) is 26%. 0.0%, (I) 18.0%, third component chiral compound (J) 5.3%, fourth component polymerization initiator Irgacure 907 5.0%, fifth component The chain transfer agent AMSD was mixed at 1.0%, PP as the sixth component was mixed at 0.1%, and MEHQ was mixed at 0.1% as the other components, and a thin film was obtained by the method described above. The haze of this thin film was as low as 2.0%, there was no unevenness, and all 100 squares remained in the cross cut test.

(Example 8)
The first component polymerizable liquid crystal compound (A) is 8.0%, (B) is 3.5%, the second component polymerizable liquid crystal compound (E) is 26.0%, and (F) is 27%. 0.0%, (G) 24.0%, third compound chiral compound (J) 5.3%, fourth component polymerization initiator Irgacure 907 5.0%, fifth component The chain transfer agent 1,1-diphenylethylene was mixed with 1.0%, PP as the sixth component was mixed with 0.1%, and MEHQ was mixed with 0.1% as the other components, and a thin film was obtained by the method described above. . The thin film had a low haze of 1.8%, no unevenness, and 70 squares remained in the cross cut test.

Example 9
The first component polymerizable liquid crystal compound (A) is 8.0%, (B) is 3.5%, the second component polymerizable liquid crystal compound (E) is 26.0%, and (F) is 27%. 0.0%, (G) 24.0%, third compound chiral compound (J) 5.3%, fourth component polymerization initiator Irgacure 907 5.0%, fifth component The compound (5-3) was mixed with 1.0%, PP as the sixth component was mixed with 0.1%, and MEHQ was mixed with 0.1% of the other components, and a thin film was obtained by the method described above. The thin film had a low haze of 1.8%, no unevenness, and 50 squares remained in the cross cut test.

(Example 10)
9.0% of the polymerizable liquid crystal compound (A) as the first component, 4.0% of (B), 61.0% of the polymerizable liquid crystal compound (C) as the second component, and 13 of (D). 0.0%, chiral compound (J), the third component, 4.8%, polymerization initiator Irgacure 907, the fourth component, 5.0%, chain transfer agent AMSD, the fifth component, 3.0% Then, 0.1% of PP as the sixth component and 0.1% of MEHQ as the other components were mixed, and a thin film was obtained by the method described above. The thin film had a low haze of 1.9%, no unevenness, and 90 squares remained in the cross cut test.

(Example 11)
The first component polymerizable liquid crystal compound (A) is 8.5%, (B) is 3.5%, the second component polymerizable liquid crystal compound (C) is 60.5%, and (D) is 12%. 0.5%, chiral compound (J) as the third component 4.8%, polymerization initiator Irgacure 907 as the fourth component 5.0%, chain transfer agent AMSD as the fifth component 5.0% Then, 0.1% of PP as the sixth component and 0.1% of MEHQ as the other components were mixed, and a thin film was obtained by the method described above. The haze of this thin film was as low as 2.0%, there was no unevenness, and 80 squares remained in the cross cut test.

(Comparative Example 1)
The polymerizable liquid crystal compound (A) as the first component is 9.0%, (B) is 4.0%, the polymerizable liquid crystal compound (C) as the second component is 63.0%, and (D) is 14%. 0.0%, chiral compound (J) as the third component 4.8%, polymerization initiator Irgacure 907 as the fourth component 5.0%, PP as the sixth component without adding the fifth component And 0.1% of MEHQ as other components were mixed, and a thin film was obtained by the method described above. The haze of this thin film was as low as 1.8% and there was no unevenness, but neither 0 square nor 1 square remained in the cross cut test.

(Comparative Example 2)
9.0% of the polymerizable liquid crystal compound (A) as the first component, 4.0% of (B), 62.0% of the polymerizable liquid crystal compound (C) as the second component, and 14 of (D). 0.0%, chiral compound (J) as the third component 4.8%, polymerization initiator Irgacure 907 as the fourth component 5.0%, chain transfer agent TMMP as the fifth component 1.0% Then, 0.1% of PP as the sixth component and 0.1% of MEHQ as the other components were mixed, and a thin film was obtained by the method described above. The haze of this thin film was as low as 2.5% and there was no unevenness, but neither 0 square nor 1 square remained in the cross cut test.

(Comparative Example 3)
9.0% of the polymerizable liquid crystal compound (A) as the first component, 4.0% of (B), 61.0% of the polymerizable liquid crystal compound (C) as the second component, and 13 of (D). 0.0%, chiral compound (J) as the third component 4.8%, polymerization initiator Irgacure 907 as the fourth component 5.0%, chain transfer agent TMMP as the fifth component 3.0% Then, 0.1% of PP as the sixth component and 0.1% of MEHQ as the other components were mixed, and a thin film was obtained by the method described above. The thin film had a high haze of 42.0%, resulting in severe unevenness. In the crosscut test, a total of 100 squares remained.
When the drying temperature of this composition was lowered to 90 ° C., the haze was as low as 4.5%, but severe unevenness did not disappear. In the crosscut test, a total of 100 squares remained.

(Comparative Example 4)
9.5% of the polymerizable liquid crystal compound (A) as the first component, 4.5% of (B), 65.8% of the polymerizable liquid crystal compound (C) as the second component, and 14 of (D). 0.0%, without addition of chiral compound as third component, 5.0% of polymerization initiator Irgacure 907 as fourth component, 1.0% of chain transfer agent AMSD as fifth component, sixth component PP 0.1% and MEHQ 0.1% as other components were mixed, and a thin film was obtained by the method described above. Although the haze of this thin film was as low as 1.7% and there was no unevenness, 0 square and 1 square did not remain in the cross cut test.

  The above results are summarized in Tables 1-3. The table also lists Tni as another physical property. The cross cut test indicates the number of remaining squares in 100 squares.

  In comparison between Example 1 and Comparative Examples 1, 2, and 3, good adhesion is obtained with a film obtained from a polymerizable liquid crystal composition that does not use the compound represented by the general formula (5) as the fifth component chain transfer agent. It can be seen that it is impossible to achieve both the properties and the low haze and non-uniformity. Comparative Example 3 succeeded in improving the adhesion by increasing the amount of chain transfer agent TMMP added, but the decrease in Tni due to this TMMP was large, Tni was 94 ° C and the drying temperature was 100 ° C. It was lower, haze was high, and intense unevenness occurred. Thus, a compound having a skeleton greatly different from the liquid crystal structure greatly reduces liquid crystallinity. The drying temperature was 90 ° C., which was equal to or lower than Tni, but in this case, the drying speed was slow and unevenness occurred. However, in Example 10 in which TMMP of Comparative Example 3 was changed to AMSD, Tni was not decreased by 106 ° C. due to addition, and Tni was 105 ° C. in Example 11 in which 5% by mass of AMSD was further added. The haze was as low as 1.9% in Example 10 and 2.0% in Example 11, and there was no occurrence of unevenness. Comparison between Example 1 and Comparative Example 4 shows that the effect can be obtained with a composition containing the third component chiral compound. It turns out that an effect is acquired even if it changes a liquid crystalline compound and a chain transfer agent in Examples 1-9.

Claims (7)

Containing at least one compound represented by the general formula (1) as the first component,

(Wherein P ¹ and P ² each independently represent an acrylate group or a methacrylate group,
E ¹ and E ² each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or two or more methylene groups present in the alkylene group have an oxygen atom mutually As those not directly bonded, they may be substituted with an oxygen atom, —CO—, —OCO—, —COO—, or —CH═CH—, and A ¹ , A ² and A ³ are each independently 1 , 4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, decahydronaphthalene -2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2,5-diyl group or 1,3-dioxane- Represents a 2,5-diyl group These groups may be unsubstituted, fluorine atom, chlorine atom, cyano group, nitro group, alkyl group having 1 to 7 carbon atoms, alkoxy group having 1 to 7 carbon atoms, or 1 to carbon atoms. 7 alkyl groups, alkoxy groups or alkanoyl groups in which one or more hydrogen atoms may be replaced by fluorine atoms or chlorine atoms, and Z ¹ and Z ² are each independently substituted. _{to, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - CO-S -, - S-CO -, - CO-NH -, - NH-CO -, - SCH 2 - _{, -CH 2 S -, - CF} 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CH 2 -, _{-CF 2 CF 2 -, - CH} = C -COO -, - CH = CH- OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH _{2 -OCO -, - CH 2 CH} 2 -COO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -OCO -, - CH 2 -COO -, - CH = CH -, - C ≡C— or a single bond. )
Containing at least one compound of the general formula (2) as the second component,

(Wherein P ³ represents an acrylate group or a methacrylate group, E ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or two or more present in the alkylene group) The methylene group may be substituted with an oxygen atom, —CO—, —OCO—, —COO—, or —CH═CH—, assuming that oxygen atoms are not directly bonded to each other, and A ⁴ , A ⁵ And A ⁶ are each independently 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2. 2.2] Octylene group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, pyridine-2,6-diyl group, pyrimidine-2,5 -Diyl group or 1,3 Although it represents a dioxane-2,5-diyl group, these groups may be unsubstituted, fluorine atom, chlorine atom, cyano group, nitro group, alkyl group having 1 to 7 carbon atoms, carbon atom number 1 May be substituted by an alkoxy group having 1 to 7 carbon atoms or an alkanoyl group having 1 to 7 carbon atoms, and these alkyl groups, alkoxy groups or alkanoyl groups may have one or more hydrogen atoms replaced by fluorine atoms or chlorine atoms. Z ³ and Z ⁴ are each independently —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CO—S—, —S—CO—, —CO—NH—. , —NH—CO—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH ₂ CH ₂ —, —CH _{2 CF 2 -, - CF 2 CH} 2 _{-, - CF 2 CF 2 -} , - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, _{-OCO-CH 2 CH 2 -,} - CH 2 CH 2 -OCO -, - CH 2 CH 2 -COO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -OCO -, - CH ₂ —COO—, —CH═CH—, —C≡C—, or a single bond, and R ¹ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, or an alkyl group having 1 to 15 carbon atoms. , One methylene group in the alkyl group, or two or more methylene groups that are not adjacent to each other independently represent an oxygen atom, a sulfur atom, -CO-, -COO-, -OCO-, -CO-S. -, -S-CO-, -O-CO-O-, -CO-NH-, -NH CO -, - CH = CH -, - CH = CF -, - CF = CH- or may be replaced by -C≡C-, n represents 0 or 1. )
As a third component, at least one kind of chiral compound is contained,
As the fourth component, at least one polymerization initiator is contained,
As a 5th component, 0.1-5.0 mass% of chain transfer agents represented by General formula (5) are contained,

(In the formula, A ⁷ represents a 1,4-phenylene group or a naphthalene-2,6-diyl group, and A ⁸ represents a phenyl group or a naphthyl group (the phenyl group or naphthyl group may be unsubstituted). , A fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkanoyl group having 1 to 7 carbon atoms, These alkyl groups, alkoxy groups or alkanoyl groups represent one or more hydrogen atoms may be replaced by fluorine atoms or chlorine atoms), and A ⁹ is a 1,4-phenylene group, 1,4-cyclohexylene Group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, decahydronaphthalene-2.6-diyl group, pyridine-2,5-diyl group Represents a pyrimidine-2,5-diyl group, a pyrazine-2.5-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or a naphthalene-2,6-diyl group; 4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or naphthalene-2,6-diyl group is unsubstituted or has one or more fluorine atoms as substituents , A chlorine atom, a methyl group, a methoxy group, a CF ₃ group, or an OCF ₃ group, G ¹ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and one of the alkylene groups The above hydrogen atoms may be substituted with a methyl group, a methoxy group, an ethyl group or an ethoxy group, and one or more methylene groups in the alkylene group may be an oxygen atom, —CO—, —COO— or —OCO—. Replaced by At ^{best, Z} 5 _{is, -OCH 2 -, - CH 2} O -, - COO -, - OCO -, - CO-S -, - S-CO -, - CO-NH -, - NH-CO- , —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ —, —CH ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH _{2 -, - OCO-CH 2} CH 2 -, - CH 2 CH 2 -OCO -, - CH 2 CH 2 -COO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -OCO- , —CH ₂ —COO—, —CH═CH—, —C≡C—, or a single bond, and m is 0, 1, or 2 and R ² represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, a halogen atom, a cyano group, or an NCS group, and the alkyl group or alkenyl group is unsubstituted. Or one or two or more fluorine atoms, chlorine atoms, cyano groups, methyl groups, methoxy groups or CF ₃ groups as a substituent, and one which is present in the alkyl group or alkenyl group Alternatively, two or more methylene groups may be substituted with an oxygen atom, —CO—, or —COO— as those in which oxygen atoms are not directly bonded to each other. )
A polymerizable cholesteric liquid crystal composition containing, as a sixth component, a surfactant or a compound having a repeating unit represented by the general formula (6) and having a weight average molecular weight of 100 or more.

(In the formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one hydrogen atom in the hydrocarbon group. It may be substituted with the above halogen atoms.) The polymerizable cholesteric liquid crystal composition according to claim 1, wherein the content of the compound represented by the general formula (1) of the first component is 5 to 30% by mass. The polymerizable cholesteric liquid crystal composition according to claim 1 or 2, wherein the content of the compound represented by the general formula (2) of the second component is 50 to 90% by mass. The polymerizable cholesteric liquid crystal composition according to claim 1, wherein the third component chiral compound is a chiral compound having a polymerizable functional group. The polymerizable cholesteric liquid crystal composition according to claim 1, wherein the third component chiral compound is a chiral compound having an acryl group or a methacryl group. Formula (5) ^{A 7} of a chain transfer agent represented by the 1,4-phenylene groups of the fifth component, ^{A 8} is a phenyl group, ^{G 1} is a single bond or a 1,1-dimethylethylene group, ^{R 2} is hydrogen The polymerizable cholesteric liquid crystal composition according to any one of claims 1 to 5, wherein the atom m represents 0. A thin film formed by polymerizing the polymerizable cholesteric liquid crystal composition according to any one of claims 1 to 6.