TW202448972A - Polymerizable liquid crystal composition - Google Patents

Abstract

A polymerizable liquid crystal composition comprising (i) a polymerizable liquid crystal compound capable of exhibiting birefringence of reverse wavelength dispersibility when the polymerizable liquid crystal compound is in an oriented state, and (ii) a polymerization initiator, which is represented by the following formula (I) exhibits a favorable high temperature stability. A liquid crystal film, which may be obtained via curing of the polymerizable product, is useful in the manufacture of an optical device or an electro-optical device.

Description

Polymerizable liquid crystal composition

The present invention provides a polymerizable liquid crystal composition, a cured liquid crystal film as a cured product of the polymerizable liquid crystal composition, a method for manufacturing the cured liquid crystal film, and use of the liquid crystal film in manufacturing optical or electro-optical devices.

There is a need for an anisotropic liquid crystal film that exhibits negative optical retardation dispersion. For example, a quarter wave film made of a negative dispersion birefringent material will be largely achromatic. A device such as a reflective LCD using such a quarter wave film will have an uncolored dark state.

WO 2021/037774 relates to a composition for an optical film, comprising at least two anisotropic liquid crystal compounds. The optical film exhibits a reverse retardation pattern of polarized light over a wide wavelength band.

A cured liquid crystal film formed of a liquid crystal composition containing a polymerizable liquid crystal (LCP) compound is usually formed by aligning the polymerizable liquid crystal compound in a liquid crystal state on an alignment substrate to obtain a polymerizable liquid crystal layer in which the molecules have a predetermined orientation, and polymerizing the liquid crystal to form a network in which the orientation of the liquid crystal is fixed. The film in which the orientation of the liquid crystal is fixed can be removed from the alignment substrate and can be transferred to another substrate (for example, by using an adhesive).

In many cases, polymerization is initiated by irradiation with light (such as ultraviolet light), and a photopolymerization initiator is used as the polymerization initiator.

WO 2021/175855 discloses α-oxoxime ester compounds based on carbazole derivatives having specific substituents, which can be used as photopolymerization initiators.

Liquid crystal polymer (LCP) materials, although stable at room temperature, degrade at elevated temperatures. In particular, optical properties such as retardation decrease, and thus the performance of the LC film degrades over time.

The reasons for the degradation are not fully elucidated. However, it may be at least partially due to the low polymerization rate and high free radical content. The polymerizable liquid crystal compound that can show reverse wavelength dispersion has maximum absorption in the wavelength region of active energy rays, which are usually represented by ultraviolet rays, thereby cracking the photopolymerization initiator. A portion of the active energy rays irradiated to the polymerizable liquid crystal compound is absorbed by the polymerizable liquid crystal compound, which tends to hinder the cracking of the photopolymerization initiator, making it difficult to achieve a high polymerization rate.

In order to increase the polymerization rate of such a polymerizable liquid crystal compound, it is necessary to irradiate with high-intensity active energy rays in consideration of the absorption of active energy rays by the polymerizable liquid crystal compound. As a result, structural destruction of the polymerizable liquid crystal compound and accompanying alignment defects tend to occur, and it may be difficult to impart high optical properties to the resulting liquid crystal film.

Therefore, there is a need for an LCP composition for preparing aligned polymer films that exhibit favorable high temperature stability.

The present invention provides a polymerizable liquid crystal composition, comprising: (i) a polymerizable liquid crystal compound capable of exhibiting reverse wavelength dispersibility birefringence when the polymerizable liquid crystal compound is in an oriented state; and (ii) a polymerization initiator represented by the following formula (I): (I) wherein R ¹ is hydrogen, C ₁ -C ₂₀ alkyl, C _{1 -C 6} alkyl-C ₃ -C ₆ cycloalkyl, C ₃ -C ₂₀ cycloalkyl or C ₂ -C ₁₂ alkenyl, wherein the C ₃ -C ₂₀ cycloalkyl or C ₂ -C ₁₂ alkenyl is uninterrupted or interrupted by one or more O, S, CO, NR ¹⁰ or COOR ⁴ ; or R ¹ is C ₁ -C ₂₀ alkyl, which is unsubstituted or interrupted by one or more halogens, OR ⁴ , SR ⁹ , NR ¹⁰ R ¹¹ , COOR ⁴ CONR ¹⁰ R ¹¹ , CN, PO(OR ^3a ) ₂ , S(O) _m -R ^3a , , C ₃ -C ₈ cycloalkyl, the C ₃ -C ₈ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ¹⁰ ; or is substituted by one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, C ₁ -C ₄ halogenated alkyl, CN, NO ₂ , OR ⁴ , SR ⁹ , NR ¹⁰ R ¹¹ , PO(OR ^3a ) ₂ or S(O) _m -R ^3a ; or R ¹ is C ₂ -C The C2- _C20 alkyl group is interrupted by one or more O, CO, S, C(O)O, OC(O), SO, _SO2 , phenylene, naphthylene or ^NR10 , wherein the interrupted _C2 - _{C20 alkyl group is unsubstituted or substituted by one or more halogen, C3-C8 cycloalkyl, OH, SH, OR4, SR9, COOR4, O(CO)-R3a, CONR10R11, NR10R11, C6-C20 aryl, C3-C20 heteroaryl ,} ^{C6 - C20 aromatic acyl or C3-C20 heteroarylcarbonyl, wherein the C6-C20 aryl, C3-C20 heteroaryl, C6-C20 aromatic acyl or C3-C20 heteroarylcarbonyl group is substituted by one or more halogen, C3-C8 cycloalkyl, OH, SH, OR4 , SR9 ,} _{COOR4 , O} ⁽ _{CO )} ^-R3a , CONR10R11, NR10R11, C6-C20 aryl, C3- _C20 heteroaryl, C6- _C20 aromatic acyl or C3- _{C20 heteroarylcarbonyl, wherein the C6-C20 aryl , C3} - _C20 heteroaryl, _C6 - _C20 aromatic acyl or C3- _C20 heteroarylcarbonyl R ¹ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, _each of which _{is unsubstituted or substituted with one or more C 1 -C 20 alkyl, phenyl, halogen, C 1 -C 4 halogenated alkyl , CN} , NO ² , OR ₄ , SR ⁹ , NR ¹⁰ R ¹¹ , COOR ⁴ , ₍ ^CO )-R ^3a , ^{(CO)NR 10 R 11 , PO} (OR ^3a ) ₂ , S(O) ^m _-R ^3a or ^a group or substituted by one or more C ₂ -C ₂₀ alkyl groups, the C ₂ -C ₂₀ alkyl groups being interrupted by one or more O, S or NR ¹⁰ ; or substituted by one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl groups being unsubstituted or substituted by one or more halogens, COOR ⁴ , CONR ¹⁰ R ¹¹ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthyl groups, each of which is unsubstituted or substituted by OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or R ¹ is C ₂ -C or R 1 is a phenyloxycarbonyl _group , which is unsubstituted or substituted with a C ₁ -C ₆ alkyl group, a halogen, a phenyl group, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or R ¹ is a hydrogen, a C ₁ -C ₂₀ alkyl group, a CN, a (CO)-R ^3a , a COOR ⁴ , a CONR ¹⁰ R ¹¹ , a NO 2 , a PO(OR ^{3a ) 2} or a S ^{(O) m -R 3a ; R 1a is} a hydrogen, a C ₁ -C ₂₀ alkyl group, a CN, a (CO)-R ^3a , a CONR ¹⁰ R ¹¹ , a NO ₂ , a PO( _OR ^3a _{) 2} or a S(O) _m -R ^3a ; or R ^1a is C ₁ -C ₂₀ alkyl which is substituted by one or more halogens, OR ^4a , SR ^{9a ,} _NR ^10a R ^11a , ^CN , COOR ^4a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a , or C ₃ -C ₈ cycloalkyl which is uninterrupted or interrupted by one or more O, S, CO or NR 10a ; or R 1a is C ₁ -C 20 alkyl which is substituted by one or more halogens, OR 4a , SR 9a , NR 10a R 11a , CN, COOR ^4a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a , or C 3 -C ₈ cycloalkyl which is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; or R 1a is C ₁ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C or R _1a is C ₁ -C ₂₀ alkyl, which is interrupted by one _or more O, _{S, NR 10a , CO, SO or SO 2, which is unsubstituted or substituted by C 3 -C 8 cycloalkyl} , OH, _SH , O( _CO )R 3a , COOR ^4a , CONR ^10a R 11a , C ₆ -C ₂₀ aryl, C ₃ -C ₈ cycloalkyl, OH, ^{SH, O(CO)R 3a , COOR 4a} , CONR ^10a R ^11a , C 6 -C 20 aryl, C ₃ -C ₈ cycloalkyl, OH, SH, O(CO)R ^3a , COOR ^4a , CONR ^10a _R ^11a , C ₆ -C ₂₀ aryl, C ₃ -C C ₆ -C ₂₀ heteroaryl, C 6 -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, wherein C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl is unsubstituted or substituted with one or more halogens, C ₁ -C ₈ alkyl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or R ^1a is C ₂ -C ₁₂ alkenyl or C ₃ -C ₂₀ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR ^10a or COOR ^4a ; or R ^1a is C ₆ -C ₂₀ aryl or C ₃ -C 20 heteroarylcarbonyl. ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more halogen, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R ^3a CONR ^10a R ^11a , PO(OR ^3a ) ₂ or S(O) _m -R ^3a ; or substituted with one or more C _1- C ₂₀ alkyl groups, the C _1- C ₂₀ alkyl groups are unsubstituted or substituted with one or more halogen, COOR ^4a , CONR ^10a R ^11a , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or substituted with one or more C ₂ -C ₂₀ alkyl groups, the C ₂ -C _{R 2} is hydrogen, C 1 -C 20 alkyl or C 1 -C 6 alkyl-C 3 -C 6 cycloalkyl, which is unsubstituted or substituted with one or more halogens, OR ⁴ , SR ⁹ , COOR 4 CONR 10 R ¹¹ , NR ¹⁰ R ¹¹ , PO(OR ^{3a ) 2 , COR 3a} ; R ² is C ₂ -C ₂₀ alkyl or C _{1 -C 6} alkyl-C ₃ -C ₆ cycloalkyl, which is unsubstituted or substituted with one or more halogens, OR ⁴ , SR ⁹ , _COOR ⁴ CONR ¹⁰ R ¹¹ , NR ¹⁰ R ¹¹ , _PO (OR ^3a _{) 2} , COR ^3a _; wherein the interrupted _C2 - ^C20 _alkyl group is unsubstituted or substituted by one or more halogens, OR4, ^SR9 , _COOR4 , ^CONR10R11 , ^NR10R11 ; or ^R2 is _C2 - _C4 hydroxyalkyl, C2- _C10 alkoxyalkyl, _C3 - ^C5 alkenyl, _C3 - _{C8 cycloalkyl} , phenyl- _C1 - _C3 alkyl, _C2 - _C8 alkanoyl, _C3 - _{C12 alkenyl ,} benzoyl; or ^R2 is ^C6 _- ^C20 aryl or _{C3 -} ^C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more C ₁ -C ₁₂ alkyl, C ₁ -C ₄ halogenated alkyl, phenyl, halogen, CN, NO ₂ , OR ⁴ , SR ⁹ , NR ¹⁰ R ¹¹ , (CO)-R ^3a , or substituted with a C ₂ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkyl group is interrupted by one or more O, S or NR ¹⁰ , or each of which is substituted with one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more halogen, COOR ⁴ , CONR ¹⁰ R ¹¹ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ is substituted; or R ² is a group ; R ³ is hydrogen or C ₁ -C ₂₀ alkyl; or R ³ is C ₁ -C ₂₀ alkyl, which is substituted with one or more halogens, OR ⁴ , SR ⁹ , NR ¹⁰ R ¹¹ , CN, COOR ⁴ , CONR ¹⁰ R ¹¹ , C ₃ -C ₈ cycloalkyl, which C ₃ -C ₈ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ¹⁰ ; or is substituted with one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, C ₁ -C or R ³ is C ₁ -C ₂₀ alkyl, which is interrupted by one or more O, S, NR ¹⁰ , CO, SO or SO ^{2 ,} which is unsubstituted or substituted by C ₃ -C ₈ cycloalkyl, ^OH , ^SH , O( _CO )-R ^3a , COOR ⁴ , _CONR ¹⁰ R ¹¹ C ₆ -C 20 aryl, C 3 -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C 3 -C ₂₀ heteroaromatic carbonyl, wherein C ₆ -C 20 aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroaromatic carbonyl is substituted by one or more O, S, _{NR 10 , CO} , SO or SO ₂ ; or R ³ is C ₆ -C ₂₀ aryl or C ₃ ^{-C 20 heteroaryl} , _each of which is unsubstituted or substituted by one or more halogens, C ₁ -C ₂₀ alkyl, C _{1 -C 4} halogenated alkyl, ^phenyl , C ₁ -C ₂₀ alkylphenyl, C _{1 -C 8} alkoxyphenyl, CN, NO ₂ , OR ⁴ , SR ^{9 ,} NR ₁₀ R ¹¹ _{, COOR} ^{4 ,} ₍ ^CO ₎ ^-R or R ³ is C ₁ -C ₂₀ alkoxy, which is unsubstituted or substituted by one or more C ₁ -C ₁₀ alkyl, C ₁ ^-C ₄ halogenated alkyl, _halogen , phenyl, C ₁ -C ₂₀ alkylphenyl or C ₁ -C ₈ alkoxyphenyl; or ^{R 3} is C ₁ -C ₂₀ alkoxy, which is interrupted by one or more O, S, NR ¹⁰ , CO, SO or SO ₂ ; or R ³ is C ₆ -C ₂₀ aryloxy or C ₃ -C ₂₀ heteroaryloxy, each of which is unsubstituted or substituted by one or more halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ halogenated alkyl, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, CN, NO ₂ , OR ⁴ , SR ⁹ R ^3a is hydrogen or C ₁ -C ₂₀ alkyl; or R ^3a is C ₁ -C ₂₀ alkyl, which is substituted by ^one or more ^halogens , OR ^4a , SR ^9a , NR ^10a R ^11a , CN, COOR ^4a , CONR _10a R ^11a , C ₃ -C ₈ cycloalkyl, which is uninterrupted or interrupted by one or more O, S, CO or NR ^{10a ;} or by ^one or ^more C _{6 -C 20} aryl, _C ³ _{-C 20 heteroaryl, C 6 -C 20 aromatic acyl or} C ₃ -C R _3a is C ₁ -C ₂₀ alkyl, which is interrupted by one or more O, S, NR 10a , CO, SO or SO 2, which is unsubstituted or substituted by C ₃ -C ₈ cycloalkyl, OH, _{SH, O(CO)} -(C ₁ -C 8 alkyl), COOR ^4a , CONR ^10a R ^11a , C 6 -C 20 aryl, C 3 -C 20 heteroaryl, C ₆ -C 20 aromatic acyl or C ₃ -C ₈ cycloalkyl, which is unsubstituted or substituted by one or more halogen, phenyl, C 1 -C _{20 alkylphenyl, C 1 -C 8 alkoxyphenyl, C 1 -C 4 halogenated alkyl, CN, NO 2 , OR 4a , SR 9a or NR 10a R 11a ; or R 3a is C 1 -C 20} ^{alkyl ,} which is interrupted by one or more O, S, NR ^10a , CO, SO or SO ₂ , which is unsubstituted or substituted by C 3 -C ₈ cycloalkyl, OH, SH, O(CO)-(C ₁ -C ₈ alkyl), COOR ^4a , CONR ^10a R ^11a , C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C _{C6 - C20} aryl, C3- _C20 heteroaryl, C6- _C20 arylyl or _C3 - _C20 heteroarylcarbonyl is unsubstituted or substituted with one or more halogens, _C1 - _C8 alkyl, ^OR4a , ^SR9a or ^NR10aR11a ; or ^R3a is _{C2 - C12} alkenyl or _C3 - _C20 cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, ^NR10a or ^COOR4a ; or ^R3a is _C6 - _C20 aryl or _C3 - _C20 heteroaryl, each of _which is unsubstituted or substituted with one or more halogens, _C1 - _C20 alkyl, ^C1 _- C or R 3a is C 1 -C 20 alkoxy which is unsubstituted or substituted with _{one or more} C ₁ -C ₁₀ alkyl, C ₁ -C 4 halogenated alkyl, halogen, phenyl, C 1 -C 20 alkylphenyl, C ₁ -C ₈ alkoxyphenyl, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-(C ₁ -C ₈ alkyl) or SO ₂ -(C 1 -C ₄ halogenated alkyl); or R ^3a is C ₁ -C ₂₀ alkoxy which is unsubstituted or substituted with one or more C ₁ -C ₁₀ alkyl, C ₁ -C ₄ halogenated alkyl, halogen, phenyl, C ₁ -C ₂₀ alkylphenyl or C ₁ -C ₈ alkoxyphenyl; or R ^3a is C ₁ -C ₂₀ alkoxy which is interrupted by one or more O, S, NR ^10a , CO, SO or SO ₂ ; or R ^3a is C ₆ -C _{R 3a is a group ​ ​ ​ ​ ​ ​ ​} ^{​ ​ ​ ​ ​} _{​ ​ ​ ​ ​} ^​ R ^3b is hydrogen or C ₁ -C ₂₀ alkyl; or R ^3b is C ₁ -C ₂₀ alkyl, which is substituted with one or more halogens, OR ^4a , SR ^9a , NR ^10a R ^11a , CN, COOR ^4a , CONR ^10a R ^11a , C ₃ -C ₈ cycloalkyl, which C ₃ -C ₈ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; or is substituted with one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C R ^3b is C _{1 -C 20 alkyl, which is interrupted by one or more O, S, NR 10a , CO, SO or SO 2, which is unsubstituted or substituted by C 3 -C 8 cycloalkyl, OH, SH, O(CO)-(C 1 -C 8 alkyl), COOR 4a , CONR 10a R 11a , C 6 -C 20} ^aryl _, ^C _{3 -C 20} ^heteroaryl _{, C} ^{6 -C 20} _{arylyl or} C ₃ -C ₂₀ heteroarylcarbonyl, wherein C ₆ -C 20 aryl, C ₃ ^{-C 20} heteroaryl, C 6 -C ₂₀ arylcarbonyl or C 3 _{-C 20} heteroarylcarbonyl is substituted by C 6 -C 20 aryl, C _{3 -C 20 heteroaryl, C 6} -C ₂₀ arylcarbonyl or C 3 -C 20 heteroarylcarbonyl is substituted by C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C R ^3b is C ₂ -C ₁₂ alkenyl or C ₃ -C ₂₀ cycloalkyl, each ^of which is uninterrupted or interrupted by one or more O, S, CO, NR ^10a or ^{COOR 4a ;} or R ^3b is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is uninterrupted or interrupted by one or more halogen, C _{1 -C 20} alkyl, C ₁ -C ₄ halogenated alkyl, _{phenyl, C 1 -C 20 alkylphenyl, C 1 -C 8 alkoxyphenyl, CN, NO 2 , OR 4a , SR 9a} ^{, or} NR _10a R ^11a _. ^{R 9a} , NR ^10a R ^11a , COOR ^4a , (CO)-(C ₁ -C ₈ alkyl) or SO ₂ -(C ₁ -C ₄ halogenated alkyl) substituted; or R ^3b is C ₁ -C ₂₀ alkoxy, which is unsubstituted or substituted by one or more C ₁ -C ₁₀ alkyl, C ₁ -C ₄ halogenated alkyl, halogen, phenyl, C ₁ -C ₂₀ alkylphenyl or C ₁ -C ₈ alkoxyphenyl; or R ^3b is C ₁ -C ₂₀ alkoxy, which is interrupted by one or more O, S, NR ^10a , CO, SO or SO ₂ ; or R ^3b is C ₆ -C ₂₀ aryloxy or C ₃ -C ₂₀ heteroaryloxy, each of which is unsubstituted or substituted by one or more halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ halogenated alkyl, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-(C ₁ -C ₈ alkyl) or SO ₂ -(C ₁ -C ₄ halogenated alkyl); R ⁴ is hydrogen, (CO)-R ^3a , COOR ^4a , CO NR ^10a R ^11a , S(O) _m -R ^3a or PO(OR ^3a ) ₂ ; or R ⁴ is C ₁ -C ₂₀ alkyl which is substituted by one or more halogens, OR ^4a , SR ^9a , NR ^10a R ^11a , CN, COOR ^4a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a , C ₃ -C ₈ cycloalkyl group, the C ₃ -C ₈ cycloalkyl group is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; or is substituted by one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, C ₁ -C ₄ halogenated alkyl, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , PO(OR ^3a ) ₂ or S(O) _m -R ^3a ; or R ⁴ is C _C1 - _C20 alkyl, which is interrupted by one or more O, S, ^NR10a , CO, SO or _SO2 , which is unsubstituted or substituted by _C3 - _C8 cycloalkyl, OH, SH, O(CO) ^-R3a , ^COOR4a , ^CONR10aR11a , C6-C20 ^aryl , C3- _{C20 heteroaryl, C6-C20 aromatic} acyl or C3- _C20 heteroarylcarbonyl, _wherein the _{C6 - C20} aryl, _{C3 - C20} heteroaryl, _C6 - _C20 aromatic acyl ^or C3- _C20 heteroarylcarbonyl is unsubstituted or substituted by ^one _or more halogen, _C1 - _C8 alkyl, _OR4a , _SR9a or ^NR10aR or R ⁴ is C ₂ -C ₁₂ alkenyl or C ₃ -C ₂₀ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR ^10a or COOR ^4a ; or R ⁴ is C ₆ -C ₂₀ ^aryl , which is interrupted by one or more halogen, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R ^3a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a or a group or substituted by one or more C _{1 -C 20} alkyl groups, which are _{unsubstituted} or substituted by one or more halogens, COOR ^4a , CONR ^10a R ^11a , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or substituted by one or more C _{2 -C 20} alkyl groups, which are interrupted by one or more O, S or NR ^10a ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthyl groups, each of which is unsubstituted or substituted by OR ^4a _, SR ^9a or NR ^10a R ^11a ; or R ⁴ is C ₃ -C ₂₀ heteroaryl groups, each of which is unsubstituted or substituted with one or more halogens, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R ^3a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a or a group or substituted by one or more C _{1 -C 20} alkyl groups, which are _{unsubstituted} or substituted by one or more halogens, COOR ^4a , CONR ^10a R ^11a , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or substituted by one or more C _{2 -C 20} alkyl groups, which are interrupted by one or more O, S or NR ^10a ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthyl groups, each of which is unsubstituted or substituted by OR ^4a _, SR ^9a or NR ^10a R ^11a ; or R ⁴ and R 1 together with one of the carbon atoms of ¹ to form a 5-membered or 6-membered saturated or unsaturated ring, which is uninterrupted or interrupted by O, S or NR ^10a , and the 5-membered or 6-membered saturated or unsaturated ring is unsubstituted or substituted with one or more C ₁ -C ₂₀ alkyl groups, OR ^4a , SR ^9a , NR ^10a R ^11a , (CO)-R ^3a , NO ₂ , halogen, C ₁ -C ₄ halogenated alkyl, CN, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, or C ₃ -C ₂₀ cycloalkyl substituted, the C ₃ -C ₂₀ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; R ^4a is hydrogen, C ₁ -C ₂₀ alkyl, (CO)O(C ₁ -C ₈ alkyl) or CON(C ₁ -C ₈ alkyl) ₂ ; or R ^4a is C ₁ -C ₂₀ alkyl substituted by one or more halogen, OH, SH, CN, C ₃ -C ₈ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₈ alkyl), O(CO)-(C ₁ -C ₈ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₈ alkyl), C ₃ -C _{R 4a} is C ₂ -C ₂₀ alkyl, which is interrupted by one _or more O, _S , N(C ₁ -C ₈ alkyl), CO, SO or SO _{2 ,} which is _{unsubstituted} or substituted by C _{3 -C 8} cycloalkyl, OH, SH, O(CO ⁾ (C _{1 -C 8} alkyl), (CO) _O (C ₁ -C ₈ alkyl), (CO)N(C _{1 -C 8} alkyl) ₂ , C ₆ -C _{20 aryl} , C _{3 -C 20} heteroaryl, _{C 6 -C 20} C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroarylcarbonyl, wherein C ₆ -C 20 aryl, C 3 -C 20 heteroaryl, C 6 -C 20 aryl or C ₃ -C ₂₀ heteroarylcarbonyl is unsubstituted or substituted with one or more halogens, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylhydrosulfanyl or N (C ₁ -C ₈ alkyl) ₂ ; or R ^4a is C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or substituted with one or more halogens, CN, NO ₂ , OH, C ₁ -C ₈ alkyl, C ₁ -C 8 R _4a is substituted by C ₂ -C ₁₂ alkenyl, (CO)O(C _{1 -C 8 alkenyl) or C 3 -C 8 cycloalkyl} , each of which is uninterrupted or interrupted by _one or more _O , S, CO, N(C ₁ -C ₈ alkyl) or COO(C _{1 -C 8 alkyl} ); or R ^4a is C _{1 -C 20 alkyl, C 3} -C ₁₂ alkenyl, (CO)O(C _{1 -C 8} alkenyl) or _{C 3} -C ₈ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, _N (C ₁ -C ₈ alkyl) or ^COO (C ₁ -C _{8 alkyl )} ; -C ₁₂ alkenyl, each of which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, OH, C ₁ -C ₈ alkoxy, phenoxy, C ₁ -C ₈ alkylthiohydrogen, phenylthiohydrogen, N(C ₁ -C ₈ alkyl) ₂ or diphenylamino; R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen, C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ arylC ₁ -C ₂₀ -alkyl, hydroxy-C ₁ -C ₂₀ alkyl, hydroxy-C ₁ -C ₂₀ alkoxy-C ₁ -C ₂₀ alkyl, C ₃ -C ₁₀ cycloalkyl, amine, CN, NO _2. Hydroxyl, , (CO)-R ^3a , OR ^4a or COOR ⁴ ; R ⁹ is hydrogen or C ₁ -C ₂₀ alkyl; or R ⁹ is C ₁ -C ₂₀ alkyl, which is substituted by one or more halogens, OR ^4a , SR ^9a , NR ^10a R ^11a , CN, COOR ^4a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a , C _{3 -C 8} cycloalkyl, which is _{uninterrupted} or interrupted by one or more O, S, CO or NR ^10a ; or by one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C or R ₉ is C ₁ -C ₂₀ alkyl, which is interrupted by one or more O, S, NR 10a , CO, SO or _{SO 2} ^, which is unsubstituted or substituted by _{C 3} -C ₈ cycloalkyl, OH, _SH , O( ^CO )-R ^3a , COOR ^4a , CONR ^10a R ^11a , C ₆ -C ₂₀ aryl, C 3 -C ₂₀ ^heteroaryl , C 6 -C 20 heteroaryl, C 6 -C 20 heteroaryl, C 6 -C 20 heteroaryl, C 6 -C 20 heteroaryl, C ₆ ^-C ₂₀ heteroaryl, C ₆ -C ₂₀ heteroaryl, C 6 -C ²⁰ heteroaryl, ^{C 6 -C} 20 ^heteroaryl , C 6 -C 20 heteroaryl, C ₆ -C 20 heteroaryl, C 6 -C ²⁰ heteroaryl, C ₆ -C ₂₀ heteroaryl, C ₆ -C C _{6 -C 20} aryl, C ₃ -C _{20 heteroaryl, C 6 -C 20 aryl} or C ₃ -C ₂₀ heteroarylcarbonyl is unsubstituted or substituted with one or more halogens, C ₁ -C ₈ alkyl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or R ⁹ is C 2 -C ₁₂ alkenyl or C _{3 -C 20 cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR 10a or COOR 4a; or R 9 is C 6 -C 20 aryl or C 3 -C 20} ^{heteroaryl , each} _{of which is unsubstituted or substituted} with one or more halogens, CN, NO ₂ , OR 11a. ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R ^3a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a or a group or substituted by one or more C _{1 -C 20} alkyl groups, which are _{unsubstituted} or substituted by one or more halogens, COOR ^4a , CONR ^10a R ^11a , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or substituted by one or more C _{2 -C 20} alkyl groups, which are interrupted by one or more O, S or NR ^10a ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthyl groups, each of which is unsubstituted or substituted by OR ^4a _, SR ^9a or NR ^10a R ^11a ; or R ⁹ and R ¹ , 1 or more carbon atoms of the phenyl group, phenyl group, C ₁ ^-C ₂₀ ^alkylphenyl group, _C ^{1 -C} ₈ alkoxyphenyl group _, or _{C 1} ^-C ₂₀ ^alkylphenyl _group . or C ₃ -C ₂₀ cycloalkyl substituted, the C ₃ -C ₂₀ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; R ^9a is hydrogen or C ₁ -C ₂₀ alkyl; or R ^9a is C ₁ -C ₂₀ alkyl which is substituted by one or more halogen, OH, SH, CN, C ₃ -C ₈ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₈ alkyl), O(CO)-(C ₁ -C ₈ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₈ alkyl), C ₃ -C ₈ cycloalkyl, SO ₂ -(C ₁ -C ₄ halogenated alkyl), O(C ₁ -C R ^9a is C _{2 -C 20} alkyl, which is interrupted by one or more O, S, N(C ₁ -C ₈ alkyl), _CO , SO or SO ₂ , which is unsubstituted _or substituted by C _{3 -C 8} cycloalkyl, OH, SH, O(CO)(C ₁ -C ₈ alkyl), (CO)O(C ₁ -C ₈ alkyl), (CO)N(C _{1 -C 8} alkyl) ₂ , C ₆ -C ₂₀ aryl, _{C 3} -C ₂₀ heteroaryl, C ₆ -C _{20 arylyl} or C ₃ -C ₂₀ heteroarylcarbonyl, _wherein C ₆ -C _{20 R 9a} is C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, N(C ₁ -C ₈ alkyl) or COO(C ₁ -C ₈ alkyl); or R ^9a is C ₆ -C ₂₀ aryl, C ₃ -C 20 heteroaryl, C 6 -C ₂₀ aromatic acyl or C ₃ -C 20 heteroaromatic carbonyl, which is unsubstituted or substituted by one or more halogen, C ₁ -C 8 alkyl, C 1 -C _{8 alkoxy, C 1 -C 8 alkylhydrosulfanyl or N(C 1 -C 8 alkyl) 2; or R 9a is C 2 -C 12 alkenyl or C 3 -C 8 cycloalkyl , each of} which is uninterrupted or interrupted by one or more O, S, CO, N(C ₁ -C ₈ alkyl) or COO(C ₁ -C ₈ alkyl); or R ^9a is C ₆ -C ₂₀ aryl, C 3 -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C R _9a is C 1 -C 20 alkyl, C 3 -C ₁₂ alkenyl, each of which is unsubstituted or substituted with one or more halogens, CN, NO ₂ , OH, C ₁ -C 8 alkyl, C ₁ -C ₄ halogenated alkyl, C ₁ -C ₈ alkoxy, phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₈ alkylthio, phenylthio, N (C ₁ -C ₈ alkyl) ₂ , diphenylamino, (CO) O (C ₁ -C ₈ alkyl), (CO) -C ₁ -C ₈ alkyl or (CO) N (C ₁ -C ₈ ) ₂ , phenyl or benzoyl; or R ^9a is C ₁ -C ₂₀ alkyl, C ₃ -C ₁₂ alkenyl, each of which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C R ₁₀ and R ¹¹ are independently hydrogen _{, C 1 -C 20} alkyl, S(O) _m -R ^3a , O(CO)-R _3a (CO)-R ^3a or CONR ^10a R _{11a ; or R 10 and R 11 are independently C 1 -C 20} ^{alkyl which} _{is substituted by one} or more halogens, OR ^4a , SR ^9a , NR ^{10a R 11a} , CN _, COOR ^4a _, CONR ^10a R ^11a , PO( _OR ^3a ) ² , S ⁽ O) _m -R ^3a , C ₃ -C The C ₃ -C ₈ cycloalkyl group is uninterrupted or _interrupted by one or more O, S, CO or NR ^10a ; or is substituted by one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, C ₁ -C ₄ halogenated alkyl, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , PO(OR ^3a ) ₂ or S(O) _m -R ^3a ; or R ¹⁰ and R ¹¹ are independently C ₁ -C 20 R ^11a , C 6 ^-C ₂₀ aryl, C ³ -C ₂₀ heteroaryl, C ₆ -C _{20 aryl or C 3 -C 20 heteroarylcarbonyl, wherein the C 6 -C 20 aryl ,} C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryl or C _{3 -C 20 heteroarylcarbonyl} is _{unsubstituted} ^or _substituted with one or _more halogens, C _{1 -C 8} alkyl, OR ^4a , SR ^9a _{or NR} ^{10a R 11a} ; or R ^{R 10} and R ¹¹ are independently C ₂ -C ₁₂ alkenyl or C ₃ -C ₂₀ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR ^10a or COOR ^4a ; or R ¹⁰ and R ¹¹ are independently C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or interrupted by one or more halogens, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R ^3a CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a or a group or substituted by one or more C _{1 -C 20} alkyl groups, which are _{unsubstituted} or substituted by one or more halogens, COOR ^4a , CONR ^10a R ^11a , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or substituted by one or more C _{2 -C 20} alkyl groups, which are interrupted by one or more O, S or NR ^10a ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthyl groups, each of which is unsubstituted or substituted by OR ^4a _, SR ^9a or NR ^10a R ^11a ; or R ¹⁰ and R ¹¹ are independently C ₁ -C 20 R ^{10 and R 11 are independently C 1 -C 20 alkoxy groups, which are unsubstituted or substituted with one or more halogens, phenyl, C 1 -C 8 alkylphenyl or C 1 -C 8 alkoxyphenyl groups; or R 10 and R 11} _{are independently C 1 -C 20 alkoxy groups , which are} interrupted by one or more O, S, NR ^10a , CO, SO or SO ₂ ; or R ¹⁰ and R ¹¹ are independently C ₆ -C ₂₀ aryloxy groups or C ₃ -C ₂₀ heteroaryloxy groups, each of which is unsubstituted or substituted with one or more halogens, C ₁ -C ₈ alkyl, C ₁ -C ₄ halogenated alkyl, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C ₈ alkoxyphenyl groups, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R or R ¹⁰ and one of ^the carbon atoms _of ^{R 1} together form a 5-membered or 6-membered saturated or unsaturated ring which is uninterrupted or interrupted by O, S or NR ^10a , and the 5-membered or 6-membered saturated or unsaturated ring is unsubstituted or substituted by one or more C ₁ -C ₂₀ alkyl groups, OR ^4a , SR ^9a , NR ^10a R ^11a , (CO)-R ^3a , NO ₂ , halogen, C ₁ -C ₄ halogenated alkyl, CN, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, or substituted by a C ₃ -C ₂₀ cycloalkyl group, the C ₃ -C ₂₀ cycloalkyl group being uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; or R ¹⁰ and R ¹¹ together with the N atom to which they are attached form a 5-membered or 6-membered saturated or unsaturated ring, which is uninterrupted or interrupted by O, S or NR ^10a , and the 5-membered or 6-membered saturated or unsaturated ring is unsubstituted or substituted by one or more C ₁ -C ₂₀ alkyl groups, OR ^4a , SR ^9a , NR ^10a R ^11a , (CO)-R ^3a , NO ₂ , halogen, C ₁ -C ₄ halogenated alkyl, CN, phenyl, or C ₃ -C ₂₀ cycloalkyl substituted, the C ₃ -C ₂₀ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; R ^10a and R ^11a are independently hydrogen, C ₁ -C ₂₀ alkyl, S(O) _m -(C ₁ -C ₈ alkyl), O(CO)(C ₁ -C ₈ alkyl), (CO)(C ₁ -C ₈ alkyl), (CO)O(C ₁ -C ₈ alkyl) or CON(C ₁ -C ₈ alkyl) ₂ ; or R ^10a and R ^11a are independently C ₁ -C ₂₀ alkyl, which is substituted by one or more halogen, OH, SH, CN, C ₃ -C ₈ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C 8 alkyl) _R 10a and R 11a are independently C ₂ -C ₂₀ alkyl, which is _{interrupted by one or more} O _{, S} , ^N ( _{C 1 -C 8 alkyl} ), CO _{, SO or} ^SO _{2 ,} which _{is unsubstituted} or _interrupted by _{C 3 -C 8 cycloalkyl . R} 10a and R 10b are substituted with C ₁ -C ₈ cycloalkyl, OH, SH, O(CO)(C ₁ -C ₈ alkyl), (CO)O(C ₁ -C ₈ alkyl), (CO)N(C ₁ -C ₈ alkyl) ₂ , C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C _{6 -C 20 arylacyl or C 3} -C ₂₀ heteroarylcarbonyl, wherein the C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ arylacyl or C ₃ -C ₂₀ heteroarylcarbonyl is unsubstituted or substituted with one or more halogens, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthiohydrogen or N(C ₁ -C ₈ alkyl) ₂ ; or R ^10a and R ^{R 11a} are independently C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, N(C ₁ -C ₈ alkyl), or COO(C ₁ -C ₈ alkyl); or R ^10a and R ^11a are independently C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or interrupted by one or more halogen, CN, NO ₂ , OH, C ₁ -C ₈ alkyl, C ₁ -C ₄ halogenated alkyl, C ₁ -C ₈ alkoxy, phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C _R 10a and R 11a are independently C 1 -C ₂₀ alkylyl, C ₃ -C 12 alkenyl, each of which is unsubstituted or substituted with _one or more halogens, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C 8 alkoxyphenyl, OH, C 1 -C ₈ alkoxy, phenoxy, C 1 -C 8 alkylhydrothio, phenylhydrothio, N (C ₁ -C ₈ alkyl) ₂ or diphenylamino; or R ^10a and R ^11a are independently C ₁ -C ₂₀ alkylyl, C ₃ -C ₁₂ alkenyl, each of which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, OH, C ₁ -C ₈ alkoxy, phenoxy, C ₁ -C ₈ alkylhydrothio, ^{phenylhydrothio} , N (C ₁ -C ₈ alkyl) ₂ or diphenylamino; ^{R 11a} are independently C ₁ -C ₂₀ alkoxy, which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₈ alkylphenyl or C ₁ -C ₈ alkoxyphenyl; or R ^10a and R ^11a are independently C ₁ -C ₂₀ alkoxy, which is interrupted by one or more O, S, N (C ₁ -C ₈ alkyl), CO, SO or SO ₂ ; or R ^10a and R ^11a are independently C ₆ -C ₂₀ aryloxy or C ₃ -C ₂₀ heteroaryloxy, each of which is unsubstituted or substituted with one or more halogens, C ₁ -C ₈ alkyl, C ₁ -C ₄ halogenated alkyl, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, CN, NO ₂ , C ₁ -C ₈ alkoxy, C ₁ -C or R _10a and R _11a together with the nitrogen atom _to which _they are attached form a _5- or 6 _- membered saturated or unsaturated ring which is uninterrupted or interrupted by O ^, S or _N ( _{C 1 -C 8} alkyl), and wherein the 5- or 6 ^- membered saturated or unsaturated ring is unsubstituted or substituted by one or more C ₁ -C ₈ alkyl, C ₁ -C 8 alkoxy, C ₁ -C ₈ alkylthio, N( _{C 1 -C 8 alkyl) 2, NO 2, halogen, C 1 -C 4 halogenated alkyl , CN , phenyl or} C ₃ -C ₈ R ₁₂ and R ^{13 are independently hydrogen, C 1 -C 12 alkyl, which is optionally substituted with one or more halogen, phenyl, CN, -OH, -SH, C 1 -C 4 alkoxy, (CO) OH or (CO) O(C 1 -C 4 alkyl); or R 12 and R 13} _{are phenyl , which is optionally substituted with one} ^{or more} _{C 1 -C 6 alkyl , halogen ,} CN, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or R ¹² and R ¹³ are halogen, CN, OR ⁴ , SR ⁹ , ^{SOR 9} , SO ₂ R ⁹ or NR ¹⁰ R ¹¹ , wherein the substituents OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ optionally form a 5-membered or 6-membered ring via the groups R ⁴ , R ⁹ , R ¹⁰ and/or R ¹¹ with one of the carbon atoms of phenyl, naphthyl, benzoyl or naphthyl or the carbon atom of the substituent R ^3a ; or R ¹² and R ¹³ together are the group , wherein R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are independently hydrogen, C ₁ -C ₁₂ alkyl, the C ₁ -C ₁₂ alkyl being optionally substituted with one or more halogen, phenyl, CN, -OH, -SH, C ₁ -C ₄ alkoxy, (CO) OH or (CO) O(C ₁ -C ₄ alkyl); or R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are phenyl, which is optionally substituted with one or more C ₁ -C ₆ alkyl, halogen, CN, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are halogen, CN, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or R ¹² and R ¹³ together are a group , wherein R ¹⁸ and R ¹⁹ are independently hydrogen, C ₁ -C ₁₂ alkyl, the C ₁ -C ₁₂ alkyl being optionally substituted with one or more halogens, phenyl, CN, -OH, -SH, C ₁ -C ₄ alkoxy, (CO) OH or (CO) O(C ₁ -C ₄ alkyl); or R ¹⁸ and R ¹⁹ are phenyl, which is optionally substituted with one or more C ₁ -C ₆ alkyl, halogens, CN, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; m is 1 or 2; and Q is CO or a direct bond.

The polymerization initiator is a carbazolyl α-oxoxime ester compound according to formula (I).

In a preferred embodiment, ^R1 is _C1 - _C20 alkyl, _C1 - _C6 alkyl- _C3 - _C6 cycloalkyl, _C3 - _C20 cycloalkyl; or ^R1 is _C2 - _C20 alkyl interrupted by one or more O, CO, S, C(O)O, OC(O), SO or _SO2 ; or ^R1 is _C6 - _C20 aryl which is unsubstituted or substituted by one or more _C1 - _C20 alkyl.

In a particularly preferred embodiment, R ¹ is C ₁ -C ₂₀ alkyl, preferably linear C ₁ -C ₈ alkyl, especially linear C ₂ -C ₆ alkyl.

In a preferred embodiment, ^R2 is _C1 - _C20 alkyl; or ^R2 is _C2 - _C20 alkyl or _C1 - _C6 alkyl- _C3 - _C6 cycloalkyl, which is interrupted by one or more O, CO, S, C(O)O, OC(O), SO or _SO2 ; or ^R2 is _C6 - _C20 aryl, which is unsubstituted or substituted by one or more _C1 - _C12 alkyl or (CO) ^-R3a .

In a particularly preferred embodiment, R ² is C ₂ -C ₁₀ alkyl.

In another preferred embodiment, R ³ is hydrogen or C ₁ -C ₂₀ alkyl, preferably C ₁ -C ₂₀ alkyl, especially straight chain C ₁ -C ₂₀ alkyl, such as straight chain C ₁ -C ₆ alkyl, most preferably methyl.

In another preferred embodiment, R ^3a is C ₁ -C ₂₀ alkyl; or R ^3a is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ halogenated alkyl, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-(C ₁ -C ₈ alkyl) or SO ₂ -(C ₁ -C ₄ halogenated alkyl).

In a particularly preferred embodiment, R ^3a is C ₁ -C ₂₀ alkyl, more preferably R ^3a is C ₁ -C ₁₀ alkyl.

In another preferred embodiment, R ⁴ is (CO)-R ^3a , COOR ^4a , CONR ^10a R ^11a , S(O) _m -R ^3a or PO(OR ^3a ) ₂ , especially (CO)-R ^3a .

In another preferred embodiment, R ^4a is C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl.

In a particularly preferred embodiment, R ^4a is C ₁ -C ₂₀ alkyl, preferably C ₁ -C ₈ alkyl.

In another preferred embodiment, R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen or C ₁ -C ₂₀ alkyl.

In a particularly preferred embodiment, R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen.

In another preferred embodiment, R ⁹ is hydrogen or C ₁ -C ₂₀ alkyl.

In a particularly preferred embodiment, R ⁹ is hydrogen or C ₁ -C ₈ alkyl.

In another preferred embodiment, R ¹⁰ and R ¹¹ are independently hydrogen, C ₁ -C ₂₀ alkyl, S(O) _m -R ^3a , O(CO)-R ^3a (CO)-R ^3a or CONR ^10a R ^11a .

In a particularly preferred embodiment, R ¹⁰ and R ¹¹ are independently hydrogen or C ₁ -C ₈ alkyl.

In another preferred embodiment, R ^10a and R ^11a are independently hydrogen, C ₁ -C ₂₀ alkyl, S(O) _m -(C ₁ -C ₈ alkyl), O(CO)(C ₁ -C ₈ alkyl), (CO)(C ₁ -C ₈ alkyl), (CO)O(C ₁ -C ₈ alkyl) or CON(C ₁ -C ₈ alkyl) ₂ .

In a particularly preferred embodiment, R ^10a and R ^11a are independently hydrogen or C ₁ -C ₈ alkyl.

In a specific embodiment, the compound of formula (I) is a compound, wherein R ¹ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₆ alkyl-C ₃ -C ₆ cycloalkyl, C ₃ -C ₂₀ cycloalkyl or C ₂ -C ₁₂ alkenyl, wherein the C ₃ -C ₂₀ cycloalkyl or C ₂ -C ₁₂ alkenyl is uninterrupted or interrupted by one or more O, S, CO, NR ¹⁰ or COOR ⁴ ; R ² is hydrogen, C ₁ -C ₂₀ alkyl or C ₁ -C ₆ alkyl-C ₃ -C ₆ cycloalkyl, which is unsubstituted or interrupted by one or more halogen, OR ⁴ , SR ⁹ , COOR ⁴ , CONR ¹⁰ R ¹¹ , NR ¹⁰ R ¹¹ , PO(OR ^3a ) ₂ , COR ^R3a is substituted by: ^R3 is hydrogen or _C1 - _C20 alkyl; ^R3a is hydrogen or _C1 - _C20 alkyl; ^R4 is hydrogen, (CO) ^-R3a , ^COOR4a , ^CONR10aR11a , S(O) _m ^{-R3a or} PO( ^OR3a ) ₂ ; ^R4a is hydrogen, _C1 - _C20 alkyl, (CO)O( _C1 - _C8 alkyl) or CON( _C1 - _C8 alkyl) ₂ ; ^R5 , ^R6 , ^R7 and ^R8 are independently hydrogen, _C1 - _C20 alkyl, _C6 - _C20 aryl, _C1 - _C20 alkoxy, _C6 - _C20 arylC1- _{C20 alkyl} , hydroxy- _C1 -C C ₂₀ alkyl, hydroxy-C ₁ -C ₂₀ alkoxy-C ₁ -C ₂₀ alkyl, C ₃ -C ₁₀ cycloalkyl, amine, CN, NO ₂ , hydroxy, , (CO)-R ^3a , OR ^4a or COOR ⁴ ; R ⁹ is hydrogen or C ₁ -C ₂₀ alkyl; R ¹⁰ and R ¹¹ are independently hydrogen, C ₁ -C ₂₀ alkyl, S(O) _m -R ^3a , O(CO)R ^3a (CO)-R ^3a or CONR ^10a R ^11a ; and R ^10a and R ^11a are independently hydrogen, C ₁ -C ₂₀ alkyl, S(O) _m -(C ₁ -C ₈ alkyl), O(CO)(C ₁ -C ₈ alkyl), (CO)(C ₁ -C ₈ alkyl), (CO)O(C ₁ -C ₈ alkyl) or CON(C ₁ -C ₈ alkyl) ₂ ; and Q is CO or a direct bond.

Preferred compounds of formula (I) include compounds of formula (Ia) and (Ib): (Ia) (Ib) wherein R ¹ is a linear C ₁ -C ₈ alkyl group, in particular a C ₂ -C ₆ alkyl group; R ²⁰ and R ²¹ are independently C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, in particular a C ₁ -C ₈ alkyl group.

A particularly preferred compound of formula (Ia) is a compound of formula (Ia-1): (Ia-1)

The polymerizable liquid crystal composition preferably comprises the polymerization initiator of formula (I) in an amount of 0.015 to 10 wt.-%, more preferably 0.5 to 8.0 wt.-%, even more preferably 1.0 to 6.0 wt.-%, and most preferably 1.5 to 4.0 wt.-%, relative to the total weight of the polymerizable liquid crystal composition.

Suitable α-oxoxime ester compounds are known to the skilled person. The synthesis of such compounds is described, for example, in WO 2021/175855. For example, compounds of formula (I) can be prepared by reacting the corresponding oxime with an acyl halide (especially a chloride) or an anhydride in the presence of an alkali or an alkali mixture (for example triethylamine or pyridine) in an inert solvent such as, for example, tert-butyl methyl ether (TBME), tetrahydrofurane (THF), dimethoxyethane (DME), dimethylacetamide (DMA), dichloromethane (DCM), ethyl acetate or dimethylformamide (DMF)) or in an alkaline solvent such as pyridine, as shown in the following scheme: ^R1 to ^R8 have the meanings given above, and ^R3 is preferably methyl. Hal means a halogen atom, in particular Cl. Such reactions are described, for example, in WO 201/2045736 and are generally carried out at a temperature of -15 to +50°C, preferably 0 to 25°C.

α-Ketoximes can be obtained by a variety of methods described in standard chemistry textbooks (e.g. J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992) or in specialized monographs, such as SR Sandler & W. Karo, Organic functional group preparations, Vol. 3, Academic Press. One of the most convenient methods is the nitrosation of "active" methylene groups, for example with nitrous acid or alkyl nitrites. Two kinds of alkaline conditions (such as described in Organic Synthesis coll. Vol. VI (J. Wiley & Sons, New York, 1988), pp 199 and 840) and acidic conditions (such as described in Organic Synthesis coll. Vol. V, pp 32 and 373, coll. Vol. Ill, pp 191 and 513, coll. Vol. II, pp 202, 204 and 363) are suitable for preparing the oxime used as starting material in the present invention. Nitrous acid is usually generated by sodium nitrite. Alkyl nitrite can be, for example, methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, amyl nitrite or isoamyl nitrite.

The corresponding ketone intermediates are prepared, for example, by methods described in the literature, such as the standard chemistry textbook (J. March. Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992). In addition, the continuous Friedel-Crafts reaction is effective for the synthesis of the intermediates. Such reactions are well known to those skilled in the art.

The corresponding ketone intermediate can be synthesized, for example, by the following method, but is not limited thereto. A reasonable synthesis scheme is described below. Arylation and acylation of [A], and demethylation of [B] give the corresponding ketone intermediate [C]. Coupling reaction of [C] and [D] gives the corresponding ketone intermediate [E]. Alternatively, [D] can be introduced after subsequent oximation or oxime esterification (Scheme 1).

Solution 1

The polymerizable liquid crystal composition includes a polymerizable liquid crystal compound capable of showing birefringence with reverse wavelength dispersion when the polymerizable liquid crystal compound is in an aligned state.

Useful parameters for evaluating birefringence against wavelength dispersion in a material are the Re ₄₅₀ value, representing the retardation of the material at a wavelength of 450 nm, the Re ₅₅₀ value, representing the retardation of the material at a wavelength of 550 nm, and the Re ₆₅₀ value, representing the retardation of the material at a wavelength of 650 nm. The retardation Re of a material (in nm) is defined as the product of the birefringence Δn at a given wavelength and the layer thickness d (in nm).

In birefringent materials having reverse wavelength dispersion, the Re ₄₅₀ /Re ₅₅₀ value is lower than 1.0 and the Re ₆₅₀ /Re ₅₅₀ value is higher than 1.0, which means that the magnitude of birefringence Δn increases with increasing wavelength λ.

The anisotropic layer formed by uniformly aligning only the polymerizable liquid crystal compound having reverse wavelength dispersion of the polymerizable liquid crystal composition satisfies the following relationship: the Re ₄₅₀ /Re ₅₅₀ value is lower than 1.0 and the Re ₆₅₀ /Re ₅₅₀ value is higher than 1.0.

The polymerizable liquid crystal compound with reverse wavelength dispersion includes a main chain mesogen and a side chain mesogen bonded to the main chain mesogen in its molecule. When the polymerizable liquid crystal compound with reverse wavelength dispersion is uniformly oriented, the optical axis of the main chain mesogen and the optical axis of the side chain mesogen are oriented in different directions.

The polymerizable liquid crystal compound is preferably at least one anisotropic compound of formula (II) (II) wherein the moieties C and D are independently selected from the group consisting of phenyl, biphenyl, naphthyl, cycloalkyl, bicycloalkyl, , ,or ; wherein *1 represents the bonding sites of moiety C and ^X2 and moiety D and ^X1 , respectively, and *2 represents the bonding sites of moieties C and D and their adjacent carboxyl groups bonded to moiety E; moiety E is selected from the group consisting of phenyl, biphenyl and naphthyl; moiety F is selected from the group consisting of a group of formula (IIIa), (IIIb) or (IIIc) (IIIa); (IIIb); or (IIIc) wherein * represents the bonding site of the moiety F to the imine nitrogen atom of formula II; wherein at least one of ^X1 and ^X2 is independently represented by a group of formula (IV): (IV) wherein n is an integer between 0 and 24, and wherein one or more C atoms may be replaced by -O-, -COO-, -OCO-, -OOC-, -O(CO)O-, -N-, -NR ^a -, -CON-, wherein ^Ra is a C ₁ -C ₁₂ alkyl group; and PG represents a polymerizable group selected from the group consisting of CH ₂ =C(Ph)-, CH ₂ =CW-COO-, CH ₂ =CH-COO-Ph-, CH ₂ =CW-CO-NH-, CH ₂ =CH-O-, CH ₂ =CH-OOC-, Ph-CH=CH-, CH ₂ =CH-Ph-, CH ₂ =CH-Ph-O-, R ^b -Ph-CH=CH-COO-, R ^b -OOC-CH=CH-Ph-O- and 2-W-epoxyethyl; wherein W represents H, Cl, Ph or lower alkyl and ^R represents lower alkyl, with the proviso that when ^R is attached to phenylene (-Ph-), it may also represent hydrogen or lower alkoxy, and, if applicable, ^X1 and ^X2 not represented by a radical of formula (IV) are selected from the group consisting of hydrogen, _C1 - _C12 substituted or unsubstituted linear or branched alkyl, _C3 - _C12 substituted or unsubstituted linear or branched alkenyl and _C1 - _C12 alkoxy, wherein one or more carbon atoms may be replaced by -O-, -COO-, -OCO-, -OOC-, -O(CO)O-, -N-, ^-NRa- , -CON-, wherein ^Ra is _C1 -C wherein Y is selected from the group consisting of H, or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms; R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are independently selected from the group consisting of hydrogen, C ₁ -C ₁₂ straight or branched alkyl, C ₃ -C ₁₂ alkenyl, C ₁ -C _{12 alkoxy, C 3 -C 12 alkenyloxy , -} (CH ₂ ) _m -C(CH ₃ ) ₃ , NO ₂ , CN, COR ¹⁰⁴ , -COOR ¹⁰⁴ , -OCOR ¹⁰⁴ , -CONR ¹⁰⁵ R ¹⁰⁴ , -NR ¹⁰⁵ COR ¹⁰⁴ , OCOOR ¹⁰⁴ , -OCONR ¹⁰⁵ R ¹⁰⁴ , -NR ¹⁰⁵ COOR ¹⁰⁴ , -F, -Cl, -CF ₃ and -OCF ₃ ; wherein m is an integer between 0 and 12; R ¹⁰⁴ is selected from the group consisting of hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl having a double bond at the 3rd position or higher, -(CH ₂ ) _P -C-(CF ₃ ) ₃ , CN and an unsubstituted or substituted benzene ring, wherein the substituent of the benzene ring is selected from the group consisting of C ₁ -C ₆ straight or branched alkyl, C ₁ -C ₆ alkoxy, -C-(CH ₃ ) ₃ , halogen, -CF ₃ , NO ₂ , CN, COR ¹⁰⁷ , -COOR ¹⁰⁷ , -OCOR ¹⁰⁷ , -CONR ¹⁰⁶ R ¹⁰⁷ , -NR ¹⁰⁶ COR ^{R 107} , OCOOR ¹⁰⁷ , -OCONR ¹⁰⁶ R ¹⁰⁷ , -NR ¹⁰⁶ COOR ¹⁰⁷ , -F, -Cl, -CF ₃ and -OCF ₃ ; wherein R ¹⁰⁶ is selected from the group consisting of hydrogen, lower alkyl and lower alkenyl; R ¹⁰⁷ is selected from the group consisting of hydrogen, C ₁ -C ₁₈ alkyl and C ₃ -C ₁₈ alkenyl having a double bond at position 3 or higher; p is an integer between 0 and 12; R ¹⁰⁵ is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkoxy; and wherein n is 0, 1, 2 or 3; Z is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, wherein one or more carbon atoms may be replaced by -O-COO-, -OCO-, -OOC-, -O(CO)O-, -N-, NR ^a -, -CON-, -CO-R ^b1 or -NH-R ^c , wherein ^Ra is C ₁ -C ₁₂ alkyl, R ^b1 and R ^c are independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an organic group having 2 to 30 carbon atoms including at least one aromatic ring, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms.

The term "lower alkyl" is understood to include _C1-6 branched or straight chain alkyl groups. Examples of lower alkyl groups include methyl, ethyl, propyl, butyl, pentyl and hexyl.

The term "lower alkenyl" is understood to include _C3-6 branched or straight chain alkenyl groups wherein the double bond is located at position 2 or higher. Examples of lower alkenyl groups include 2-propenyl, 3-butenyl, 3-isopentenyl, 4-pentenyl, 5-hexenyl and 4-isohexenyl.

The term "lower alkoxy" should be understood to include _C1-6 achiral, branched or straight chain alkoxy. Examples of lower alkoxy include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, etc.

In one embodiment, moieties C and D are independently selected from phenyl or cyclohexyl, with the proviso that at least one of moieties C or D is phenyl.

In a preferred embodiment, the moiety E is a benzene ring.

In another embodiment, the moiety F is a group of formula (IIIb) or (IIIc).

In one embodiment, at least one of the moieties C and D is an aromatic ring or contains an aromatic ring and the group of formula (IV) is Where n is an integer between 0 and 24.

Suitable polymerizable liquid crystal compounds are known to those skilled in the art, for example, from WO 2020/260621 A1, WO 2021/037774 A1. Preferred polymerizable liquid crystal compounds include: ; ; ; ;and .

The polymerizable liquid crystal composition preferably comprises the polymerizable liquid crystal compound in an amount of 1.5 to 50 wt.-%, more preferably 5 to 40 wt.-%, even more preferably 8 to 30 wt.-%, and most preferably 10 to 30 wt.-%, relative to the total weight of the polymerizable liquid crystal composition.

The polymerizable liquid crystal composition comprises a polymerizable liquid crystal compound and a polymerization initiator of formula (I). In addition, the polymerizable liquid crystal composition may comprise at least one solvent and/or at least one additive.

Suitable solvents include ketones such as acetone, cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MBE), ketone (MIBK) and methylethylketone (MEK), amides such as N,N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone, N-vinylpyrrolidone and N,N-dimethylacetamide (AN), ethers such as tetrahydrofuran (THF), dipropylene glycol monomethyl ether, diethylene glycol butyl ether and 1,3-dioxolane (DXG), glycols such as ethylene glycol and dipropylene glycol, esters such as ethylcarbitol acetate, ethyl acetate (EA), 1-methoxy-2-propanol acetate (DXG), and 1-methoxy-2-propanol acetate (DXG). The preferred solvents include ketones, especially cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK) and methyl ethyl ketone (MEK), esters, especially ethyl acetate (EA) and 1-methoxy-2-propanol acetate (MPA), ethers, especially 1,3-dioxane (DXG), organic sulfur compounds, especially dimethyl sulfoxide (DMSO), and aromatic compounds, especially toluene.

The polymerizable liquid crystal composition preferably comprises a total amount of solvent in the range of 50 to 90 wt.-%, preferably 60 to 80 wt.-%, relative to the total weight of the polymerizable liquid crystal composition.

Suitable additives include antioxidants, promoters, dyes, polymerization inhibitors, activators, fillers, chain transfer inhibitors, pigments, antistatic agents, flame retardants, thickeners, tactile detackifiers, surfactants, viscosity regulators, extender oils, plasticizers, tackifiers, catalysts, sensitizers, stabilizers, lubricants, dispersants, polymeric binders and/or Monomeric compounds which form polymeric binders or, in the case of emulsion coatings and printing inks, dispersing aids, hydrophobic agents, tackifiers, flow improvers, leveling agents, defoamers, deaerators, diluents, additives, colorants, dyes and pigments, curing inhibitors, chiral additives, isotropic or anisotropic fluorescent and/or non-fluorescent dyes, dichroic dyes and crosslinking agents.

In order to improve the storage stability, a polymerization inhibitor is preferably added to the polymerizable liquid crystal composition. Suitable polymerization inhibitors include aromatic polymerization inhibitors such as 4-tert-butylcatechol (TBC), 4-methoxyphenol (MEHQ), 2,6-di-tert-butyl-4-methylphenol (BHT) and hydroquinone (HQ), especially 2,6-di-tert-butyl-4-methylphenol (BHT).

The crosslinking agent is a compound containing one or more complementary reactive units (such as hydroxyl, thiol or amine) or one or more polymerizable groups (such as olefinic double bonds) which can react with the polymerizable groups of the anisotropic compound of formula (II). In order to maintain the liquid crystal phase, the amount of the crosslinking agent is preferably 0.015 to 10 wt.-%, preferably 0.25 to 3.0 wt.-%, relative to the total weight of the polymerizable liquid crystal composition.

Preferably, the crosslinking agent is selected from monofunctional, difunctional and polyfunctional compounds containing at least one olefinic double bond and polythiols having two or more thiol groups per molecule.

Suitable polythiols include monomeric aliphatic polythiols, oligomeric and polymeric polythiols.

A suitable polymeric polythiol is poly(propylene ether glycol) bis(β-butyl propionate).

Preferred aliphatic dithiols include 1,2-ethanedithiol, butanedithiol, 1,3-propanedithiol, 1,5-pentanedithiol, 2,3-dialkyl-1-propanol, dithioerythritol, 3,6-dioxa-1,8-octanedithiol, 1,8-octanedithiol hexanedithiol, diethylene glycol dithiodiol, pentanedithiol, decanedithiol, 2-methyl-1,4-butanedithiol, dibutylethylphenylmethane, 1,9-nonanedithiol (1,9-dibutylnonane), and dibutylacetate.

Preferred oligomeric dithiols include difunctional alkylformate oligomers derived from end-capping moieties of hydroxyethyl mercaptan, hydroxypropyl mercaptan, dialkylpropane, dialkylethane, as described in US Pat. No. 5,744,514.

Preferred trithiol functional compounds include trimethylolpropane tris-mercaptopropionate, trimethylolpropane tris-mercaptopropionate (TMPTSH), trimethylolpropane tris-mercaptopropionate, trimethylolpropane tris-mercaptopropionate, trimethylolpropane tris-mercaptopropionate (11-pentyl undecanoate), and trimethylolpropane tris-mercaptopropionate (11-pentyl undecanoate).

Preferred tetrafunctional thiols include pentaerythritol tetrakis(3-mercaptopropionate); PTMP, pentaerythritol tetrakis(3-mercaptopropionate); and pentaerythritol tetrakis(11-mercaptoundecanoate).

A particularly preferred polythiol crosslinking agent is pentaerythritol tetra(3-pentyl propionate) (PTMP).

Monofunctional, difunctional and polyfunctional compounds containing at least one olefinic double bond are generally capable of photopolymerization. Examples of such compounds are vinyl esters of carboxylic acids (e.g. lauric acid, myristic acid, palmitic acid and stearic acid), and vinyl esters of dicarboxylic acids (e.g. succinic acid, adipic acid, allyl and vinyl ethers), and methacrylates and acrylates of monofunctional alcohols (e.g. lauryl alcohol, myristyl alcohol, palmitic acid and stearyl alcohol), and diallyl and divinyl ethers of difunctional alcohols (e.g. ethylene glycol and 1,4-butanediol).

Other examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, styrene, core-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinyl pyridine, N-vinyl pyrrolidone, vinyl sulfonic acid, fatty acid vinyl esters, a,b-ethylenically unsaturated carboxylic acids, alkyl esters of (meth)acrylic acid wherein the alkyl group has 1 to 18 carbon atoms, hydroxyalkyl esters of (meth)acrylic acid wherein the hydroxyalkyl group has 1 to 18 carbon atoms, aminoalkyl esters of (meth)acrylic acid wherein the aminoalkyl group has 1 to 18 carbon atoms, ether oxyalkyl esters of (meth)acrylic acid wherein the ether oxyalkyl group has 3 to 18 carbon atoms, N-vinyl acetamide, vinyl tert-butylbenzoate, vinyl N,N-dimethylaminobenzoate, vinyl benzoate, vinyl pivalate (vinyl ester), vinyl benzoate, vinyl pivalate (vinyl ester), vinyl benzoate, vinyl pivalate (vinyl ester), vinyl benzoate, vinyl pivalate (vinyl ester), vinyl benzoate, vinyl pivalate (vinyl ester), vinyl benzoate, vinyl pivalate (vinyl ester), vinyl benzoate, vinyl pivalate, ... pivalate), 2,2-dimethylvinyl butyrate, 2,2-dimethylvinyl valerate, 2-methyl-2-butyric acid vinyl, vinyl propionate, vinyl stearate, 2-ethyl-2-methylbutyric acid vinyl, dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyl adamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-acryloyloxyethyl succinate, 2-propenyl As non-liquid crystal polymerizable compounds as monofunctional compounds, acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, mono(meth)acrylate, polypropylene glycol having a degree of polymerization of 2 to 100 and terminated with di(meth)acrylate or an alkyl group having 1 to 6 carbon atoms, and mono(meth)acrylate of a copolymer of polyethylene glycol with ethylene oxide and polypropylene oxide, etc.

Examples of the difunctional compound include 1,4-divinyloxybutane (BDDV), 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, dihydroxymethyltricyclodecane diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A EO addition diacrylate, bisphenol A diacrylate glycidyl, polyethylene glycol diacrylate, and methacrylate.

BDDV is a particularly preferred crosslinking agent.

Examples of trifunctional or higher functional polyfunctional compounds include pentaerythritol triacrylate, trihydroxymethylpropane triacrylate, trihydroxymethyl EO addition triacrylate, triacryloxyethyl phosphate, tris(acryloxyethyl) isocyanate, alkyl-modified dipentaerythritol triacrylate, EO-modified trihydroxymethylpropane triacrylate, PO-modified trihydroxymethylpropane triacrylate, pentaerythritol tetraacrylate, alkyl-modified dipentaerythritol tetraacrylate, ditrihydroxymethylpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxy pentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, pentaerythritol tri(meth)acrylate, tris(meth)acrylate, and di(meth)acrylate. Hydroxymethylpropane tri(meth)acrylate, trihydroxymethyl EO addition tri(meth)acrylate, tris(meth)acryloxyethyl phosphate, tris(meth)acryloxyethyl, isocyanate, alkyl-modified dipentatriol tri(meth)acrylate, EO-modified trihydroxymethylpropane tri(meth)acrylate, PO-modified trihydroxymethylpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, alkyl-modified dipentatriol tetra(meth)acrylate, ditrihydroxymethylpropane tetra(meth)acrylate, dipentatriol hexa(meth)acrylate, dipentatriol monohydroxy pentamethacrylate, and alkyl-modified dipentatriol pentamethacrylate. Other examples include dipentatriol hexaacrylate in which dipentatriol is modified with caprolactone, which is commercially available, for example, as Kayarad DPCA-20, Kayarad DPCA-30, Kayarad DPCA-60, and Kayarad DPCA-120 from Nippon Kayaku Co., Ltd. Kayarad DPCA-20 is a particularly preferred crosslinking agent.

In one embodiment, the crosslinking agent is selected from monofunctional, difunctional and polyfunctional compounds containing at least one olefinic double bond and polythiols comprising molecules having two or more thiol groups per molecule.

In order to reduce the unevenness of film thickness when forming thin films such as optical anisotropes and optical films, it is preferred to add a leveling agent to the polymerizable liquid crystal composition. Suitable leveling agents include polysiloxanes such as modified polydimethylsiloxane (PDMS), acrylate-based agents such as polyacrylates, fluorocarbon-based agents, and hydrocarbon-based leveling agents, especially polyacrylates such as Tego ^® Flow available from Evonik.

The polymerizable liquid crystal composition preferably comprises a leveling agent in an amount of 0.0075 to 2.0 wt.-%, preferably 0.02 to 0.5 wt.-%, relative to the total weight of the polymerizable liquid crystal composition.

In addition to the polymerizable liquid crystal compound (i), other polymerizable compounds may be added to the polymerizable liquid crystal composition to increase the mechanical strength of the liquid crystal film, or to increase the chemical resistance, or both. Such compounds are preferably mesogens. Preferably, the other polymerizable compounds are selected from reactive mesogens, most preferably from monoreactive and direactive mesogens.

The term "mesogenic" means a compound comprising one or more calamitic (rod-shaped or plate/lath-shaped) or discotic (disk-shaped) mesogenic groups. The term "mesogenic group" means a group having the ability to induce liquid crystal (LC) phase behavior. A compound comprising a mesogenic group does not necessarily have to exhibit a liquid crystal phase by itself. It may also exhibit liquid crystal phase behavior only in a mixture with other compounds or when the mesogenic compound or material or a mixture thereof is polymerized.

The rod-shaped liquid crystal group typically comprises a liquid crystal core composed of one or more aromatic or non-aromatic cyclic groups connected to each other directly or via a linking group, optionally comprising an end group connected to the end of the liquid crystal core, and optionally comprising one or more side groups connected to the long side of the liquid crystal core, wherein these end groups and side groups can be selected from ethylene (carbyl) or alkyl groups, polar groups (such as halogen, nitro, hydroxyl, etc.) or polymerizable groups. The term "reactive mesogen" (RM) means a polymerizable liquid crystal compound. A polymerizable compound having one polymerizable group is also called a "single-reactive" compound, a compound having two polymerizable groups is also called a "di-reactive" compound, and a compound having more than two polymerizable groups is called a "multi-reactive" compound. Examples of such compounds are well known to those skilled in the art and are described, for example, in WO 2018/099883. An example of another polymerizable compound is [3-methyl-4-[4-(6-prop-2-enyloxyhexyloxy)benzoyl]oxy-phenyl]4-(6-prop-2-enyloxyhexyloxy)benzoate (FPC-1), as shown in the figure below.

The present invention further relates to a liquid crystal film which is a cured product of a polymerizable liquid crystal composition.

The present invention also relates to a method for manufacturing a liquid crystal film, which comprises aligning a polymerizable liquid crystal compound to obtain a polymerizable liquid crystal layer in which the polymerizable liquid crystal compound has a predetermined orientation; polymerizing the polymerizable liquid crystal compound to form a network in which the orientation of the liquid crystal is fixed; and pressing the liquid crystal film layer onto a pressure-sensitive adhesive coated on a substrate.

The alignment of the polymerizable liquid crystal composition can be achieved, for example, by coating an organic solution of the polymerizable liquid crystal composition onto an alignment substrate provided with an alignment layer. The alignment layer generally comprises a photo-orientable substance, wherein anisotropic properties can be induced when exposed to alignment light. The induced anisotropy appropriately provides alignment capability for the polymerizable liquid crystal composition of the present invention. The term "alignment direction" refers to a preferred direction induced in the polymerizable liquid crystal composition, i.e., the alignment direction is the direction in which the liquid crystal molecules are aligned.

The photo-orientable material comprises a photo-orientable portion which is capable of forming a preferred direction when exposed to aligning light and thus producing anisotropic properties. Such photo-orientable portions preferably have anisotropic absorption properties. Typically, such portions exhibit absorption in a wavelength range of 230 to 500 nm. Preferably, the photo-orientable portion exhibits light absorption in a wavelength range of 300 to 450 nm, more preferably a portion that exhibits absorption in a wavelength range of 310 to 380 nm.

Preferably, the photo-orientable moiety has carbon-carbon, carbon-nitrogen or nitrogen-nitrogen double bonds.

For example, the photo-orientable moiety is a substituted or unsubstituted azo dye such as anthraquinone, coumarin, mericyanine, 2-phenylazothiazole, 2-phenylazobenzothiazole, stilbene, cyanostilbene, fluorostilbene, cinnamonitrile, chalcones, cinnamate, cyanocinnamate, stilbazolium, 1,4-bis(2-phenylethylenyl)benzene, 4,4'-bis(arylazo)stilbene, perylene, 4,8-diamino-1,5-naphthoquinone dye, aryloxycarboxylic acid derivatives, aryl esters, N-arylamide, polyimide, and diaryl ketones having a ketone moiety or ketone derivative conjugated to two aromatic rings, such as, for example, substituted diphenyl ketones, diphenylketone imines, phenylhydrazones, and semicarbazones.

The preparation of the anisotropic absorbent materials listed above is well known, as shown, for example, in U.S. Patent No. 4,565,424 to Hoffman et al., U.S. Patent No. 4,401,369 to Jones et al., U.S. Patent No. 4,122,027 to Cole, Jr. et al., U.S. Patent No. 4,667,020 to Etzbach et al., and U.S. Patent No. 5,389,285 to Shannon et al.

Preferably, the photo-orientable moiety comprises an arylazo, a poly(arylazo), a stilbene, a cyanostilbene, a cinnamate, or a chalcone.

The photo-orientable substance may be, in particular, a monomer, an oligomer or a polymer. The photo-orientable moiety may be covalently bonded, for example, within the main chain or within the side chains of a polymer or oligomer, or it may be part of a non-polymerizable monomer or other compound. The photo-orientable substance may further be a copolymer comprising different types of photo-orientable moieties, or it may be a copolymer comprising side chains with and without photo-orientable moieties.

The polymer refers to, for example, polyacrylate, polymethacrylate, polyimide, polyurethane, polyamide, polymaleimide, poly-2-chloroacrylate, poly-2-phenylacrylate; unsubstituted or C ₁ -C ₆ alkyl-substituted polyacrylamide, polymethacrylamide, poly-2-chloroacrylamide, poly-2-phenylacrylamide, polyether, polyvinyl ether, polyester, polyvinyl ester, polystyrene derivative, polysiloxane, linear or branched alkyl ester of polyacrylic acid or polymethacrylic acid; polyphenoxyalkyl acrylate, polyphenoxyalkyl methacrylate, polyphenylalkyl methacrylate having an alkyl residue of 1 to 20 carbon atoms; polyacrylonitrile, polymethacrylonitrile, cycloolefin polymer, polystyrene, poly-4-methylstyrene or a mixture thereof.

The photo-orientable material may also include photosensitizers such as ketocoumarins and diphenyl ketones.

In addition, preferred photo-orientable monomers or oligomers or polymers are described in US Patents US 5,539,074, US 6,201,087, US 6,107,427, US 6,632,909 and US 7,959,990.

After coating, the organic solvent is removed to obtain a solvent-free liquid crystal layer in which the molecules have a predetermined orientation.

The alignment of the polymerizable liquid crystal composition can also be achieved by other known means for aligning liquid crystals, such as coating the polymerizable liquid crystal composition on a substrate that has been pre-treated by a rubbing technique.

The polymerizable liquid crystal compound is polymerized to form a network in which the orientation of the liquid crystals is fixed.

The steps of polymerizing the polymerizable liquid crystal composition and exposing it to the aligning light may be performed in any order. Polymerization may be initiated before or after exposure to the aligning light, or polymerization and exposure may occur simultaneously.

The liquid crystal composition may also be applied on a carrier, and the carrier may have an aligning surface, which would mean that the surface has the ability to align the liquid crystal. The carrier may already provide alignment without further treatment. For example, if a plastic substrate is used as a carrier, it may provide alignment on the surface due to the manufacturing method (e.g. extrusion or stretching of the substrate). The carrier may also be brushed or rubbed or embossed with directional microstructures to produce the alignment ability.

The carrier may be rigid or flexible and may have any form or shape. In principle, it may consist of any material. Preferably, the carrier comprises plastic, glass or metal or is a silicon wafer. In the case where the carrier is flexible, preferably, the carrier is plastic or a metal foil. Preferably, the surface of the carrier is flat. For some applications, the carrier may comprise topographical surface structures, such as microstructures like microlenses or microprisms, or structures showing shape mutations, such as rectangular structures. Preferably, the carrier is transparent. The carrier may also be subjected to a treatment before being coated with the polymerizable liquid crystal composition according to the invention.

The carrier may be moved during the deposition of the polymerizable liquid crystal composition. For example, a layer of the polymerizable liquid crystal composition may be produced in a continuous roll-to-roll process by depositing the composition onto a moving flexible foil (preferably plastic or metal). The resulting film may then be wound up on a roll together with the carrier foil, or the film may be peeled off the carrier and then wound up as a free-standing film without a carrier.

The carrier may have additional layers, such as organic layers, dielectric layers or metal layers. The layers may have different functions, for example, an organic layer may be applied as a primer layer, which increases the compatibility of the material to be applied with the carrier. The metal layer may be used as an electrode, for example when used in an electro-optical device such as a display, or may have the function of a reflector. The carrier may also be an optical element or device with certain functions, such as a substrate for an LCD, which may include, for example, thin film transistors, electrodes or color filters. In another example, the carrier is a device comprising an OLED layer structure. The carrier may also be a polarizer, such as a polarizing film or a sheet polarizer, a reflective polarizer, such as the commercially available Vikuity™ DBEF film.

The polymerizable liquid crystal composition can be applied to the substrate by general coating and printing methods known in the art. Coating methods include, for example, spin coating, blade coating, knife coating, reverse roll coating, transfer roll coating, gravure roll coating, contact-on-gel roll coating, casting, spray coating, slit-hole coating, roll coating, electrodeposition coating, dip coating or mold coating. Printing methods include relief printing, such as flexographic printing, inkjet printing, gravure printing, such as direct gravure printing or indirect gravure printing, lithographic printing, such as plate printing, or stencil printing, such as screen printing. The preferred printing method is inkjet printing.

Liquid crystal films exhibit birefringence with reversed wavelength dispersion.

The reverse wavelength dispersion of a material can be evaluated by the Re ₄₅₀ value (indicating the retardation of the material at a wavelength of 450 nm), the Re ₅₅₀ value (indicating the retardation of the material at a wavelength of 550 nm), and the Re ₆₅₀ value (indicating the retardation of the material at a wavelength of 650 nm). In a birefringent material with reverse wavelength dispersion, the Re ₄₅₀ /Re ₅₅₀ value is less than 1.0 and the Re ₆₅₀ /Re ₅₅₀ value is greater than 1.0, indicating that the magnitude of birefringence (Δn) increases with increasing wavelength λ.

The present invention further provides a use of the liquid crystal film according to the present invention, which is used to manufacture optical devices or electro-optical devices, such as optical compensators for viewing angle enhancement of liquid crystal displays, or achromatic retarders for display applications (including OLED anti-reflection).

The present invention will be described in more detail with reference to the accompanying drawings and the following embodiments. Embodiments

The following abbreviations are used: BDDV 1,4-divinyloxybutane BHT 2,6-bis(tert-butyl)-4-methylphenol CE1 [(E)-1-(4-phenylthiohydrogen benzoyl) heptylene amino] benzoate CE2 [(Z)-1-[9-ethyl-6-(2-methylbenzoyl) carbazole-3-yl] ethylene amino] acetate CE3 [(Z)-[1-[4-[4-(benzofuran-2-carbonyl)phenyl]thiohydrogen phenyl]-4-methylpentylene] amino] acetate DPCA Kayarad DPCA-20, a dipentylthritol multifunctional acrylate in which dipentylthritol is caprolactone modified FPC-1 [3-methyl-4-[4-(6-prop-2-enyloxyhexyloxy) benzoyl] oxyphenyl] 4-(6-prop-2-enyloxyhexyloxy)benzoate LPP Linear photopolymerizable polymer PH1 [4-[6-[(2)-2-acetyloxyiminohexyl]-9-(2-ethylhexyl)carbazole-3-carbonyl]phenyl]acetate PH2 [4-[6-[(2)-2-acetyloxyiminohexyl]-9-ethyl-carbazole-3-carbonyl]phenyl]hexanoate PH3 [1-[9-(2-ethylhexyl)-6-(4-methoxycarbonyloxybenzyl)carbazole-3-carbonyl]propylideneamino]acetate PH4 [1-[9-ethyl-6-(4-propoxycarbonyloxybenzyl)carbazole-3-carbonyl]pentylideneamino]acetate PH5 [1-[6-(4-Butoxycarbonyloxybenzyl)-9-ethyl-carbazole-3-carbonyl]hexylideneamino] acetate PH6 [1-[6-(4-ethoxycarbonyloxybenzyl)-9-ethyl-carbazole-3-carbonyl]hexylideneamino] acetate PTMP Pentaerythritol tetra(3-pentylpropionate) RWD1 [2-[[1,3-Benzothiazol-2-yl(hexyl)hydrazono]methyl]-4-(4-pentylcyclohexanecarbonyl)oxy-phenyl] 4-(6-prop-2-enyloxyhexyloxy)benzoate RWD2 [3-[[1,3-Benzothiazol-2-yl(hexyl)hydrazono]methyl]-4-(4-ethylcyclohexanecarbonyl)oxy-phenyl] 4-(6-prop-2-enyloxyhexyloxy)benzoate RWD3 [3-[[1,3-benzothiazol-2-yl(hexyl)hydrazono]methyl]-4-[4-(6-prop-2-enyloxyhexyloxy)benzoyl]oxy-phenyl] 4-(6-prop-2-enyloxyhexyloxy)benzoate RWD4 3-[[hexyl(quinoline) [(4-(6-prop-2-enyloxyhexyloxy)benzoyl]oxy-phenyl] 4-(6-prop-2-enyloxyhexyloxy)benzoate] cellulose triacetate

method

Alignment quality

The alignment quality of the liquid crystal in the film is checked by placing the film between two crossed polarizers and adjusting to obtain a dark state. If the dark state shows no defects and the liquid crystal is well oriented, the alignment quality is defined as very good. If the dark state has light leakage due to uneven liquid crystal orientation, the alignment quality is defined as good. If the dark state has light leakage and some areas have crystals, the alignment quality is defined as medium. If the liquid crystal is not oriented and there is no dark state, the alignment quality is defined as poor.

Thermal reliability

Film layers of composition 1 to composition X below were pressed onto a pressure sensitive adhesive PSA OC8171 (3M) coated onto a glass substrate. The TAC substrate was then peeled off. The total stack of glass/PSA/polymer film was then subjected to a thermal reliability experiment. The film was stressed at 85°C for up to 200 hours. An Axoscan ellipsoidal polarimeter was used to determine the delay before and after thermal stress. The reliability % of the heat treatment was quantified by the difference in delay at 550 nm before and after heating at 85°C, ΔRe, divided by the delay before stress.

The thermal reliability evaluation results are summarized in Table 1.

Preparation of alignment layer

TAC 80 μm (FT TD80ULM from Fujifilm) substrates were spin coated with a photoalignment composition (LPP polymer with a solid content of 3% in cyclopentanone, as described in WO 2012/085048). The coated substrates were dried at 80°C for 30 seconds. The thickness of the resulting polymer layer was about 100 nm. Subsequently, the polymer layer was exposed to collimated and linearly polarized UV (LPUV) light (280-320 nm) at 250 mJ/ ^cm2 . The polarization plane was 0° relative to a reference edge on the substrate.

Preparation of liquid crystal film

The polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition are shown below. RWD1 RWD2 RWD3

RWD1 and RWD2 were obtained according to the procedure described in WO 2021/037774 A1. RWD3 was obtained according to the procedure described in US 2014/0142266 A1.

The photopolymerization initiator used in the polymerizable liquid crystal composition is shown below. CE1 CE3 CE2 Omnirad 819 Omnirad 369 PH1 PH2 PH3 PH4 PH5 PH6

Embodiment 1

A 35.0 wt.-% solution was prepared by mixing 15.050 wt.-% RWD1, 12.443 wt.-% RWD2, 0.0175 wt.-% BHT (obtained from Sigma-Aldrich), 0.7 wt.-% BDDV (obtained from BASF), 3.92 wt.-% FPC-1 (obtained from Synthon Chemicals), 2.8 wt.-% PH1 (obtained from BASF) and 0.070 wt.-% Tego ^® Flow 300 (obtained from Evonik) in cyclohexanone/toluene 40/60. The solution was stirred well at 40°C until the solid was completely dissolved. The solution was spin-coated at 800 rpm onto the alignment layer of the substrate obtained as described above to obtain a film. The film was annealed in an oven at 68° C. for 5 minutes. Photopolymerization was performed by irradiating UV light using a high-pressure mercury lamp for about 2 minutes (total UV amount: 2.3 J) at 40° C. and 50° C. in a nitrogen atmosphere, respectively.

Embodiment 2

A film was prepared as in Example 1 except that PH2 was used instead of PH1. The film was annealed in an oven at 69°C for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes (total UV amount: 2.3 J) at 50°C in a nitrogen atmosphere.

Embodiment 3

A film was prepared as in Example 1 except that PH3 was used instead of PH1. The film was annealed in an oven at 69°C for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes (total UV amount: 2.3 J) at 50°C in a nitrogen atmosphere.

Embodiment 4

A film was prepared as in Example 1 except that PH4 was used instead of PH1. The film was annealed in an oven at 69°C for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes (total UV amount: 2.3 J) at 50°C in a nitrogen atmosphere.

Embodiment 5

A film was prepared as in Example 1 except that PH 5 was used instead of PH 1. The film was annealed in an oven at 69° C. for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes (total UV amount: 2.3 J) at 50° C. in a nitrogen atmosphere.

Embodiment 6

A film was prepared as in Example 1 except that PH 6 was used instead of PH 1. The film was annealed in an oven at 69° C. for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes (total UV amount: 2.3 J) at 50° C. in a nitrogen atmosphere.

Embodiment 7

A 35.0 wt.-% solution was prepared by mixing 15.050 wt.-% RWD1, 12.443 wt.-% RWD2, 0.0175 wt.-% BHT, 0.7 wt.-% BDDV, 3.92 wt.-% FPC-1, 2.8 wt.-% CE4 (obtained from BASF), 0.070 wt.% Tego ^® Flow 300 in cyclohexanone/toluene 40/60. The solution was stirred well at 40°C until the solid was completely dissolved. The solution was spin-coated at 800 rpm onto the alignment layer of the substrate obtained as described above to obtain a film. The film was annealed in an oven at 71°C for 5 minutes. The sample was cooled to room temperature. Photopolymerization was performed by irradiating UV light using a high-pressure mercury lamp in a nitrogen atmosphere for about 2 minutes at 40°C and 50°C respectively (total UV dose: 2.3 J).

Embodiment 8

A 35.0 wt.-% solution was prepared by mixing 15.050 wt.-% RWD1, 12.443 wt.-% RWD2, 0.0175 wt.-% BHT, 0.7 wt.-% BDDV, 3.92 wt.-% FPC-1, 2.8 wt.-% CE2 (obtained from BASF), 0.070 wt.-% Tego ^® Flow 300 in cyclohexanone/toluene 40/60. The solution was stirred well at 40°C until the solid was completely dissolved. The solution was spin-coated at 800 rpm onto the alignment layer of the substrate obtained as described above to obtain a film. The film was annealed in an oven at 61°C for 5 minutes. The sample was cooled to room temperature. Photopolymerization was performed by irradiating UV light using a high-pressure mercury lamp in a nitrogen atmosphere for about 2 minutes at 40°C and 50°C (total UV dose: 2.3 J).

Embodiment 9

A 35.0 wt.-% solution was prepared by mixing 15.050 wt.-% RWD1, 12.443 wt.-% RWD2, 0.0175 wt.-% BHT, 0.7 wt.-% BDDV, 3.92 wt.-% FPC-1, 2.8 wt.-% CE1 (obtained from BASF), 0.070 wt.-% Tego ^® Flow 300 in cyclohexanone/toluene 40/60. The solution was stirred well at 40°C until the solid was completely dissolved. The solution was spin-coated at 800 rpm onto the alignment layer of the substrate obtained as described above to obtain a film. The film was annealed in an oven at 63°C for 5 minutes. The sample was cooled to room temperature. Photopolymerization was performed by irradiating UV light using a high-pressure mercury lamp in a nitrogen atmosphere for about 2 minutes at 40°C and 50°C (total UV dose: 2.3 J).

Embodiment 10

A 35.0 wt.-% solution was prepared by mixing 15.050 wt.-% RWD1, 12.443 wt.-% RWD2, 0.0175 wt.-% BHT, 0.7 wt.-% BDDV, 3.92 wt.-% FPC-1, 2.8 wt.-% Omnirad® 819 (obtained from IGM Resins), 0.070 wt.-% ^Tego® Flow 300 in cyclohexanone/toluene 40/60. The solution was stirred well at 40°C until the solid was completely dissolved. The solution was spin-coated at 800 rpm onto the alignment layer of the substrate obtained as described above to obtain a film. The film was annealed in an oven at 63°C for 5 minutes. The sample was cooled to room temperature. Photopolymerization was performed by irradiating UV light using a high-pressure mercury lamp in a nitrogen atmosphere for about 2 minutes at 40°C and 50°C (total UV dose: 2.3 J).

Embodiment 11

A 35.0 wt.-% solution was prepared by mixing 15.050 wt.-% RWD1, 12.443 wt.-% RWD2, 0.0175 wt.-% BHT, 0.7 wt.-% BDDV, 3.92 wt.-% FPC-1, 2.8 wt.-% Omnirad® 369 (obtained from IGM Resins), 0.070 wt.-% ^Tego® Flow 300 in cyclohexanone/toluene 40/60. The solution was stirred well at 40°C until the solid was completely dissolved. The solution was spin-coated at 800 rpm onto the alignment layer of the substrate obtained as described above to obtain a film. The film was annealed in an oven at 56°C for 5 minutes. The sample was cooled to room temperature. Photopolymerization was performed by irradiating UV light using a high-pressure mercury lamp in a nitrogen atmosphere for about 2 minutes at 40°C and 50°C, respectively (total UV dose: 2.3 J).

Embodiment 12

A 35.0 wt.-% solution was prepared by mixing 15.4 wt.-% RWD1, 13.493 wt.-% RWD2, 0.0175 wt.-% BHT, 0.7 wt.-% BDDV, 3.92 wt.-% FPC-1, 1.4 wt.-% PH1, 0.070 wt.-% Tego ^® Flow 300 in cyclohexanone/toluene 40/60. The solution was stirred well at 40°C until the solid was completely dissolved. The solution was spin-coated at 800 rpm onto the alignment layer of the substrate obtained as described above to obtain a film. The film was annealed in an oven at 77°C for 5 minutes. The sample was cooled to room temperature and then photopolymerized by irradiating UV light using a high-pressure mercury lamp at 50°C for about 2 minutes (total UV dose: 2.3 J) in a nitrogen atmosphere.

Embodiment 13

A film was prepared as in Example 12, except that CE4 was used instead of PH1. The film was annealed in an oven at 81°C for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes at 50°C in a nitrogen atmosphere (total UV amount: 2.3 J).

Embodiment 14

A film was prepared as in Example 12, except that CE2 was used instead of PH1. The film was annealed in an oven at 74°C for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes (total UV amount: 2.3 J) at 50°C in a nitrogen atmosphere.

Embodiment 15

A film was prepared as in Example 12, except that CE1 was used instead of PH1. The film was annealed in an oven at 75°C for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes at 50°C in a nitrogen atmosphere (total UV amount: 2.3 J).

Embodiment 16

A 35.0 wt.-% solution was prepared by mixing 15.75 wt.-% RWD1, 11.74 wt.-% RWD2, 0.0175 wt.-% BHT, 0.7 wt.-% DPCA (obtained from Nikka Fine), 3.92 wt.% FPC-1, 2.8 wt.% PH1, 0.070 wt.% Tego ^® Flow 300 in cyclohexanone/toluene 40/60. The solution was then stirred well until the solid was completely dissolved at 40°C. The solution was stirred well at 40°C until the solid was completely dissolved. The solution was spin-coated at 800 rpm onto the alignment layer of the substrate obtained as described above to obtain a film. The film was annealed in an oven at 67°C for 5 minutes. The sample was cooled to room temperature and then photopolymerized by irradiating UV light using a high-pressure mercury lamp at 50°C for about 2 minutes (total UV dose: 2.3 J) in a nitrogen atmosphere.

Embodiment 17

A film was prepared as in Example 16, except that Ominrad® 819 was used instead of PH1. The film was annealed in an oven at 60° C. for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes (total UV amount: 2.3 J) at 50° C. in a nitrogen atmosphere.

Embodiment 18

A film was prepared as in Example 16, except that PTMP (obtained from Sigma-Aldrich) was used instead of DPCA in the example. The film was annealed in an oven at 65°C for 5 minutes, and then photopolymerized at 50°C by irradiating UV light using a high-pressure mercury lamp in a nitrogen atmosphere for about 2 minutes (total UV amount: 2.3 J).

Embodiment 19

A film was prepared as in Example 16, except that PH1 was replaced with Omnirad 819 and DPCA was replaced with PTMP. The film was annealed in an oven at 60°C for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes (total UV amount: 2.3 J) at 50°C in a nitrogen atmosphere.

Embodiment 20

A film was prepared as in Example 16 except that DPCA was not added. The film was annealed in an oven at 69° C. for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes at 50° C. in a nitrogen atmosphere (total UV amount: 2.3 J).

Embodiment 21

A film was prepared as in Example 16, except that Omnirad 819 was used instead of PH1 and DPCA was not added. The film was annealed in an oven at 63°C for 5 minutes and then photopolymerized by irradiating UV light using a high-pressure mercury lamp for about 2 minutes (total UV amount: 2.3 J) at 50°C in a nitrogen atmosphere.

Embodiment 22

A 35.0 wt.-% solution was prepared by mixing 31.41 wt.-% RWD3, 0.0175 wt.-% inhibitor BHT, 0.7 wt.-% BDDV, 2.8 wt.-% PH1, 0.070 wt.-% Tego ^® Flow 300 in cyclohexanone/toluene 40/60. The solution was stirred well at 40°C until the solid was completely dissolved. The solution was spin-coated at 800 rpm onto the alignment layer of the substrate obtained as described above to obtain a film. The film was annealed in an oven at 61°C for 5 minutes. The sample was cooled to room temperature and then photopolymerized by irradiating UV light using a high-pressure mercury lamp at 50°C for about 2 minutes (total UV dose: 2.3 J) in a nitrogen atmosphere.

Table 1 - Thermal Reliability Evaluation Embodiment RWD LCP Photoinitiator** Crosslinking agent Temperature during UV exposure [°C] Re ₄₅₀ /Re ₅₅₀ Reliability % at 550 nm (85°C) 1 RWD1/RWD2 PH1, 2.8 wt.-% BDDV 40 0.926 11.3% 2 RWD1/RWD2 PH2, 2.8 wt.-% BDDV 50 0.947 11.4% 3 RWD1/RWD2 PH3, 2.8 wt.-% BDDV 50 0.947 9.5% 4 RWD1/RWD2 PH4, 2.8 wt.-% BDDV 50 0.957 7.3% 5 RWD1/RWD2 PH5, 2.8 wt.-% BDDV 50 0.945 10.1% 6 RWD1/RWD2 PH6, 2.8 wt.-% BDDV 50 0.943 11.2% 7 * RWD1/RWD2 CE4, 2.8 wt.-% BDDV 40 0.936 19.5% 8 * RWD1/RWD2 CE2, 2.8 wt.-% BDDV 40 0.929 22.9% 9 * RWD1/RWD2 CE1, 2.8 wt.-% BDDV 40 0.895 21.6% 10 * RWD1/RWD2 Omnirad 819, 2.8 wt.-% BDDV 40 0.880 23.5% 11 * RWD1/RWD2 Omnirad 369, 2.8 wt.-% BDDV 40 0.899 32.5% 1 RWD1/RWD2 PH1, 2.8 wt.-% BDDV 50 0.926 7.1% 7 * RWD1/RWD2 CE4, 2.8 wt.-% BDDV 50 0.936 14.1% 8 * RWD1/RWD2 CE2, 2.8 wt.-% BDDV 50 0.929 14.4% 9 * RWD1/RWD2 CE1, 2.8 wt.-% BDDV 50 0.895 15.6% 10 * RWD1/RWD2 Omnirad 819, 2.8 wt.-% BDDV 50 0.880 12.0% 11 * RWD1/RWD2 Omnirad 369, 2.8 wt.-% BDDV 50 0.899 28.6% 12 RWD1/RWD2 PH1, 1.4 wt.-% BDDV 50 0.892 13.4% 13 * RWD1/RWD2 CE4, 1.4 wt.-% BDDV 50 0.906 17.0% 14 * RWD1/RWD2 CE2, 1.4 wt.-% BDDV 50 0.895 22.4% 15 * RWD1/RWD2 CE1, 1.4 wt.-% BDDV 50 0.874 28.3% 16 RWD1/RWD2 PH1, 2.8 wt.-% DPCA 50 0.941 5.2% 17 * RWD1/RWD2 Omnirad 819, 2.8 wt.-% DPCA 50 0.902 12.2% 18 RWD1/RWD2 PH1, 2.8 wt.-% PTMP 50 0.939 4.2% 19 * RWD1/RWD2 Omnirad, 2.8 wt.-% PTMP 50 0.903 12.6% 20 RWD1/RWD2 PH1, 2.8 wt.-% - 50 0.933 5.2% twenty one * RWD1/RWD2 Omnirad, 2.8 wt.-% - 50 0.900 10.5% twenty two RWD3 PH1, 2.8 wt.-% BDDV 50 0.976 5.0% *Comparative Example** Amount provided relative to the total weight of the polymerizable liquid crystal composition

The films of Example compositions 1 to 22 all showed very good alignment quality. The results shown in Table 1 illustrate the improved reliability of the Examples in which the α-oxoxime ester photoinitiator according to formula (I) was used.

without

without

Claims (15)

A polymerizable liquid crystal composition comprising: (i) a polymerizable liquid crystal compound capable of exhibiting birefringence with reverse wavelength dispersion when the polymerizable liquid crystal compound is in an aligned state; and (ii) a polymerization initiator represented by the following formula (I): (I) wherein R ¹ is hydrogen, C ₁ -C ₂₀ alkyl, C _{1 -C 6} alkyl-C ₃ -C ₆ cycloalkyl, C ₃ -C ₂₀ cycloalkyl or C ₂ -C ₁₂ alkenyl, wherein the C ₃ -C ₂₀ cycloalkyl or C ₂ -C ₁₂ alkenyl is uninterrupted or interrupted by one or more O, S, CO, NR ¹⁰ or COOR ⁴ ; or R ¹ is C ₁ -C ₂₀ alkyl, which is unsubstituted or interrupted by one or more halogens, OR ⁴ , SR ⁹ , NR ¹⁰ R ¹¹ , COOR ⁴ CONR ¹⁰ R ¹¹ , CN, PO(OR ^3a ) ₂ , S(O) _m -R ^3a , , C ₃ -C ₈ cycloalkyl, the C ₃ -C ₈ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ¹⁰ ; or is substituted by one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, C ₁ -C ₄ halogenated alkyl, CN, NO ₂ , OR ⁴ , SR ⁹ , NR ¹⁰ R ¹¹ , PO(OR ^3a ) ₂ or S(O) _m -R ^3a ; or R ¹ is C ₂ -C The C2- _C20 alkyl group is interrupted by one or more O, CO, S, C(O)O, OC(O), SO, _SO2 , phenylene, naphthylene or ^NR10 , wherein the interrupted _C2 - _{C20 alkyl group is unsubstituted or substituted by one or more halogen, C3-C8 cycloalkyl, OH, SH, OR4, SR9, COOR4, O(CO)-R3a, CONR10R11, NR10R11, C6-C20 aryl, C3-C20 heteroaryl ,} ^{C6 - C20 aromatic acyl or C3-C20 heteroarylcarbonyl, wherein the C6-C20 aryl, C3-C20 heteroaryl, C6-C20 aromatic acyl or C3-C20 heteroarylcarbonyl group is substituted by one or more halogen, C3-C8 cycloalkyl, OH, SH, OR4 , SR9 ,} _{COOR4 , O} ⁽ _{CO )} ^-R3a , CONR10R11, NR10R11, C6-C20 aryl, C3- _C20 heteroaryl, C6- _C20 aromatic acyl or C3- _{C20 heteroarylcarbonyl, wherein the C6-C20 aryl , C3} - _C20 heteroaryl, _C6 - _C20 aromatic acyl or C3- _C20 heteroarylcarbonyl R ¹ is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, _each of which _{is unsubstituted or substituted with one or more C 1 -C 20 alkyl, phenyl, halogen, C 1 -C 4 halogenated alkyl , CN} , NO ² , OR ₄ , SR ⁹ , NR ¹⁰ R ¹¹ , COOR ⁴ , ₍ ^CO )-R ^3a , ^{(CO)NR 10 R 11 , PO} (OR ^3a ) ₂ , S(O) ^m _-R ^3a or ^a group or substituted by one or more C ₂ -C ₂₀ alkyl groups, the C ₂ -C ₂₀ alkyl groups being interrupted by one or more O, S or NR ¹⁰ ; or substituted by one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl groups being unsubstituted or substituted by one or more halogens, COOR ⁴ , CONR ¹⁰ R ¹¹ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthyl groups, each of which is unsubstituted or substituted by OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or R ¹ is C ₂ -C or R 1 is a phenyloxycarbonyl _group , which is unsubstituted or substituted with a C ₁ -C ₆ alkyl group, a halogen, a phenyl group, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or R ¹ is a hydrogen, a C ₁ -C ₂₀ alkyl group, a CN, a (CO)-R ^3a , a COOR ⁴ , a CONR ¹⁰ R ¹¹ , a NO 2 , a PO(OR ^{3a ) 2} or a S ^{(O) m -R 3a ; R 1a is} a hydrogen, a C ₁ -C ₂₀ alkyl group, a CN, a (CO)-R ^3a , a CONR ¹⁰ R ¹¹ , a NO ₂ , a PO( _OR ^3a _{) 2} or a S(O) _m -R ^3a ; or R ^1a is C ₁ -C ₂₀ alkyl which is substituted by one or more halogens, OR ^4a , SR ^{9a ,} _NR ^10a R ^11a , ^CN , COOR ^4a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a , or C ₃ -C ₈ cycloalkyl which is uninterrupted or interrupted by one or more O, S, CO or NR 10a ; or R 1a is C ₁ -C 20 alkyl which is substituted by one or more halogens, OR 4a , SR 9a , NR 10a R 11a , CN, COOR ^4a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a , or C 3 -C ₈ cycloalkyl which is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; or R 1a is C ₁ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C or R _1a is C ₁ -C ₂₀ alkyl, which is interrupted by one _or more O, _{S, NR 10a , CO, SO or SO 2, which is unsubstituted or substituted by C 3 -C 8 cycloalkyl} , OH, _SH , O( _CO )R 3a , COOR ^4a , CONR ^10a R 11a , C ₆ -C ₂₀ aryl, C ₃ -C ₈ cycloalkyl, OH, ^{SH, O(CO)R 3a , COOR 4a} , CONR ^10a R ^11a , C 6 -C 20 aryl, C ₃ -C ₈ cycloalkyl, OH, SH, O(CO)R ^3a , COOR ^4a , CONR ^10a _R ^11a , C ₆ -C ₂₀ aryl, C ₃ -C C ₆ -C ₂₀ heteroaryl, C 6 -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, wherein C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl is unsubstituted or substituted with one or more halogens, C ₁ -C ₈ alkyl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or R ^1a is C ₂ -C ₁₂ alkenyl or C ₃ -C ₂₀ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR ^10a or COOR ^4a ; or R ^1a is C ₆ -C ₂₀ aryl or C ₃ -C 20 heteroarylcarbonyl. ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more halogen, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R ^3a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ or S(O) _m -R ^3a ; or substituted with one or more C _1- C ₂₀ alkyl, the C _1- C ₂₀ alkyl being unsubstituted or substituted with one or more halogen, COOR ^4a , CONR ^10a R ^11a , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or substituted with one or more C ₂ -C ₂₀ alkyl, the C ₂ -C _{R 2} is hydrogen, C 1 -C 20 alkyl or C 1 -C 6 alkyl-C 3 -C 6 cycloalkyl, which is unsubstituted or substituted with one or more halogens, OR ⁴ , SR ⁹ , COOR 4 CONR 10 R ¹¹ , NR ¹⁰ R ¹¹ , PO(OR ^{3a ) 2 , COR 3a} ; R ² is C ₂ -C ₂₀ alkyl or C _{1 -C 6} alkyl-C ₃ -C ₆ cycloalkyl, which is unsubstituted or substituted with one or more halogens, OR ⁴ , SR ⁹ , _COOR ⁴ CONR ¹⁰ R ¹¹ , NR ¹⁰ R ¹¹ , _PO (OR ^3a _{) 2} , COR ^3a _; wherein the interrupted _C2 - ^C20 _alkyl group is unsubstituted or substituted by one or more halogens, OR4, ^SR9 , _COOR4 , ^CONR10R11 , ^NR10R11 ; or ^R2 is _C2 - _C4 hydroxyalkyl, C2- _C10 alkoxyalkyl, _C3 - ^C5 alkenyl, _C3 - _{C8 cycloalkyl} , phenyl- _C1 - _C3 alkyl, _C2 - _C8 alkanoyl, _C3 - _{C12 alkenyl ,} benzoyl; or ^R2 is ^C6 _- ^C20 aryl or _{C3 -} ^C ₂₀ heteroaryl, each of which is unsubstituted or substituted with one or more C ₁ -C ₁₂ alkyl, C ₁ -C ₄ halogenated alkyl, phenyl, halogen, CN, NO ₂ , OR ⁴ , SR ⁹ , NR ¹⁰ R ¹¹ , (CO)-R ^3a , or substituted with a C ₂ -C ₂₀ alkyl group, the C ₂ -C ₂₀ alkyl group is interrupted by one or more O, S or NR ¹⁰ , or each of which is substituted with one or more C ₁ -C ₂₀ alkyl groups, the C ₁ -C ₂₀ alkyl group is unsubstituted or substituted with one or more halogen, COOR ⁴ , CONR ¹⁰ R ¹¹ , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryloxycarbonyl, C ₃ -C ₂₀ heteroaryloxycarbonyl, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ is substituted; or R ² is a group ; R ³ is hydrogen or C ₁ -C ₂₀ alkyl; or R ³ is C ₁ -C ₂₀ alkyl, which is substituted with one or more halogens, OR ⁴ , SR ⁹ , NR ¹⁰ R ¹¹ , CN, COOR ⁴ , CONR ¹⁰ R ¹¹ , C ₃ -C ₈ cycloalkyl, which C ₃ -C ₈ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ¹⁰ ; or is substituted with one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, C ₁ -C or R ³ is C _{1 -C 20 alkyl, which is interrupted by one or more O, S, NR 10 , CO, SO or SO 2, which is unsubstituted or substituted by C 3 -C 8 cycloalkyl, OH, SH, O(CO)-R 3a , COOR 4 , CONR 10 R 11 , C 6 -C 20} ^aryl _, ^{C 3} _{-C 20 heteroaryl} ^{, C} ₆ ^{-C 20 aromatic acyl} _{or C 3 -C 20 heteroarylcarbonyl, wherein C 6 -C 20 aryl, C 3 -C 20 heteroaryl , C 6 -C 20 aromatic} acyl or C ₃ -C 20 heteroarylcarbonyl or R ³ is C ₆ -C ₂₀ aryl or C ₃ ^{-C 20 heteroaryl} , _each of which is unsubstituted or substituted by one or more halogens, C ₁ -C ₂₀ alkyl, C _{1 -C 4} halogenated alkyl, ^phenyl , C ₁ -C ₂₀ alkylphenyl, C _{1 -C 8} alkoxyphenyl, CN, NO ₂ , OR ⁴ , SR ^{9 ,} NR ₁₀ R ¹¹ _{, COOR} ^{4 ,} ₍ ^CO ₎ ^-R or R ³ is C ₁ -C ₂₀ alkoxy, which is unsubstituted or substituted by one or more C ₁ -C ₁₀ alkyl, C ₁ ^-C ₄ halogenated alkyl, _halogen , phenyl, C ₁ -C ₂₀ alkylphenyl or C ₁ -C ₈ alkoxyphenyl; or ^{R 3} is C ₁ -C ₂₀ alkoxy, which is interrupted by one or more O, S, NR ¹⁰ , CO, SO or SO ₂ ; or R ³ is C ₆ -C ₂₀ aryloxy or C ₃ -C ₂₀ heteroaryloxy, each of which is unsubstituted or substituted by one or more halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ halogenated alkyl, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, CN, NO ₂ , OR ⁴ , SR ⁹ R ^3a is hydrogen or C ₁ -C ₂₀ alkyl; or R ^3a is C ₁ -C ₂₀ alkyl, which is substituted by ^one or more ^halogens , OR ^4a , SR ^9a , NR ^10a R ^11a , CN, COOR ^4a , CONR _10a R ^11a , C ₃ -C ₈ cycloalkyl, which is uninterrupted or interrupted by one or more O, S, CO or NR ^{10a ;} or by ^one or ^more C _{6 -C 20} aryl, _C ³ _{-C 20 heteroaryl, C 6 -C 20 aromatic acyl or} C ₃ -C R _3a is C ₁ -C ₂₀ alkyl, which is interrupted by one or more O, S, NR 10a , CO, SO or SO 2, which is unsubstituted or substituted by C ₃ -C ₈ cycloalkyl, OH, _{SH, O(CO)} -(C ₁ -C 8 alkyl), COOR ^4a , CONR ^10a R ^11a , C 6 -C 20 aryl, C 3 -C 20 heteroaryl, C ₆ -C 20 aromatic acyl or C ₃ -C ₈ cycloalkyl, which is unsubstituted or substituted by one or more halogen, phenyl, C 1 -C _{20 alkylphenyl, C 1 -C 8 alkoxyphenyl, C 1 -C 4 halogenated alkyl, CN, NO 2 , OR 4a , SR 9a or NR 10a R 11a ; or R 3a is C 1 -C 20} ^{alkyl ,} which is interrupted by one or more O, S, NR ^10a , CO, SO or SO ₂ , which is unsubstituted or substituted by C 3 -C ₈ cycloalkyl, OH, SH, O(CO)-(C ₁ -C ₈ alkyl), COOR ^4a , CONR ^10a R ^11a , C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C _{C6 - C20} aryl, C3- _C20 heteroaryl, C6- _C20 arylyl or _C3 - _C20 heteroarylcarbonyl is unsubstituted or substituted with one or more halogens, _C1 - _C8 alkyl, ^OR4a , ^SR9a or ^NR10aR11a ; or ^R3a is _{C2 - C12} alkenyl or _C3 - _C20 cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, ^NR10a or ^COOR4a ; or ^R3a is _C6 - _C20 aryl or _C3 - _C20 heteroaryl, each of _which is unsubstituted or substituted with one or more halogens, _C1 - _C20 alkyl, ^C1 _- C or R 3a is C 1 -C 20 alkoxy which is unsubstituted or substituted with _{one or more} C ₁ -C ₁₀ alkyl, C ₁ -C 4 halogenated alkyl, halogen, phenyl, C 1 -C 20 alkylphenyl, C ₁ -C ₈ alkoxyphenyl, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-(C ₁ -C ₈ alkyl) or SO ₂ -(C 1 -C ₄ halogenated alkyl); or R ^3a is C ₁ -C ₂₀ alkoxy which is unsubstituted or substituted with one or more C ₁ -C ₁₀ alkyl, C ₁ -C ₄ halogenated alkyl, halogen, phenyl, C ₁ -C ₂₀ alkylphenyl or C ₁ -C ₈ alkoxyphenyl; or R ^3a is C ₁ -C ₂₀ alkoxy which is interrupted by one or more O, S, NR ^10a , CO, SO or SO ₂ ; or R ^3a is C ₆ -C _{R 3a is a group ​ ​ ​ ​ ​ ​ ​} ^{​ ​ ​ ​ ​} _{​ ​ ​ ​ ​} ^​ R ^3b is hydrogen or C ₁ -C ₂₀ alkyl; or R ^3b is C ₁ -C ₂₀ alkyl, which is substituted with one or more halogens, OR ^4a , SR ^9a , NR ^10a R ^11a , CN, COOR ^4a , CONR ^10a R ^11a , C ₃ -C ₈ cycloalkyl, which C ₃ -C ₈ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; or is substituted with one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C R ^3b is C _{1 -C 20 alkyl, which is interrupted by one or more O, S, NR 10a , CO, SO or SO 2, which is unsubstituted or substituted by C 3 -C 8 cycloalkyl, OH, SH, O(CO)-(C 1 -C 8 alkyl), COOR 4a , CONR 10a R 11a , C 6 -C 20} ^aryl _, ^C _{3 -C 20} ^heteroaryl _{, C} ^{6 -C 20} _{arylyl or} C ₃ -C ₂₀ heteroarylcarbonyl, wherein C ₆ -C 20 aryl, C ₃ ^{-C 20} heteroaryl, C 6 -C ₂₀ arylcarbonyl or C 3 _{-C 20} heteroarylcarbonyl is substituted by C 6 -C 20 aryl, C _{3 -C 20 heteroaryl, C 6} -C ₂₀ arylcarbonyl or C 3 -C 20 heteroarylcarbonyl is substituted by C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C R ^3b is C ₂ -C ₁₂ alkenyl or C ₃ -C ₂₀ cycloalkyl, each ^of which is uninterrupted or interrupted by one or more O, S, CO, NR ^10a or ^{COOR 4a ;} or R ^3b is C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is uninterrupted or interrupted by one or more halogen, C _{1 -C 20} alkyl, C ₁ -C ₄ halogenated alkyl, _{phenyl, C 1 -C 20 alkylphenyl, C 1 -C 8 alkoxyphenyl, CN, NO 2 , OR 4a , SR 9a} ^{, or} NR _10a R ^11a _. ^{R 9a} , NR ^10a R ^11a , COOR ^4a , (CO)-(C ₁ -C ₈ alkyl) or SO ₂ -(C ₁ -C ₄ halogenated alkyl) substituted; or R ^3b is C ₁ -C ₂₀ alkoxy, which is unsubstituted or substituted by one or more C ₁ -C ₁₀ alkyl, C ₁ -C ₄ halogenated alkyl, halogen, phenyl, C ₁ -C ₂₀ alkylphenyl or C ₁ -C ₈ alkoxyphenyl; or R ^3b is C ₁ -C ₂₀ alkoxy, which is interrupted by one or more O, S, NR ^10a , CO, SO or SO ₂ ; or R ^3b is C ₆ -C ₂₀ aryloxy or C ₃ -C ₂₀ heteroaryloxy, each of which is unsubstituted or substituted by one or more halogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₄ halogenated alkyl, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-(C ₁ -C ₈ alkyl) or SO ₂ -(C ₁ -C ₄ halogenated alkyl); R ⁴ is hydrogen, (CO)-R ^3a , COOR ^4a , CO NR ^10a R ^11a , S(O) _m -R ^3a or PO(OR ^3a ) ₂ ; or R ⁴ is C ₁ -C ₂₀ alkyl which is substituted by one or more halogens, OR ^4a , SR ^9a , NR ^10a R ^11a , CN, COOR ^4a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a , C ₃ -C ₈ cycloalkyl group, the C ₃ -C ₈ cycloalkyl group is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; or is substituted by one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, C ₁ -C ₄ halogenated alkyl, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , PO(OR ^3a ) ₂ or S(O) _m -R ^3a ; or R ⁴ is C _C1 - _C20 alkyl, which is interrupted by one or more O, S, ^NR10a , CO, SO or _SO2 , which is unsubstituted or substituted by _C3 - _C8 cycloalkyl, OH, SH, O(CO) ^-R3a , ^COOR4a , ^CONR10aR11a , C6-C20 ^aryl , C3- _{C20 heteroaryl, C6-C20 aromatic} acyl or C3- _C20 heteroarylcarbonyl, _wherein the _{C6 - C20} aryl, _{C3 - C20} heteroaryl, _C6 - _C20 aromatic acyl ^or C3- _C20 heteroarylcarbonyl is unsubstituted or substituted by ^one _or more halogen, _C1 - _C8 alkyl, _OR4a , _SR9a or ^NR10aR or R ⁴ is C ₂ -C ₁₂ alkenyl or C ₃ -C ₂₀ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR ^10a or COOR ^4a ; or R ⁴ is C ₆ -C ₂₀ ^aryl , which is interrupted by one or more halogen, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R ^3a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a or a group or substituted by one or more C _{1 -C 20} alkyl groups, which are _{unsubstituted} or substituted by one or more halogens, COOR ^4a , CONR ^10a R ^11a , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or substituted by one or more C _{2 -C 20} alkyl groups, which are interrupted by one or more O, S or NR ^10a ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthyl groups, each of which is unsubstituted or substituted by OR ^4a _, SR ^9a or NR ^10a R ^11a ; or R ⁴ is C ₃ -C ₂₀ heteroaryl groups, each of which is unsubstituted or substituted with one or more halogens, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R ^3a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a or a group or substituted by one or more C _{1 -C 20} alkyl groups, which are _{unsubstituted} or substituted by one or more halogens, COOR ^4a , CONR ^10a R ^11a , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or substituted by one or more C _{2 -C 20} alkyl groups, which are interrupted by one or more O, S or NR ^10a ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthyl groups, each of which is unsubstituted or substituted by OR ^4a _, SR ^9a or NR ^10a R ^11a ; or R ⁴ and R 1 together with one of the carbon atoms of ¹ to form a 5-membered or 6-membered saturated or unsaturated ring, which is uninterrupted or interrupted by O, S or NR ^10a , and the 5-membered or 6-membered saturated or unsaturated ring is unsubstituted or substituted with one or more C ₁ -C ₂₀ alkyl groups, OR ^4a , SR ^9a , NR ^10a R ^11a , (CO)-R ^3a , NO ₂ , halogen, C ₁ -C ₄ halogenated alkyl, CN, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, or C ₃ -C ₂₀ cycloalkyl substituted, the C ₃ -C ₂₀ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; R ^4a is hydrogen, C ₁ -C ₂₀ alkyl, (CO)O(C ₁ -C ₈ alkyl) or CON(C ₁ -C ₈ alkyl) ₂ ; or R ^4a is C ₁ -C ₂₀ alkyl substituted by one or more halogen, OH, SH, CN, C ₃ -C ₈ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₈ alkyl), O(CO)-(C ₁ -C ₈ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₈ alkyl), C ₃ -C _{R 4a} is C ₂ -C ₂₀ alkyl, which is interrupted by one _or more O, _S , N(C ₁ -C ₈ alkyl), CO, SO or SO _{2 ,} which is _{unsubstituted} or substituted by C _{3 -C 8} cycloalkyl, OH, SH, O(CO ⁾ (C _{1 -C 8} alkyl), (CO) _O (C ₁ -C ₈ alkyl), (CO)N(C _{1 -C 8} alkyl) ₂ , C ₆ -C _{20 aryl} , C _{3 -C 20} heteroaryl, _{C 6 -C 20 C6} -C20 aryl, _C3 - _C20 heteroaryl, C6-C20 aryl or _C3 - _C20 heteroarylcarbonyl, wherein _C6 - _C20 aryl, C3- _C20 heteroaryl, _C6 - _{C20 aryl or C3-C20 heteroarylcarbonyl} is unsubstituted or substituted with one or more halogens, _C1 - _C8 alkyl, _C1 - _C8 alkoxy, _C1 -C8 alkylthio or N( _C1 - _C8 alkyl) ₂ ; or ^R4a is _C6 - _C20 aryl, _C3 - _C20 heteroaryl, _C6 - _{C20 aryl} or _C3 - _C20 heteroarylcarbonyl, each of which is unsubstituted or substituted with one or more halogens, CN, _NO2 , OH, _C1 - _C8 alkyl, _C1 -C8 R _4a is substituted by C ₂ -C ₁₂ alkenyl, (CO)O(C _{1 -C 8 alkenyl) or C 3 -C 8 cycloalkyl} , each of which is uninterrupted or interrupted by _one or more _O , S, CO, N(C ₁ -C ₈ alkyl) or COO(C _{1 -C 8 alkyl} ); or R ^4a is C _{1 -C 20 alkyl, C 3} -C ₁₂ alkenyl, (CO)O(C _{1 -C 8} alkenyl) or _{C 3} -C ₈ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, _N (C ₁ -C ₈ alkyl) or ^COO (C ₁ -C _{8 alkyl )} ; -C ₁₂ alkenyl, each of which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, OH, C ₁ -C ₈ alkoxy, phenoxy, C ₁ -C ₈ alkylthiohydrogen, phenylthiohydrogen, N(C ₁ -C ₈ alkyl) ₂ or diphenylamino; R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen, C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ arylC ₁ -C ₂₀ -alkyl, hydroxy-C ₁ -C ₂₀ alkyl, hydroxy-C ₁ -C ₂₀ alkoxy-C ₁ -C ₂₀ alkyl, C ₃ -C ₁₀ cycloalkyl, amine, CN, NO _2. Hydroxyl, , (CO)-R ^3a , OR ^4a or COOR ⁴ ; R ⁹ is hydrogen or C ₁ -C ₂₀ alkyl; or R ⁹ is C ₁ -C ₂₀ alkyl, which is substituted by one or more halogens, OR ^4a , SR ^9a , NR ^10a R ^11a , CN, COOR ^4a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a , C _{3 -C 8} cycloalkyl, which is _{uninterrupted} or interrupted by one or more O, S, CO or NR ^10a ; or by one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C or R ₉ is C ₁ -C ₂₀ alkyl, which is interrupted by one or more O, S, NR 10a , CO, SO or _{SO 2} ^, which is unsubstituted or substituted by _{C 3} -C ₈ cycloalkyl, OH, _SH , O( ^CO )-R ^3a , COOR ^4a , CONR ^10a R ^11a , C ₆ -C ₂₀ aryl, C 3 -C ₂₀ ^heteroaryl , C 6 -C 20 heteroaryl, C 6 -C 20 heteroaryl, C 6 -C 20 heteroaryl, C 6 -C 20 heteroaryl, C ₆ ^-C ₂₀ heteroaryl, C ₆ -C ₂₀ heteroaryl, C 6 -C ²⁰ heteroaryl, ^{C 6 -C} 20 ^heteroaryl , C 6 -C 20 heteroaryl, C ₆ -C 20 heteroaryl, C 6 -C ²⁰ heteroaryl, C ₆ -C ₂₀ heteroaryl, C ₆ -C C _{6 -C 20} aryl, C ₃ -C _{20 heteroaryl, C 6 -C 20 aryl} or C ₃ -C ₂₀ heteroarylcarbonyl is unsubstituted or substituted with one or more halogens, C ₁ -C ₈ alkyl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or R ⁹ is C 2 -C ₁₂ alkenyl or C _{3 -C 20 cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR 10a or COOR 4a; or R 9 is C 6 -C 20 aryl or C 3 -C 20} ^{heteroaryl , each} _{of which is unsubstituted or substituted} with one or more halogens, CN, NO ₂ , OR 11a. ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R ^3a , CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a or a group or substituted by one or more C _{1 -C 20} alkyl groups, which are _{unsubstituted} or substituted by one or more halogens, COOR ^4a , CONR ^10a R ^11a , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or substituted by one or more C _{2 -C 20} alkyl groups, which are interrupted by one or more O, S or NR ^10a ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthyl groups, each of which is unsubstituted or substituted by OR ^4a _, SR ^9a or NR ^10a R ^11a ; or R ⁹ and R ¹ , 1 or more carbon atoms of the phenyl group, phenyl group, C ₁ ^-C ₂₀ ^alkylphenyl group, _C ^{1 -C} ₈ alkoxyphenyl group _, or _{C 1} ^-C ₂₀ ^alkylphenyl _group . or C ₃ -C ₂₀ cycloalkyl substituted, the C ₃ -C ₂₀ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; R ^9a is hydrogen or C ₁ -C ₂₀ alkyl; or R ^9a is C ₁ -C ₂₀ alkyl which is substituted by one or more halogen, OH, SH, CN, C ₃ -C ₈ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C ₈ alkyl), O(CO)-(C ₁ -C ₈ alkyl), O(CO)-(C ₂ -C ₄ )alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C ₁ -C ₈ alkyl), C ₃ -C ₈ cycloalkyl, SO ₂ -(C ₁ -C ₄ halogenated alkyl), O(C ₁ -C R ^9a is C _{2 -C 20} alkyl, which is interrupted by one or more O, S, N(C ₁ -C ₈ alkyl), _CO , SO or SO ₂ , which is unsubstituted _or substituted by C _{3 -C 8} cycloalkyl, OH, SH, O(CO)(C ₁ -C ₈ alkyl), (CO)O(C ₁ -C ₈ alkyl), (CO)N(C _{1 -C 8} alkyl) ₂ , C ₆ -C ₂₀ aryl, _{C 3} -C ₂₀ heteroaryl, C ₆ -C _{20 arylyl} or C ₃ -C ₂₀ heteroarylcarbonyl, _wherein C ₆ -C _{20 R 9a} is C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, N(C ₁ -C ₈ alkyl) or COO(C ₁ -C ₈ alkyl); or R ^9a is C ₆ -C ₂₀ aryl, C ₃ -C 20 heteroaryl, C 6 -C ₂₀ aromatic acyl or C ₃ -C 20 heteroaromatic carbonyl, which is unsubstituted or substituted by one or more halogen, C ₁ -C 8 alkyl, C 1 -C _{8 alkoxy, C 1 -C 8 alkylhydrosulfanyl or N(C 1 -C 8 alkyl) 2; or R 9a is C 2 -C 12 alkenyl or C 3 -C 8 cycloalkyl , each of} which is uninterrupted or interrupted by one or more O, S, CO, N(C ₁ -C ₈ alkyl) or COO(C ₁ -C ₈ alkyl); or R ^9a is C ₆ -C ₂₀ aryl, C 3 -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C R _9a is C 1 -C 20 alkyl, C 3 -C ₁₂ alkenyl, each of which is unsubstituted or substituted with one or more halogens, CN, NO ₂ , OH, C ₁ -C 8 alkyl, C ₁ -C ₄ halogenated alkyl, C ₁ -C ₈ alkoxy, phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C ₈ alkylthio, phenylthio, N (C ₁ -C ₈ alkyl) ₂ , diphenylamino, (CO) O (C ₁ -C ₈ alkyl), (CO) -C ₁ -C ₈ alkyl or (CO) N (C ₁ -C ₈ ) ₂ , phenyl or benzoyl; or R ^9a is C ₁ -C ₂₀ alkyl, C ₃ -C ₁₂ alkenyl, each of which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C R ₁₀ and R ¹¹ are independently hydrogen _{, C 1 -C 20} alkyl, S(O) _m -R ^3a , O(CO)-R _3a (CO)-R ^3a or CONR ^10a R _{11a ; or R 10 and R 11 are independently C 1 -C 20} ^{alkyl which} _{is substituted by one} or more halogens, OR ^4a , SR ^9a , NR ^{10a R 11a} , CN _, COOR ^4a _, CONR ^10a R ^11a , PO( _OR ^3a ) ² , S ⁽ O) _m -R ^3a , C ₃ -C The C ₃ -C ₈ cycloalkyl group is uninterrupted or _interrupted by one or more O, S, CO or NR ^10a ; or is substituted by one or more C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aromatic acyl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, C ₁ -C ₄ halogenated alkyl, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , PO(OR ^3a ) ₂ or S(O) _m -R ^3a ; or R ¹⁰ and R ¹¹ are independently C ₁ -C 20 R ^11a , C 6 ^-C ₂₀ aryl, C ³ -C ₂₀ heteroaryl, C ₆ -C _{20 aryl or C 3 -C 20 heteroarylcarbonyl, wherein the C 6 -C 20 aryl ,} C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryl or C _{3 -C 20 heteroarylcarbonyl} is _{unsubstituted} ^or _substituted with one or _more halogens, C _{1 -C 8} alkyl, OR ^4a , SR ^9a _{or NR} ^{10a R 11a} ; or R ^{R 10} and R ¹¹ are independently C ₂ -C ₁₂ alkenyl or C ₃ -C ₂₀ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR ^10a or COOR ^4a ; or R ¹⁰ and R ¹¹ are independently C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, each of which is unsubstituted or interrupted by one or more halogens, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R ^3a CONR ^10a R ^11a , PO(OR ^3a ) ₂ , S(O) _m -R ^3a or a group or substituted by one or more C _{1 -C 20} alkyl groups, which are _{unsubstituted} or substituted by one or more halogens, COOR ^4a , CONR ^10a R ^11a , phenyl, C ₃ -C ₈ cycloalkyl, C ₃ -C ₂₀ heteroaryl, OR ^4a , SR ^9a or NR ^10a R ^11a ; or substituted by one or more C _{2 -C 20} alkyl groups, which are interrupted by one or more O, S or NR ^10a ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthyl groups, each of which is unsubstituted or substituted by OR ^4a _, SR ^9a or NR ^10a R ^11a ; or R ¹⁰ and R ¹¹ are independently C ₁ -C 20 R ^{10 and R 11 are independently C 1 -C 20 alkoxy groups, which are unsubstituted or substituted with one or more halogens, phenyl, C 1 -C 8 alkylphenyl or C 1 -C 8 alkoxyphenyl groups; or R 10 and R 11} _{are independently C 1 -C 20 alkoxy groups , which are} interrupted by one or more O, S, NR ^10a , CO, SO or SO ₂ ; or R ¹⁰ and R ¹¹ are independently C ₆ -C ₂₀ aryloxy groups or C ₃ -C ₂₀ heteroaryloxy groups, each of which is unsubstituted or substituted with one or more halogens, C ₁ -C ₈ alkyl, C ₁ -C ₄ halogenated alkyl, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C ₈ alkoxyphenyl groups, CN, NO ₂ , OR ^4a , SR ^9a , NR ^10a R ^11a , COOR ^4a , (CO)-R or R ¹⁰ and one of ^the carbon atoms _of ^{R 1} together form a 5-membered or 6-membered saturated or unsaturated ring which is uninterrupted or interrupted by O, S or NR ^10a , and the 5-membered or 6-membered saturated or unsaturated ring is unsubstituted or substituted by one or more C ₁ -C ₂₀ alkyl groups, OR ^4a , SR ^9a , NR ^10a R ^11a , (CO)-R ^3a , NO ₂ , halogen, C ₁ -C ₄ halogenated alkyl, CN, phenyl, C ₁ -C ₂₀ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, or substituted by a C ₃ -C ₂₀ cycloalkyl group, the C ₃ -C ₂₀ cycloalkyl group being uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; or R ¹⁰ and R ¹¹ together with the N atom to which they are attached form a 5-membered or 6-membered saturated or unsaturated ring, which is uninterrupted or interrupted by O, S or NR ^10a , and the 5-membered or 6-membered saturated or unsaturated ring is unsubstituted or substituted by one or more C ₁ -C ₂₀ alkyl groups, OR ^4a , SR ^9a , NR ^10a R ^11a , (CO)-R ^3a , NO ₂ , halogen, C ₁ -C ₄ halogenated alkyl, CN, phenyl, or C ₃ -C ₂₀ cycloalkyl substituted, the C ₃ -C ₂₀ cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR ^10a ; R ^10a and R ^11a are independently hydrogen, C ₁ -C ₂₀ alkyl, S(O) _m -(C ₁ -C ₈ alkyl), O(CO)(C ₁ -C ₈ alkyl), (CO)(C ₁ -C ₈ alkyl), (CO)O(C ₁ -C ₈ alkyl) or CON(C ₁ -C ₈ alkyl) ₂ ; or R ^10a and R ^11a are independently C ₁ -C ₂₀ alkyl, which is substituted by one or more halogen, OH, SH, CN, C ₃ -C ₈ alkenyloxy, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO)O(C ₁ -C 8 alkyl) _R 10a and R 11a are independently C ₂ -C ₂₀ alkyl, which is _{interrupted by one or more} O _{, S} , ^N ( _{C 1 -C 8 alkyl} ), CO _{, SO or} ^SO _{2 ,} which _{is unsubstituted} or _interrupted by _{C 3 -C 8 cycloalkyl . R} 10a and R 10b are substituted with C ₁ -C ₈ cycloalkyl, OH, SH, O(CO)(C ₁ -C ₈ alkyl), (CO)O(C ₁ -C ₈ alkyl), (CO)N(C ₁ -C ₈ alkyl) ₂ , C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C _{6 -C 20 arylacyl or C 3} -C ₂₀ heteroarylcarbonyl, wherein the C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ arylacyl or C ₃ -C ₂₀ heteroarylcarbonyl is unsubstituted or substituted with one or more halogens, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthiohydrogen or N(C ₁ -C ₈ alkyl) ₂ ; or R ^10a and R ^{R 11a} are independently C ₂ -C ₁₂ alkenyl or C ₃ -C ₈ cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, N(C ₁ -C ₈ alkyl), or COO(C ₁ -C ₈ alkyl); or R ^10a and R ^11a are independently C ₆ -C ₂₀ aryl, C ₃ -C ₂₀ heteroaryl, C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroarylcarbonyl, each of which is unsubstituted or interrupted by one or more halogen, CN, NO ₂ , OH, C ₁ -C ₈ alkyl, C ₁ -C ₄ halogenated alkyl, C ₁ -C ₈ alkoxy, phenyl-C ₁ -C ₃ alkoxy, phenoxy, C ₁ -C _R 10a and R 11a are independently C 1 -C ₂₀ alkylyl, C ₃ -C 12 alkenyl, each of which is unsubstituted or substituted with _one or more halogens, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C 8 alkoxyphenyl, OH, C 1 -C ₈ alkoxy, phenoxy, C 1 -C 8 alkylhydrothio, phenylhydrothio, N (C ₁ -C ₈ alkyl) ₂ or diphenylamino; or R ^10a and R ^11a are independently C ₁ -C ₂₀ alkylyl, C ₃ -C ₁₂ alkenyl, each of which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, OH, C ₁ -C ₈ alkoxy, phenoxy, C ₁ -C ₈ alkylhydrothio, ^{phenylhydrothio} , N (C ₁ -C ₈ alkyl) ₂ or diphenylamino; ^{R 11a} are independently C ₁ -C ₂₀ alkoxy, which is unsubstituted or substituted with one or more halogens, phenyl, C ₁ -C ₈ alkylphenyl or C ₁ -C ₈ alkoxyphenyl; or R ^10a and R ^11a are independently C ₁ -C ₂₀ alkoxy, which is interrupted by one or more O, S, N (C ₁ -C ₈ alkyl), CO, SO or SO ₂ ; or R ^10a and R ^11a are independently C ₆ -C ₂₀ aryloxy or C ₃ -C ₂₀ heteroaryloxy, each of which is unsubstituted or substituted with one or more halogens, C ₁ -C ₈ alkyl, C ₁ -C ₄ halogenated alkyl, phenyl, C ₁ -C ₈ alkylphenyl, C ₁ -C ₈ alkoxyphenyl, CN, NO ₂ , C ₁ -C ₈ alkoxy, C ₁ -C or R _10a and R _11a together with the nitrogen atom _to which _they are attached form a _5- or 6 _- membered saturated or unsaturated ring which is uninterrupted or interrupted by O ^, S or _N ( _{C 1 -C 8} alkyl), and wherein the 5- or 6 ^- membered saturated or unsaturated ring is unsubstituted or substituted by one or more C ₁ -C ₈ alkyl, C ₁ -C 8 alkoxy, C ₁ -C ₈ alkylthio, N( _{C 1 -C 8 alkyl) 2, NO 2, halogen, C 1 -C 4 halogenated alkyl , CN , phenyl or} C ₃ -C ₈ R ₁₂ and R ^{13 are independently hydrogen, C 1 -C 12 alkyl, which is optionally substituted with one or more halogen, phenyl, CN, -OH, -SH, C 1 -C 4 alkoxy, (CO) OH or (CO) O(C 1 -C 4 alkyl); or R 12 and R 13} _{are phenyl , which is optionally substituted with one} ^{or more} _{C 1 -C 6 alkyl , halogen ,} CN, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or R ¹² and R ¹³ are halogen, CN, OR ⁴ , SR ⁹ , ^{SOR 9} , SO ₂ R ⁹ or NR ¹⁰ R ¹¹ , wherein the substituents OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ optionally form a 5-membered or 6-membered ring via the groups R ⁴ , R ⁹ , R ¹⁰ and/or R ¹¹ with one of the carbon atoms of phenyl, naphthyl, benzoyl or naphthyl or the carbon atom of the substituent R ^3a ; or R ¹² and R ¹³ together are the group , wherein R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are independently hydrogen, C ₁ -C ₁₂ alkyl, the C ₁ -C ₁₂ alkyl being optionally substituted with one or more halogen, phenyl, CN, -OH, -SH, C ₁ -C ₄ alkoxy, (CO) OH or (CO) O(C ₁ -C ₄ alkyl); or R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are phenyl, which is optionally substituted with one or more C ₁ -C ₆ alkyl, halogen, CN, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are halogen, CN, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; or R ¹² and R ¹³ together are a group , wherein R ¹⁸ and R ¹⁹ are independently hydrogen, C _{1 -C 12} alkyl, which is optionally substituted with one or more halogens, phenyl, CN, -OH, -SH, C ₁ -C ₄ alkoxy, (CO) OH or (CO) O( _{C 1} -C ₄ alkyl); or R ¹⁸ and R ¹⁹ are phenyl, which is optionally substituted with one or more C ₁ -C ₆ alkyl, halogens, CN, OR ⁴ , SR ⁹ or NR ¹⁰ R ¹¹ ; m is 1 or 2; and Q is CO or a direct bond. The polymerizable liquid crystal composition of claim 1, wherein R ¹ is hydrogen, C ₁ -C ₂₀ alkyl, C ₁ -C ₆ alkyl-C ₃ -C ₆ cycloalkyl, C ₃ -C ₂₀ cycloalkyl or C ₂ -C ₁₂ alkenyl, wherein the C ₃ -C ₂₀ cycloalkyl or C ₂ -C ₁₂ alkenyl is uninterrupted or interrupted by one or more O, S, CO, NR ¹⁰ or COOR ⁴ ; R ² is hydrogen, C ₁ -C ₂₀ alkyl or C ₁ -C ₆ alkyl-C ₃ -C ₆ cycloalkyl, which is unsubstituted or substituted by one or more halogens, OR ⁴ , SR ⁹ , COOR ⁴ CONR ¹⁰ R ¹¹ , NR ¹⁰ R ¹¹ , PO(OR ^3a ) ₂ , COR ^3a ; ^{R 3} is hydrogen or C ₁ -C ₂₀ alkyl; R ^3a is hydrogen or C ₁ -C ₂₀ alkyl; R ⁴ is hydrogen, (CO)-R ^3a , COOR ^4a , CO NR ^10a R ^11a , S(O) _m -R ^3a or PO(OR ^3a ) ₂ ; R ^4a is hydrogen, C ₁ -C ₂₀ alkyl, (CO)O(C ₁ -C ₈ alkyl) or CON(C ₁ -C ₈ alkyl) ₂ ; R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen, C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkoxy, C ₆ -C ₂₀ aryl, C ₁ -C ₂₀ alkyl, hydroxy-C ₁ -C 20 C ₂₀ alkyl, hydroxy-C ₁ -C ₂₀ alkoxy-C ₁ -C ₂₀ alkyl, C ₃ -C ₁₀ cycloalkyl, amine, CN, NO ₂ , hydroxy, , (CO)-R ^3a , OR ^4a or COOR ⁴ ; R ⁹ is hydrogen or C ₁ -C ₂₀ alkyl; R ¹⁰ and R ¹¹ are independently hydrogen, C ₁ -C ₂₀ alkyl, S(O) _m -R ^3a , O(CO)R ^3a (CO)-R ^3a or CONR ^10a R ^11a ; and R ^10a and R ^11a are independently hydrogen, C ₁ -C ₂₀ alkyl, S(O) _m -(C ₁ -C ₈ alkyl), O(CO)(C ₁ -C ₈ alkyl), (CO)(C ₁ -C ₈ alkyl), (CO)O(C ₁ -C ₈ alkyl) or CON(C ₁ -C ₈ alkyl) ₂ ; and Q is CO or a direct bond. The polymerizable liquid crystal composition of claim 1 or 2, wherein the polymerization initiator of formula (I) is a compound of formula (Ia) or (Ib): (Ia) (Ib) wherein R ¹ is a linear C ₁ -C ₈ alkyl group, in particular a C ₂ -C ₆ alkyl group; R ²⁰ and R ²¹ are independently C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl or C ₃ -C ₂₀ heteroaryl, in particular a C ₁ -C ₈ alkyl group. The polymerizable liquid crystal composition of claim 3, wherein the polymerization initiator of formula (Ia) is a compound of formula (Ia-1): (Ia-1). The polymerizable liquid crystal composition of any of the preceding claims, wherein the polymerizable liquid crystal compound is at least one anisotropic compound of formula (II): (II) wherein the moieties C and D are independently selected from the group consisting of phenyl, biphenyl, naphthyl, cycloalkyl, bicycloalkyl, , ,or ; wherein *1 represents the bonding sites of moiety C and ^X2 and moiety D and ^X1 , respectively, and *2 represents the bonding sites of moieties C and D and their adjacent carboxyl groups bonded to moiety E; moiety E is selected from the group consisting of phenyl, biphenyl and naphthyl; moiety F is selected from the group consisting of a group of formula (IIIa), (IIIb) or (IIIc) (IIIa); (IIIb); or (IIIc) wherein * represents the bonding site of the moiety F to the imine nitrogen atom of formula II; wherein at least one of ^X1 and ^X2 is independently represented by a group of formula (IV): (IV) wherein n is an integer between 0 and 24, and wherein one or more C atoms may be replaced by -O-, -COO-, -OCO-, -OOC-, -O(CO)O-, -N-, -NR ^a -, -CON-, wherein ^Ra is a C ₁ -C ₁₂ alkyl group; and PG represents a polymerizable group selected from the group consisting of CH ₂ =C(Ph)-, CH ₂ =CW-COO-, CH ₂ =CH-COO-Ph-, CH ₂ =CW-CO-NH-, CH ₂ =CH-O-, CH ₂ =CH-OOC-, Ph-CH=CH-, CH ₂ =CH-Ph-, CH ₂ =CH-Ph-O-, R ^b -Ph-CH=CH-COO-, R ^b -OOC-CH=CH-Ph-O- and 2-W-epoxyethyl; wherein W represents H, Cl, Ph or lower alkyl and ^R represents lower alkyl, with the proviso that when ^R is attached to phenylene (-Ph-), it may also represent hydrogen or lower alkoxy, and, if applicable, ^X1 and ^X2 not represented by a radical of formula (IV) are selected from the group consisting of hydrogen, _C1 - _C12 substituted or unsubstituted linear or branched alkyl, _C3 - _C12 substituted or unsubstituted linear or branched alkenyl and _C1 - _C12 alkoxy, wherein one or more carbon atoms may be replaced by -O-, -COO-, -OCO-, -OOC-, -O(CO)O-, -N-, ^-NRa- , -CON-, wherein ^Ra is _C1 -C wherein Y is selected from the group consisting of H, or a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms; R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are independently selected from the group consisting of hydrogen, C ₁ -C ₁₂ straight or branched alkyl, C ₃ -C ₁₂ alkenyl, C ₁ -C _{12 alkoxy, C 3 -C 12 alkenyloxy , -} (CH ₂ ) _m -C(CH ₃ ) ₃ , NO ₂ , CN, COR ¹⁰⁴ , -COOR ¹⁰⁴ , -OCOR ¹⁰⁴ , -CONR ¹⁰⁵ R ¹⁰⁴ , -NR ¹⁰⁵ COR ¹⁰⁴ , OCOOR ¹⁰⁴ , -OCONR ¹⁰⁵ R ¹⁰⁴ , -NR ¹⁰⁵ COOR ¹⁰⁴ , -F, -Cl, -CF ₃ and -OCF ₃ ; wherein m is an integer between 0 and 12; R ¹⁰⁴ is selected from the group consisting of hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl having a double bond at the 3rd position or higher, -(CH ₂ ) _P -C-(CF ₃ ) ₃ , CN and an unsubstituted or substituted benzene ring, wherein the substituent of the benzene ring is selected from the group consisting of C ₁ -C ₆ straight or branched alkyl, C ₁ -C ₆ alkoxy, -C-(CH ₃ ) ₃ , halogen, -CF ₃ , NO ₂ , CN, COR ¹⁰⁷ , -COOR ¹⁰⁷ , -OCOR ¹⁰⁷ , -CONR ¹⁰⁶ R ¹⁰⁷ , -NR ¹⁰⁶ COR ^{R 107} , OCOOR ¹⁰⁷ , -OCONR ¹⁰⁶ R ¹⁰⁷ , -NR ¹⁰⁶ COOR ¹⁰⁷ , -F, -Cl, -CF ₃ and -OCF ₃ ; wherein R ¹⁰⁶ is selected from the group consisting of hydrogen, lower alkyl and lower alkenyl; R ¹⁰⁷ is selected from the group consisting of hydrogen, C ₁ -C ₁₈ alkyl and C ₃ -C ₁₈ alkenyl having a double bond at position 3 or higher; p is an integer between 0 and 12; R ¹⁰⁵ is selected from the group consisting of hydrogen, lower alkyl, lower alkenyl and lower alkoxy; and wherein n is 0, 1, 2 or 3; Z is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, wherein one or more carbon atoms may be replaced by -O-COO-, -OCO-, -OOC-, -O(CO)O-, -N-, NR ^a -, -CON-, -CO-R ^b1 or -NH-R ^c , wherein ^Ra is C ₁ -C ₁₂ alkyl, R ^b1 and R ^c are independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an organic group having 2 to 30 carbon atoms including at least one aromatic ring, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms. The polymerizable liquid crystal composition of claims 5 and 6, wherein part F is a group of formula (IIIb) or (IIIc). A polymerizable liquid crystal composition as claimed in claims 5 and 6, wherein moieties C and D are independently selected from phenyl or cyclohexyl, with the proviso that at least one of moieties C or D is phenyl. The polymerizable liquid crystal composition of claim 5 to 7, wherein part E is a benzene ring. The polymerizable liquid crystal composition of claim 5 to claim 8, wherein at least one of the moieties C and D is an aromatic ring or contains an aromatic ring and the group of formula (IV) is Where n is an integer between 0 and 24. The polymerizable liquid crystal composition of claim 5 to 9, wherein R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are independently selected from the group consisting of hydrogen, and C ₁ -C ₁₂ linear or C ₃ -C ₁₂ branched alkyl. The polymerizable liquid crystal composition of any of the preceding claims, further comprising a polymerization inhibitor. The polymerizable liquid crystal composition of any of the preceding claims, further comprising a crosslinking agent selected from the group consisting of monofunctional, bifunctional and polyfunctional compounds containing at least one olefinic double bond and polythiols having two or more thiol groups per molecule. A liquid crystal film is a cured product of the polymerizable liquid crystal composition as claimed in any one of the preceding claims. A method for manufacturing a liquid crystal film as claimed in claim 13, comprising aligning a polymerizable liquid crystal compound to obtain a polymerizable liquid crystal layer in which the polymerizable liquid crystal compound has a predetermined orientation; polymerizing the polymerizable liquid crystal compound to form a network in which the orientation of the liquid crystal is fixed; and pressing the liquid crystal film layer onto a pressure-sensitive adhesive coated on a substrate. A use of the liquid crystal film of claim 13 or the liquid crystal film obtained by the method of claim 14, which is used to manufacture optical devices or electro-optical devices.