Polymerizable liquid crystal composition

Abstract

A polymerizable liquid crystal composition comprising: (i) a polymerizable liquid crystal compound capable of exhibiting birefringence of reversed wavelength dispersivity when the polymerizable liquid crystal compound is in an oriented state; and (ii) a polymerization initiator represented by the following formula (I): The polymerizable liquid crystal composition exhibits good high temperature stability. The liquid crystal film obtainable via curing of the polymerizable product can be used in the manufacture of optical or electro-optical devices.

Description

TECHNICAL FIELD

[0001] The present application 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. BACKGROUND

[0002] There is a need for an anisotropic liquid crystal film exhibiting negative optical retardation dispersion. For example, a quarter wave film made of a negative dispersion birefringent material will largely achromatize. A device such as a reflective LCD using such a quarter wave film will have a dark state that is not colored.

[0003] WO 2021 / 037774 relates to a composition for an optical film comprising at least two anisotropic liquid crystal compounds. The optical film exhibits a reversed retardation pattern of polarized light over a wide wavelength band.

[0004] A cured liquid crystal film formed from a liquid crystal composition containing a polymerizable liquid crystal (LCP) compound is generally formed by aligning a polymerizable liquid crystal compound in a liquid crystal state on an alignment substrate to obtain a polymerizable liquid crystal layer in which 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.

[0005] In many cases, polymerization is initiated by irradiation of light such as ultraviolet light, and a photopolymerization initiator is used as a polymerization initiator.

[0006] WO 2021 / 175855 discloses an a-oximino ester compound based on a carbazole derivative having a specific substituent, which can be used as a photopolymerization initiator.

[0007] Liquid crystal polymer (LCP) materials, while 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.

[0008] The cause of the degradation has not been fully elucidated. However, this can be attributed at least in part to a low polymerization rate and a high radical content. The polymerizable liquid crystal compound exhibiting a reversed wavelength dispersion has a maximum absorption in the wavelength region of active energy rays typified by ultraviolet light, cleaving 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 cleavage of the photopolymerization initiator, making it difficult to achieve a high polymerization rate.

[0009] To increase the polymerization rate of such polymerizable liquid crystal compounds, in view of the absorption of the polymerizable liquid crystal compound to active energy rays, it is necessary to irradiate high intensity active energy rays. As a result, there is a tendency that the structure of the polymerizable liquid crystal compound is broken and the alignment defect is accompanied, and it can be difficult to impart high optical properties to the resulting liquid crystal film. SUMMARY

[0010] Therefore, there is a need for an LCP composition for preparing an aligned polymer film showing advantageous high temperature stability.

[0011] The present application provides 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 represented by the following formula (I):

[0012]

[0013] wherein

[0014] R 1 is hydrogen, C1-C 20 alkyl, C 1- C6alkyl-C3-C6cycloalkyl, C3-C 20 cycloalkyl or C2-C 12 alkenyl, wherein C3-C 20 cycloalkyl or C2-C 12 alkenyl is uninterrupted or interrupted by one or more O, S, CO, NR 10 or COOR 4 ; or

[0015] R 1 is C1-C 20 alkyl, which is unsubstituted or substituted by one or more halogen, OR 4 , SR 9 , NR 10 R 11 , COOR 4 , CONR 10 R 11 , CN, PO(OR 3a )2, S(O) m -R 3a , C3-C8cycloalkyl, which is uninterrupted or interrupted by one or more O, S, CO or NR 10 ; or substituted by one or more C6-C 20 aryl, C3-C 20 heteroaryl, C6-C20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein each is unsubstituted or substituted via one or more halogens, phenyl groups, C1-C groups. 20 Alkylphenyl, C1-C8 alkoxyphenyl, C1-C4 haloalkyl, CN, NO2, OR 4 SR 9 NR 10 R 11 PO(OR) 3a )2 or S(O) m -R 3a Replace; or

[0016] R 1 For C2-C 20 Alkyl groups, which are derived from one or more of O, CO, S, C(O)O, OC(O), SO, SO2, phenyl, naphthyl, or NR. 10 Interruption, of which C2-C is interrupted 20 Alkyl groups that are unsubstituted or derived from one or more halogens, C3-C8 cycloalkyl groups, OH, SH, OR 4 SR 9 COOR 4 O(CO)-R 3a CONR 10 R 11 NR 10 R 11 C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or via one or more halogens, C1-C8 alkyl groups, or OR groups. 4 SR 9 or NR 10 R 11 Replace; or

[0017] R 1 For C6-C 20 Aryl or C3-C 20 heteroaryl groups, each unsubstituted or via one or more C1-C... 20 Alkyl, phenyl, halogen, C1-C4 haloalkyl, CN, NO2, OR 4 SR 9 NR 10 R 11 COOR4 (CO)-R 3a (CO)NR 10 R 11 PO(OR 3a )2, S(O) m -R 3a or a group substituted; or by one or more C2-C 20 alkyl groups, which are interrupted by one or more O, S or NR 20 ; or by one or more C1-C 10 alkyl groups, which are unsubstituted or substituted by one or more halogen, COOR 20 , CONR 20 R 4 , phenyl, C3-C8cycloalkyl, C3-C 10 heteroaryl, C6-C 11 aryloxy, C3-C 20 heteroaryloxy, C6-C 20 aryloxycarbonyl, C3-C 20 heteroaryloxycarbonyl, OR 4 , SR 9 or NR 10 R 11 ; or by one or more phenyl, naphthyl, benzoyl or naphthoyl groups, each of which is unsubstituted or substituted by OR 4 , SR 9 or NR 10 R 11 ; or

[0018] R 1 is C2-C 20 alkanoyl or benzoyl, which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, OR 4 , SR 9 or NR 10 R 11 ; or

[0019] R 1 is C2-C 12 alkoxycarbonyl, which is optionally interrupted by one or more -O- and / or optionally substituted by one or more hydroxyl groups; or

[0020] R 1 is phenoxycarbonyl, which is unsubstituted or substituted by C1-C6alkyl, halogen, phenyl, OR 4 , SR 9 or NR 10 R 11 ; or

[0021] R 1CN, (CO)-R 3a , COOR 4 , CONR 10 R 11 , NO2, PO(OR 3a )2 or S(O) m -R 3a ;

[0022] R 1a is hydrogen, C1-C 20 alkyl, CN, (CO)-R 3a , COOR 4a , CONR 10a R 11a , NO2, PO(OR 3a )2 or S(O) m -R 3a ; or

[0023] R 1a is C1-C 20 alkyl, which is substituted by one or more halogen, OR 4a , SR 9a , NR 10a R 11a , CN, COOR 4a , CONR 10a R 11a , PO(OR 3a )2, S(O) m -R 3a , C3-C8cycloalkyl, which is uninterrupted or interrupted by one or more O, S, CO or NR 10a ; or by one or more C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, phenyl, C1-C 20 alkylphenyl, C1-C8alkoxyphenyl, C1-C4haloalkyl, CN, NO2, OR 4a , SR 9a , NR 10a R 11a , PO(OR 3a )2 or S(O) m -R 3a ; or

[0024] R 1a is C1-C 20 alkyl, which is substituted by one or more O, S, NR 10a, CO, SO or SO2, which is unsubstituted or substituted by C3-C8cycloalkyl, OH, SH, O(CO)R 3a , COOR 4a , CONR 10a R 11a , C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl, wherein C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl is unsubstituted or substituted by one or more halogen, C1-C8alkyl, OR 4a , SR 9a or NR 10a R 11a ; or

[0025] R 1a is C2-C 12 alkenyl or C3-C 20 cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR 10a or COOR 4a ; or

[0026] R 1a is C6-C 20 aryl or C3-C 20 heteroaryl, each of which is unsubstituted or substituted by one or more halogen, CN, NO2, 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 by one or more C 1- C 20 alkyl, which C 1- C 20 alkyl is unsubstituted or substituted by one or more halogen, COOR 4a , CONR 10a R 11a , phenyl, C3-C8cycloalkyl, C3-C 20 heteroaryl, OR 4a , SR 9aor NR 10a R 11a substituted; or substituted by one or more C2-C 20 alkyl, which C2-C 20 alkyl is interrupted by one or more O, S or NR 10a ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthoyl, each of which is unsubstituted or substituted by one or more OR 4a , SR 9a or NR 10a R 11a substituted;

[0027] R 2 is hydrogen, C1-C 20 alkyl or C1-C6alkyl-C3-C6cycloalkyl, which is unsubstituted or substituted by one or more halogen, OR 4 , SR 9 , COOR 4 , CONR 10 R 11 , NR 10 R 11 , PO(OR 3a )2, COR 3a , or

[0028] R 2 is C2-C 20 alkyl or C1-C6alkyl-C3-C6cycloalkyl, which is interrupted by one or more O, CO, S, C(O)O, OC(O), SO, SO2, phenylene, naphthylene or NR 10 ; wherein the C2-C 20 alkyl which is interrupted is unsubstituted or substituted by one or more halogen, OR 4 , SR 9 , COOR 4 , CONR 10 R 11 , NR 10 R 11 ; or

[0029] R 2 is C2-C4hydroxyalkyl, C2-C 10 alkoxyalkyl, C3-C5alkenyl, C3-C8cycloalkyl, phenyl-C1-C3alkyl, C2-C8alkanoyl, C3-C 12 alkenoyl, benzoyl; or

[0030] R 2 is C6-C 20 aryl or C3-C 20 heteroaryl, each of which is unsubstituted or substituted by one or more C1-C 12alkyl, C1-C4haloalkyl, phenyl, halogen, CN, NO2, OR 4 , SR 9 , NR 10 R 11 , (CO)-R 3a substituted or with C2-C 20 alkyl, which is interrupted by one or more O, S or NR 20 , or each of which is substituted by one or more C1-C 10 alkyl, which is unsubstituted or substituted by one or more halogen, COOR 20 , CONR 20 R 4 , phenyl, C3-C8cycloalkyl, C3-C 10 heteroaryl, C6-C 11 aryloxy, C3-C 20 heteroaryloxy, C6-C 20 aryloxycarbonyl, C3-C 20 heteroaryloxycarbonyl, OR 4 , SR 9 or NR 10 R 11 ; or

[0031] R 2 is a radical

[0032] R 3 is hydrogen or C1-C 20 alkyl; or

[0033] R 3 is C1-C 20 alkyl, which is substituted by one or more halogen, OR 4 , SR 9 , NR 10 R 11 , CN, COOR 4 , CONR 10 R 11 , C3-C8cycloalkyl, which is uninterrupted or interrupted by one or more O, S, CO or NR 10 ; or by one or more C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, phenyl, C1-C 20 alkylphenyl, C1-C8alkoxyphenyl, C1-C4haloalkyl, CN, NO2, OR 4 , SR 9or NR 10 R 11 substituted; or

[0034] R 3 C1-C 20 alkyl, which is interrupted by one or more O, S, NR 10 , CO, SO or SO2, which is unsubstituted or substituted by C3-C8cycloalkyl, OH, SH, O(CO)-R 3a , COOR 4 , CONR 10 R 11 C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl, wherein C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl is unsubstituted or substituted by one or more halogen, C1-C8alkyl, OR 4 , SR 9 or NR 10 R 11 substituted; or

[0035] R 3 C2-C 12 alkenyl or C3-C 20 cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR 10 or COOR 4 ; or

[0036] R 3 C6-C 20 aryl or C3-C 20 heteroaryl, each of which is unsubstituted or substituted by one or more halogen, C1-C 20 alkyl, C1-C4haloalkyl, phenyl, C1-C 20 alkylphenyl, C1-C8alkoxyphenyl, CN, NO2, OR 4 , SR 9 , NR 10 R 11 , COOR 4 , (CO)-R 3a or SO2-R 3a ; or

[0037] R 3 C1-C 20 alkoxy, which is unsubstituted or substituted by one or more C1-C10 Alkyl, C1-C4 haloalkyl, halogen, phenyl, C1-C 20 Alkylphenyl or C1-C8 alkoxyphenyl substituted; or

[0038] R 3 For C1-C 20 Alkyl groups, which are formed by one or more O, S, NR groups 10 Interruption of CO, SO or SO2; or

[0039] R 3 For C6-C 20 Aryloxy or C3-C 20 Heteroaryl groups, each unsubstituted or via one or more halogens, C1-C 20 Alkyl, C1-C4 haloalkyl, phenyl, C1-C 20 Alkylphenyl, C1-C8 alkoxyphenyl, CN, NO2, OR 4 SR 9 NR 10 R 11 COOR 4 (CO)-R 3a or SO2-R 3a replace;

[0040] R 3a It is hydrogen or C1-C 20 Alkyl; or

[0041] R 3a For C1-C 20 Alkyl groups, which are derived from one or more halogens, OR 4a SR 9a NR 10a R 11a CN, COOR 4a CONR 10a R 11a C3-C8 cycloalkyl substitution, wherein the C3-C8 cycloalkyl group is uninterrupted or via one or more O, S, CO or NR. 10a Interrupted; or via one or more C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein each is unsubstituted or substituted via one or more halogens, phenyl groups, C1-C groups. 20 Alkylphenyl, C1-C8 alkoxyphenyl, C1-C4 haloalkyl, CN, NO2, OR 4a SR 9a or NR 10a R 11a Replace; or

[0042] R 3a is C1-C 20 alkyl, which is interrupted by one or more O, S, NR 10a , CO, SO or SO2, which is unsubstituted or substituted by C3-C8cycloalkyl, OH, SH, O(CO)-(C1-C8alkyl), COOR 4a , CONR 10a R 11a , C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl, wherein C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl is unsubstituted or substituted by one or more halogen, C1-C8alkyl, OR 4a , SR 9a or NR 10a R 11a ; or

[0043] R 3a is C2-C 12 alkenyl or C3-C 20 cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR 10a or COOR 4a ; or

[0044] R 3a is C6-C 20 aryl or C3-C 20 heteroaryl, each of which is unsubstituted or substituted by one or more halogen, C1-C 20 alkyl, C1-C4haloalkyl, phenyl, C1-C 20 alkylphenyl, C1-C8alkoxyphenyl, CN, NO2, OR 4a , SR 9a , NR 10a R 11a , COOR 4a , (CO)-(C1-C8alkyl) or SO2-(C1-C4haloalkyl); or

[0045] R 3a is C1-C 20 alkoxy, which is unsubstituted or substituted by one or more C1-C 10 alkyl, C1-C4haloalkyl, halogen, phenyl, C1-C 20alkyl, C1-C4haloalkyl, phenyl, C1-C8alkylphenyl, C1-C8alkoxyphenyl, CN, NO2, OR

[0046] R 3a is C1-C 20 alkyl, which is interrupted by one or more O, S, NR 10a , CO, SO or SO2; or

[0047] R 3a is C6-C 20 aryloxy or C3-C 20 heteroaryloxy, each of which is unsubstituted or substituted by one or more halogen, C1-C 20 alkyl, C1-C4haloalkyl, phenyl, C1-C 20 alkylphenyl, C1-C8alkoxyphenyl, CN, NO2, OR 4a , SR 9a , NR 10a R 11a , COOR 4a , (CO)-(C1-C8alkyl) or SO2-(C1-C4haloalkyl); or

[0048] R 3a is a radical

[0049] R 3b is hydrogen or C1-C 20 alkyl; or

[0050] R 3b is C1-C 20 alkyl, which is interrupted by one or more halogen, OR 4a , SR 9a , NR 10a R 11a , CN, COOR 4a , CONR 10a R 11a , C3-C8cycloalkyl, which is uninterrupted or interrupted by one or more O, S, CO or NR 10a ; or substituted by one or more C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, phenyl, C1-C 20 alkylphenyl, C1-C8alkoxyphenyl, C1-C4haloalkyl, CN, NO2, OR 4a , SR 9a or NR 10a R 11a ; or

[0051] R 3b is C1-C 20 alkyl, which is interrupted by one or more O, S, NR 10a , CO, SO or SO2, which is unsubstituted or substituted by C3-C8cycloalkyl, OH, SH, O(CO)-(C1-C8alkyl), COOR 4a , CONR 10a R 11a , C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C 3- C 20 heteroarylcarbonyl, wherein C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl is unsubstituted or substituted by one or more halogen, C1-C8alkyl, OR 4a , SR 9a or NR 10a R 11a ; or

[0052] R 3b is C2-C 12 alkenyl or C3-C 20 cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR 10a or COOR 4a ; or

[0053] R 3b is C6-C 20 aryl or C3-C 20 heteroaryl, each of which is unsubstituted or substituted by one or more halogen, C1-C 20 alkyl, C1-C4haloalkyl, phenyl, C1-C 20 alkylphenyl, C1-C8alkoxyphenyl, CN, NO2, OR 4a , SR 9a , NR 10a R 11a , COOR 4a , (CO)-(C1-C8alkyl) or SO2-(C1-C4haloalkyl); or

[0054] R 3b is C1-C 20 alkoxy, which is unsubstituted or substituted by one or more C1-C 10 alkyl, C1-C4haloalkyl, halogen, phenyl, C1-C20 alkyl, C1-C4haloalkyl, phenyl, C1-C8alkylphenyl, C1-C8alkoxyphenyl, CN, N02, OR

[0055] R 3b is C1-C 20 alkyl, which is interrupted by one or more O, S, NR 10a , CO, SO or S02; or

[0056] R 3b is C6-C 20 aryloxy or C3-C 20 heteroaryloxy, each of which is unsubstituted or substituted by one or more halogen, C1-C 20 alkyl, C1-C4haloalkyl, phenyl, C1-C 20 alkylphenyl, C1-C8alkoxyphenyl, CN, N02, OR 4a , SR 9a , NR 10a R 11a , COOR 4a , (CO)-(C1-C8alkyl) or S02-(C1-C4haloalkyl);

[0057] R 4 is hydrogen, (CO)-R 3a , COOR 4a , CONR 10a R 11a , S(O) m -R 3a or PO(OR 3a )2; or

[0058] R 4 is C1-C 20 alkyl, which is substituted by one or more halogen, OR 4a , SR 9a , NR 10a R 11a , CN, COOR 4a , CONR 10a R 11 a, PO(OR 3a )2, S(O) m -R 3a , C3-C8cycloalkyl, which is uninterrupted or interrupted by one or more O, S, CO or NR 10a ; or by one or more C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20halogen, C1-C8alkyl, OR 20 alkyl, C1-C8alkoxy, C1-C4haloalkyl, CN, NO2, OR 4a , SR 9a , NR 10a R 11a , PO(OR 3a )2or S(O) m -R 3a substituted; or

[0059] R 4 is C1-C 20 alkyl, which is interrupted by one or more O, S, NR 10a , CO, SO or SO2, which is unsubstituted or substituted by C3-C8cycloalkyl, OH, SH, O(CO)-R 3a , COOR 4a , CONR 10a R 11a , C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl, wherein C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl is unsubstituted or substituted by one or more halogen, C1-C8alkyl, OR 4a , SR 9a or NR 10a R 11a ; or

[0060] R 4 is C2-C 12 alkenyl or C3-C 20 cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR 10a or COOR 4a ; or

[0061] R 4 is C6-C 20 aryl, which is substituted by one or more halogen, CN, NO2, OR 4a , SR 9a , NR 10a R 11a , COOR 4a , (CO)-R 3a , CONR 10a R 11aPO(OR) 3a 2. S(O) m -R 3a or groups Replacement; or via one or more C1-C 20 Alkyl substitution, the C1-C 20 Alkyl groups that are unsubstituted or derived from one or more halogens, COOR 4a CONR 10a R 11a , phenyl, C3-C8 cycloalkyl, C3-C 20 heteroaryl, OR 4a SR 9a or NR 10a R 11a Replacement; or via one or more C2-C 20 Alkyl substitution, the C2-C 20 Alkyl groups via one or more O, S, or NR 10a Interrupted; or substituted with one or more phenyl, naphthyl, benzoyl, or naphthyl groups, each of which is unsubstituted or substituted with OR 4a SR 9a or NR 10a R 11a Replace; or

[0062] R 4 For C3-C 20 Heteroaryl groups, each unsubstituted or mediated by one or more halogens, CN, NO2, 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 groups Replacement; or via one or more C1-C 20 Alkyl substitution, the C1-C 20 Alkyl groups that are unsubstituted or derived from one or more halogens, COOR 4a CONR 10a R 11a , phenyl, C3-C8 cycloalkyl, C3-C 20 heteroaryl, OR 4a SR 9a or NR 10a R 11a Replacement; or via one or more C2-C 20 Alkyl substitution, the C2-C20 alkyl, interrupted by one or more O, S or NR 10a interrupted; or substituted by one or more phenyl, naphthyl, benzoyl or naphthoyl, each of which is unsubstituted or substituted by OR 4a , SR 9a or NR 10a R 11a ; or

[0063] R 4 together with one of the carbon atoms of R 1 form a 5- or 6-membered saturated or unsaturated ring, which is uninterrupted or interrupted by O, S or NR 10a , and which 5- or 6-membered saturated or unsaturated ring is unsubstituted or substituted by one or more C1-C 20 alkyl, OR 4a , SR 9a , NR 10a R 11a , (CO)-R 3a , NO2, halogen, C1-C4haloalkyl, CN, phenyl, C1-C 20 alkylphenyl, C1-C8alkoxyphenyl, or C3-C 20 cycloalkyl, which C3-C 20 cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR 10a ;

[0064] R 4a is hydrogen, C1-C 20 alkyl, (CO)O(C1-C8alkyl) or CON(C1-C8alkyl)2; or

[0065] R 4a is C1-C 20 alkyl, which is substituted by one or more halogen, OH, SH, CN, C3-C8alkenyloxy, OCH2CH2CN, OCH2CH2(CO)O(C1-C8alkyl), O(CO)-(C1-C8alkyl), O(CO)-(C2-C4)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C1-C8alkyl), C3-C8cycloalkyl, SO2-(C1-C4haloalkyl), O(C1-C4haloalkyl), phenyl, C1-C8alkylphenyl, C1-C8alkoxyphenyl or C3-C8cycloalkyl, which C3-C8cycloalkyl is interrupted by one or more O; or

[0066] R 4a is C2-C 20alkyl, which is interrupted by one or more O, S, N(Ci-C8alkyl), CO, SO or SO2, which is unsubstituted or substituted by C3-C8cycloalkyl, OH, SH, 0(CO)(Ci-C8alkyl), (CO)O(Ci-C8alkyl), (CO)N(Ci-C8alkyl)2, C6-Ci0aryl or phenyl; 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, CN, NO2, OH, Ci-C8alkyl, Ci-C4haloalkyl, Ci-C8alkoxy, phenyl-Ci-C3alkoxy, phenoxy, Ci-C8alkylmercapto, phenylmercapto, N(Ci-C8alkyl)2, diphenylamino, (CO)O(Ci-C8alkyl), (CO)-Ci-C8alkyl or (CO)N(Ci-C8)2, phenyl or benzoyl; 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, CN, NO2, OH, Ci-C8alkyl, Ci-C4haloalkyl, Ci-C8alkoxy, phenyl-Ci-C3alkoxy, phenoxy, Ci-C8alkylmercapto, phenylmercapto, N(Ci-C8alkyl)2, diphenylamino, (CO)O(Ci-C8alkyl), (CO)-Ci-C8alkyl or (CO)N(Ci-C8)2, phenyl or benzoyl;

[0067] R 4a is C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, CN, NO2, OH, Ci-C8alkyl, Ci-C4haloalkyl, Ci-C8alkoxy, phenyl-Ci-C3alkoxy, phenoxy, Ci-C8alkylmercapto, phenylmercapto, N(Ci-C8alkyl)2, diphenylamino, (CO)O(Ci-C8alkyl), (CO)-Ci-C8alkyl or (CO)N(Ci-C8)2, phenyl or benzoyl;

[0068] R 4a is C2-C 12 alkenyl, (CO)O(Ci-C8alkenyl) or C3-C8cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, N(Ci-C8alkyl) or COO(Ci-C8alkyl); or

[0069] R 4a is Ci-C 20 alkanoyl, C3-C 12 alkenoyl, each of which is unsubstituted or substituted by one or more halogen, phenyl, Ci-C8alkylphenyl, Ci-C8alkoxyphenyl, OH, Ci-C8alkoxy, phenoxy, Ci-C8alkylmercapto, phenylmercapto, N(Ci-C8alkyl)2or diphenylamino;

[0070] R 5 , R 6 , R 7 and R8 independently of one another hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, C6-C10aryl, C3-C10heteroaryl, CN, NO2, OR, SR, NR 20 independently of one another hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, C6-C10aryl, C3-C10heteroaryl, CN, NO2, OR, SR, NR 20 independently of one another hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, C6-C10aryl, C3-C10heteroaryl, CN, NO2, OR, SR, NR 20 independently of one another hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, C6-C10aryl, C3-C10heteroaryl, CN, NO2, OR, SR, NR 20 independently of one another hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, C6-C10aryl, C3-C10heteroaryl, CN, NO2, OR, SR, NR 20 independently of one another hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, C6-C10aryl, C3-C10heteroaryl, CN, NO2, OR, SR, NR 20 independently of one another hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, C6-C10aryl, C3-C10heteroaryl, CN, NO2, OR, SR, NR 20 independently of one another hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, C6-C10aryl, C3-C10heteroaryl, CN, NO2, OR, SR, NR 20 independently of one another hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, C6-C10aryl, C3-C10heteroaryl, CN, NO2, OR, SR, NR 10 independently of one another hydrogen, Ci-C4alkyl, C3-C6cycloalkyl, C6-C10aryl, C3-C10heteroaryl, CN, NO2, OR, SR, NR (CO)-R 3a , OR 4a or COOR 4 ;

[0071] R 9 is hydrogen or Ci-C4alkyl; or 20 ;

[0072] R 9 is Ci-C4alkyl, which is substituted by one or more halogen, OR 20 , SR 4a , NR 9a R 10a , CN, COOR 11a , CONR 4a R 10a , PO(OR 11a )2, S(O) 3a -R m , C3-C8cycloalkyl, which is uninterrupted or interrupted by one or more O, S, CO or NR 3a ; or by one or more C6-C10aryl, C3-C10heteroaryl, C6-C10aroyl or C3-C10heteroarylcarbonyl, each of which is unsubstituted or substituted by one or more halogen, phenyl, Ci-C4alkylphenyl, Ci-C8alkoxyphenyl, Ci-C4haloalkyl, CN, NO2, OR 10a , SR 20 , NR 20 R 20 , PO(OR 20 )2 or S(O) 20 -R 4a ; or

[0073] R 9a is Ci-C4alkyl, which is substituted by one or more halogen, OR 10a , SR 11a , NR 3a R m , CN, COOR 3a , CONR 9 R 20Alkyl groups, which are derived from one or more O, S, NR atoms 10a Disruptions involving CO, SO, or SO2, which are unsubstituted or via C3-C8 cycloalkyl groups, OH, SH, or O(CO)-R 3a COOR 4a CONR 10a R 11a C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or via one or more halogens, C1-C8 alkyl groups, or OR groups. 4a SR 9a or NR 10a R 11a Replace; or

[0074] R 9 For C2-C 12 alkenyl or C3-C 20 cycloalkyl groups, each without interruption or via one or more O, S, CO, NR 10a or COOR 4a Interruption; or

[0075] R 9 For C6-C 20 Aryl or C3-C 20 Heteroaryl groups, each unsubstituted or mediated by one or more halogens, CN, NO2, 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 groups Replacement; or via one or more C1-C 20 Alkyl substitution, the C1-C 20 Alkyl groups that are unsubstituted or derived from one or more halogens, COOR 4a CONR 10a R 11a , phenyl, C3-C8 cycloalkyl, C3-C 20 heteroaryl, OR4a , SR 9a or NR 10a R 11a substituted; or substituted by one or more C2-C 20 alkyl, which C2-C 20 alkyl is interrupted by one or more O, S or NR 10a ; or substituted by one or more phenyl, naphthyl, benzoyl or naphthoyl, each of which is unsubstituted or substituted by one or more OR 4a , SR 9a or NR 10a R 11a ; or

[0076] R 9 together with one of the carbon atoms of R 1 form a 5- or 6-membered saturated or unsaturated ring, which is uninterrupted or interrupted by O, S or NR 10a , and which 5- or 6-membered saturated or unsaturated ring is unsubstituted or substituted by one or more C1-C 20 alkyl, OR 4a , SR 9a , NR 10a R 11a , (CO)-R 3a , NO2, halogen, C1-C4haloalkyl, CN, phenyl, C1-C 20 alkylphenyl, C1-C8alkoxyphenyl, or C3-C 20 cycloalkyl, which C3-C 20 cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or NR 10a ;

[0077] R 9a is hydrogen or C1-C 20 alkyl; or

[0078] R 9a is C1-C 20 alkyl, which is substituted by one or more halogen, OH, SH, CN, C3-C8alkenyloxy, OCH2CH2CN, OCH2CH2(CO)O(C1-C8alkyl), O(CO)-(C1-C8alkyl), O(CO)-(C2-C4)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C1-C8alkyl), C3-C8cycloalkyl, SO2-(C1-C4haloalkyl), O(C1-C4haloalkyl), phenyl, C1-C8alkylphenyl, C1-C8alkoxyphenyl or C3-C8cycloalkyl, which C3-C8cycloalkyl is interrupted by one or more O; or

[0079] R9a For C2-C 20 Alkyl groups interrupted by one or more O, S, N (C1-C8 alkyl), CO, SO, or SO2, which are unsubstituted or interrupted by C3-C8 cycloalkyl, OH, SH, O(CO)(C1-C8 alkyl), (CO)O(C1-C8 alkyl), (CO)N(C1-C8 alkyl)2, C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or substituted with one or more halogens, C1-C8 alkyl groups, C1-C8 alkoxy groups, C1-C8 alkyl thio groups, or N(C1-C8 alkyl)2 groups; or

[0080] R 9a For C2-C 12 Alkenyl or C3-C8 cycloalkyl, each uninterrupted or interrupted by one or more O, S, CO, N (C1-C8 alkyl) or COO (C1-C8 alkyl); or

[0081] R 9a For C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl groups, each unsubstituted or substituted with one or more halogens, CN, NO2, OH, C1-C8 alkyl, C1-C4 haloalkyl, C1-C8 alkoxy, phenyl-C1-C3 alkoxy, phenoxy, C1-C8 alkyl hydrogen sulfide, phenyl hydrogen sulfide, N(C1-C8 alkyl)2, diphenylamino, (CO)O(C1-C8 alkyl), (CO)-C1-C8 alkyl or (CO)N(C1-C8)2, phenyl or benzoyl; or

[0082] R 9a For C1-C 20 Alkyl group, C3-C 12 The enoyl group is unsubstituted or substituted with one or more halogens, phenyl, C1-C8 alkylphenyl, C1-C8 alkoxyphenyl, OH, C1-C8 alkoxy, phenoxy, C1-C8 alkyl hydrogen sulfide, phenyl hydrogen sulfide, N(C1-C8 alkyl)2 or diphenylamino.

[0083] R 10 and R 11They are independently hydrogen, C1-C 20 Alkyl group, S(O) m -R 3a O(CO)-R 3a (CO)-R 3a or CONR 10a R 11a ;or

[0084] R 10 and R 11 C1-C are independent of each other. 20 Alkyl groups, which are derived from 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 C3-C8 cycloalkyl substitution, wherein the C3-C8 cycloalkyl group is uninterrupted or via one or more O, S, CO or NR. 10a Interrupted; or via one or more C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein each is unsubstituted or substituted via one or more halogens, phenyl groups, C1-C groups. 20 Alkylphenyl, C1-C8 alkoxyphenyl, C1-C4 haloalkyl, CN, NO2, OR 4a SR 9a NR 10a R 11a PO(OR) 3a )2 or S(O) m -R 3a Replace; or

[0085] R 10 and R 11 C1-C are independent of each other. 20 Alkyl groups, which are derived from one or more O, S, NR atoms 10a Disruptions involving CO, SO, or SO2, which are unsubstituted or via C3-C8 cycloalkyl groups, OH, SH, or O(CO)-R 3a COOR 4a CONR 10a R 11a C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C20 aroyl or C3-C 20 heteroarylcarbonyl, wherein the C6-C 20 aryl, C3-C 20 heteroaryl, C6-C 20 aroyl or C3-C 20 heteroarylcarbonyl unsubstituted or substituted by one or more halogen, C1-C8alkyl, OR 4a , SR 9a or NR 10a R 11a ; or

[0086] R 10 and R 11 are independently of each other C2-C 12 alkenyl or C3-C 20 cycloalkyl, each of which is uninterrupted or interrupted by one or more O, S, CO, NR 10a or COOR 4a ; or

[0087] R 10 and R 11 are independently of each other C6-C 20 aryl or C3-C 20 heteroaryl, each of which is unsubstituted or substituted by one or more halogen, CN, NO2, 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 by one or more C1-C 20 alkyl, which C1-C 20 alkyl is unsubstituted or substituted by one or more halogen, COOR 4a , CONR 10a R 11a , phenyl, C3-C8cycloalkyl, C3-C 20 heteroaryl, OR 4a , SR 9a or NR 10a R 11a ; or by one or more C2-C 20 alkyl, which C2-C 20 alkyl is substituted by one or more O, S or NR 10ainterrupted by one or more phenyl, naphthyl, benzoyl or naphthoyl, each of which is unsubstituted or substituted by OR 4a , SR 9a or NR 10a R 11a ; or

[0088] R 10 and R 11 are independently of each other CrC 20 alkoxy, which is unsubstituted or substituted by one or more halogen, phenyl, CrC8alkylphenyl or CrC8alkoxyphenyl; or

[0089] R 10 and R 11 are independently of each other CrC 20 alkoxy, which is interrupted by one or more O, S, NR 10a , CO, SO or SO2; or

[0090] R 10 and R 11 are independently of each other C6-C 20 aryloxy or C3-C 20 heteroaryloxy, each of which is unsubstituted or substituted by one or more halogen, CrC8alkyl, CrC4haloalkyl, phenyl, CrC8alkylphenyl, CrC8alkoxyphenyl, CN, NO2, OR 4a , SR 9a , NR 10a R 11a , COOR 4a , (CO)-R 3a or SO2-R 3a ; or

[0091] R 10 and R 1 together with one of the carbon atoms form a 5- or 6-membered saturated or unsaturated ring, which is uninterrupted or interrupted by O, S or NR 10a , and which 5- or 6-membered saturated or unsaturated ring is unsubstituted or substituted by one or more CrC 20 alkyl, OR 4a , SR 9a , NR 10a R 11a , (CO)-R 3a , NO2, halogen, CrC4haloalkyl, CN, phenyl, CrC 20 alkylphenyl, CrC8alkoxyphenyl, or C3-C 20 cycloalkyl, which C3-C 20cycloalkyl groups are uninterrupted or via one or more O, S, CO, or NR groups. 10a Interruption; or

[0092] R 10 and R 11 Together with the N atom it is attached to, it forms a 5- or 6-membered saturated or unsaturated ring, which is uninterrupted or via O, S, or NR. 10a The interruption occurs, and the 5- or 6-member saturated or unsaturated ring is not substituted or substituted via one or more C1-C14 rings. 20 Alkyl, OR 4a SR 9a NR 10a R 11a (CO)-R 3a NO2, halogens, C1-C4 haloalkyl groups, CN, phenyl Or C3-C 20 Cycloalkyl substitution, the C3-C 20 cycloalkyl groups are uninterrupted or via one or more O, S, CO, or NR groups. 10a Interruption;

[0093] R 10a and R 11a They are independently hydrogen, C1-C 20 Alkyl group, S(O) m -(C1-C8 alkyl), O(CO)(C1-C8 alkyl), (CO)(C1-C8 alkyl), (CO)O(C1-C8 alkyl) or CON(C1-C8 alkyl)2; or

[0094] R 10a and R 11a C1-C are independent of each other. 20 Alkyl groups substituted with one or more halogens, OH, SH, CN, C3-C8 alkenyloxy, OCH2CH2CN, OCH2CH2(CO)O(C1-C8 alkyl), O(CO)(C1-C8 alkyl), O(CO)-(C2-C4)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C1-C8 alkyl), C3-C8 cycloalkyl, SO2-(C1-C4 haloalkyl), O(C1-C4 haloalkyl), phenyl, C1-C8 alkylphenyl, C1-C8 alkoxyphenyl, or C3-C8 cycloalkyl, wherein the C3-C8 cycloalkyl group is interrupted by one or more O atoms; or

[0095] R 10a and R 11a C2-C are independent of each other. 20Alkyl groups interrupted by one or more O, S, N (C1-C8 alkyl), CO, SO, or SO2, which are unsubstituted or interrupted by C3-C8 cycloalkyl, OH, SH, O(CO)(C1-C8 alkyl), (CO)O(C1-C8 alkyl), (CO)N(C1-C8 alkyl)2, C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or substituted with one or more halogens, C1-C8 alkyl groups, C1-C8 alkoxy groups, C1-C8 alkyl thio groups, or N(C1-C8 alkyl)2 groups; or

[0096] R 10a and R 11a C2-C are independent of each other. 12 Alkenyl or C3-C8 cycloalkyl, each uninterrupted or interrupted by one or more O, S, CO, N (C1-C8 alkyl) or COO (C1-C8 alkyl); or

[0097] R 10a and R 11a C6-C are independent of each other. 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl groups, each unsubstituted or substituted with one or more halogens, CN, NO2, OH, C1-C8 alkyl, C1-C4 haloalkyl, C1-C8 alkoxy, phenyl-C1-C3 alkoxy, phenoxy, C1-C8 alkyl hydrogen sulfide, phenyl hydrogen sulfide, N(C1-C8 alkyl)2, diphenylamino, (CO)O(C1-C8 alkyl), (CO)-C1-C8 alkyl or (CO)N(C1-C8 alkyl)2, phenyl or benzoyl; or

[0098] R 10a and R 11a C1-C are independent of each other. 20 Alkyl group, C3-C 12 The enoyl group, each unsubstituted or substituted with one or more halogens, phenyl, C1-C8 alkylphenyl, C1-C8 alkoxyphenyl, OH, C1-C8 alkoxy, phenoxy, C1-C8 alkylhydrothio, phenylhydrothio, N(C1-C8 alkyl)2, or diphenylamino; or

[0099] R 10a and R 11a independently of one another are C1-C 20 alkyl, which is unsubstituted or substituted by one or more halogen, phenyl, C1-C8alkylphenyl or C1-C8alkoxyphenyl; or

[0100] R 10a and R 11a independently of one another are C1-C 20 alkyl, which is interrupted by one or more O, S, N(C1-C8alkyl), CO, SO or SO2; or

[0101] R 10a and R 11a independently of one another are C6-C 20 aryloxy or C3-C 20 heteroaryloxy, each of which is unsubstituted or substituted by one or more halogen, C1-C8alkyl, C1-C4haloalkyl, phenyl, C1-C8alkylphenyl, C1-C8alkoxyphenyl, CN, NO2, C1-C8alkoxy, C1-C8alkylmercapto, N(C1-C8alkyl)2, CO(OC1-C8alkyl), (CO)-(C1-C8alkyl) or SO2-(C1-C8alkyl); or

[0102] R 10a and R 11a together with the N 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(C1-C8alkyl), and wherein the 5- or 6-membered saturated or unsaturated ring is unsubstituted or substituted by one or more C1-C8alkyl, C1-C8alkoxy, C1-C8alkylmercapto, N(C1-C8alkyl)2, NO2, halogen, C1-C4haloalkyl, CN, phenyl or C3-C 20 cycloalkyl, which C3-C 20 cycloalkyl is uninterrupted or interrupted by one or more O, S, CO or N(C1-C8alkyl);

[0103] R 12 and R 13 independently of one another are hydrogen, C1-C 12 alkyl, which C1-C 12 alkyl is optionally substituted by one or more halogen, phenyl, CN, -OH, -SH, C1-C4alkoxy, (CO)OH or (CO)O(C1-C4alkyl); or

[0104] R 12 and R 13 are phenyl, which is optionally substituted by one or more C1-C6alkyl, halogen, CN, OR 4 , SR9 or NR 10 R 11 Replace; or

[0105] R 12 and R 13 For halogen, CN, OR 4 SR 9 SOR 9 SO2R 9 or NR 10 R 11 The substituent OR 4 SR 9 or NR 10 R 11 via group R as needed 4 R 9 R 10 and / or R 11 With one of the carbon atoms of phenyl, naphthyl, benzoyl or naphthyl or the substituent R 3a The carbon atoms form 5- or 6-membered rings; or

[0106] R 12 and R 13 Together as a group Where R 14 R 15 R 16 and R 17 They are independently hydrogen, C1-C 12 Alkyl, the C1-C 12 Alkyl groups are substituted as desired with one or more halogens, phenyl groups, CN groups, -OH groups, -SH groups, C1-C4 alkoxy groups, (CO)OH groups, or (CO)O groups (C1-C4 alkyl groups); or R groups. 14 R 15 R 16 and R 17 It is a phenyl group, which, as needed, is esterified by one or more C1-C6 alkyl groups, halogens, CN, OR. 4 SR 9 or NR 10 R 11 Replace; or R 14 R 15 R 16 and R 17 Halogen, CN, OR 4 SR 9 or NR 10 R 11 ;or

[0107] R 12 and R 13 Together as a group Where R18 and R 19 independently of one another hydrogen, Ci-C6alkyl, C3-C6cycloalkyl, C2-C6alkenyl, C2-C6alkynyl, phenyl, or 12 alkyl, said Ci-C6alkyl being optionally substituted by one or more halogen, phenyl, CN, -OH, -SH, Ci-C4alkoxy, (CO)OH, or (CO)O(Ci-C4alkyl); or R 12 alkyl being optionally substituted by one or more halogen, phenyl, CN, -OH, -SH, Ci-C4alkoxy, (CO)OH, or (CO)O(Ci-C4alkyl); or R 18 and R 19 is phenyl, which is optionally substituted by one or more Ci-C6alkyl, halogen, CN, OR 4 , SR 9 , or NR 10 R 11 ; substituted;

[0108] m is 1 or 2; and

[0109] Q is CO or a direct bond.

[0110] The polymerization initiator is a carbazolyl a-oximino ester compound according to formula (I). DETAILED DESCRIPTION

[0111] In a preferred particular embodiment, R 1 is Ci-C6alkyl, Ci-C6alkyl-C3-C6cycloalkyl, C3-C6cycloalkyl; or 20 In a preferred particular embodiment, R 20 is Ci-C6alkyl, Ci-C6alkyl-C3-C6cycloalkyl, C3-C6cycloalkyl; or

[0112] R 1 is C2-C6alkyl, which is interrupted by one or more O, CO, S, C(O)O, OC(O), SO, or SO2; or 20 is C2-C6alkyl, which is interrupted by one or more O, CO, S, C(O)O, OC(O), SO, or SO2; or

[0113] R 1 is C6-C10aryl, which is unsubstituted or substituted by one or more Ci-C4alkyl. 20 is C6-C10aryl, which is unsubstituted or substituted by one or more Ci-C4alkyl. 20 is C6-C10aryl, which is unsubstituted or substituted by one or more Ci-C4alkyl.

[0114] In a particularly preferred particular embodiment, R 1 is Ci-C6alkyl, preferably straight-chain Ci-C8alkyl, in particular straight-chain C2-C6alkyl. 20 is Ci-C6alkyl, preferably straight-chain Ci-C8alkyl, in particular straight-chain C2-C6alkyl.

[0115] In a preferred particular embodiment, R 2 is Ci-C6alkyl; or 20 In a preferred particular embodiment, R

[0116] R 2 is C2-C6alkyl, which is interrupted by one or more O, CO, S, C(O)O, OC(O), SO, or SO2; or 20 is C2-C6alkyl, which is interrupted by one or more O, CO, S, C(O)O, OC(O), SO, or SO2; or

[0117] R 2 is C6-C 20 aryl, which is unsubstituted or substituted by one or more C1-C 12 alkyl or (CO)-R 3a substituents.

[0118] In a particularly preferred embodiment, R 2 is C2-C 10 alkyl.

[0119] In another preferred embodiment, R 3 is hydrogen or C1-C 20 alkyl, preferably C1-C 20 alkyl, in particular straight-chain C1-C 20 alkyl, such as straight-chain C1-C6alkyl, most preferably methyl.

[0120] In another preferred embodiment, R 3a is C1-C 20 alkyl; or

[0121] R 3a is C6-C 20 aryl or C3-C 20 heteroaryl, each of which is unsubstituted or substituted by one or more halogen, C1-C 20 alkyl, C1-C4haloalkyl, phenyl, C1-C 20 alkylphenyl, C1-C8alkoxyphenyl, CN, NO2, OR 4a , SR 9a , NR 10a R 11a , COOR 4a , (CO)-(C1-C8alkyl) or SO2-(C1-C4haloalkyl).

[0122] In a particularly preferred embodiment, R 3a is C1-C 20 alkyl, preferably R 3a is C1-C 10 alkyl.

[0123] 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, in particular (CO)-R 3a .

[0124] In another preferred embodiment, R 4a is C1-C 20 alkyl, C6-C 20 aryl or C3-C 20 heteroaryl.

[0125] In a particularly preferred embodiment, R 4a is C1-C 20 alkyl, preferably C1-C8 alkyl.

[0126] In another preferred embodiment, R 5 , R 6 , R 7 and R 8 are independently of each other hydrogen or C1-C 20 alkyl.

[0127] In a particularly preferred embodiment, R 5 , R 6 , R 7 and R 8 are hydrogen.

[0128] In another preferred embodiment, R 9 is hydrogen or C1-C 20 alkyl.

[0129] In a particularly preferred embodiment, R 9 is hydrogen or C1-C8 alkyl.

[0130] In another preferred embodiment, R 10 and R 11 are independently of each other hydrogen, C1-C 20 alkyl, S(O) m -R 3a , O(CO)-R 3a (CO)-R 3a or CONR 10a R 11a .

[0131] In a particularly preferred embodiment, R 10 and R 11 are independently of each other hydrogen or C1-C8 alkyl.

[0132] In another preferred embodiment, R 10a and R 11a are independently of each other hydrogen, C1-C 20 alkyl, S(O) m(C1-C8alkyl), O(CO)(C1-C8alkyl), (CO)(C1-C8alkyl), (CO)O(C1-C8alkyl) or CON(C1-C8alkyl)2.

[0133] In a particularly preferred embodiment, R 10a and R 11a are independently of each other hydrogen or C1-C8alkyl.

[0134] In a particular embodiment, the compound of formula (I) is a compound, wherein

[0135] R 1 is hydrogen, C1-C 20 alkyl, C1-C6alkyl-C3-C6cycloalkyl, C3-C 20 cycloalkyl or C2-C 12 alkenyl, wherein C3-C 20 cycloalkyl or C2-C 12 alkenyl is uninterrupted or interrupted by one or more O, S, CO, NR 10 or COOR 4 ;

[0136] R 2 is hydrogen, C1-C 20 alkyl or C1-C6alkyl-C3-C6cycloalkyl, which is unsubstituted or substituted by one or more halogen, OR 4 , SR 9 , COOR 4 , CONR 10 R 11 , NR 10 R 11 , PO(OR 3a )2, COR 3a ;

[0137] R 3 is hydrogen or C1-C 20 alkyl;

[0138] R 3a is hydrogen or C1-C 20 alkyl;

[0139] R 4 is hydrogen, (CO)-R 3a , COOR 4a , CONR 10a R 11a , S(O) m -R 3a or PO(OR 3a )2;

[0140] R 4aHydrogen, C1-C 20 Alkyl, (CO)O (C1-C8 alkyl) or CON (C1-C8 alkyl)2;

[0141] R 5 R 6 R 7 and R 8 They are independently hydrogen, C1-C 20 Alkyl, C6-C 20 Aryl, C1-C 20 Alkoxy, C6-C 20 Aryl C1-C 20 Alkyl, hydroxy-C1-C 20 Alkyl, hydroxy-C1-C 20 Alkoxy-C1-C 20 Alkyl, C3-C 10 Cycloalkyl, amino, CN, NO2, hydroxyl (CO)-R 3a OR 4a or COOR 4 ;

[0142] R 9 It is hydrogen or C1-C 20 alkyl;

[0143] R 10 and R 11 They are independently hydrogen, C1-C 20 Alkyl group, S(O) m -R 3a O(CO)R 3a (CO)-R 3a or CONR 10a R 11a ;and

[0144] R 10a and R 11a They are independently hydrogen, C1-C 20 Alkyl group, S(O) m -(C1-C8 alkyl), O(CO)(C1-C8 alkyl), (CO)(C1-C8 alkyl), (CO)O(C1-C8 alkyl) or CON(C1-C8 alkyl)2; and

[0145] Q represents a CO bond or a direct bond.

[0146] Preferred compounds of formula (I) include compounds of formulas (Ia) and (Ib):

[0147]

[0148]

[0149] wherein

[0150] R 1 is linear C1-C8 alkyl, in particular C2-C6 alkyl;

[0151] R 20 and R 21 are independently of each other C1-C 20 alkyl, C6-C 20 aryl or C3-C 20 heteroaryl, in particular C1-C8 alkyl.

[0152] One particularly preferred compound of formula (la) is a compound of formula (la-1):

[0153]

[0154] The polymerizable liquid crystal composition preferably comprises a 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.

[0155] Suitable a-oximic 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, in particular chloride, or an acid anhydride in the presence of a base or a mixture of bases, such as, for example, triethylamine or pyridine, in an inert solvent such as, for example, t-butylmethylether (TBME), tetrahydrofurane (THF), dimethoxyethane (DME), dimethylacetamide (DMA), dichloromethane (DCM), ethylacetate or dimethylformamide (DMF), or in a basic solvent such as pyridine, as shown in the following scheme:

[0156]

[0157] R 1 to R 8 have the meaning as given above, and R 3 is preferably methyl. Hal means a halogen atom, in particular Cl. Such reactions are described, for example, in WO 201 / 2045736 and are typically carried out at temperatures of -15 to +50 °C, preferably 0 to 25 °C.

[0158] Alpha-keto oximes 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 S.R. Sandler & W. Karo, Organic functional group preparations, Vol. 3, Academic Press. One of the most convenient methods is the nitrosation of a "reactive" methylene group, for example with nitrous acid or an alkyl nitrite. Both basic conditions (as described in, for example, Organic Synthesis coll. Vol. VI (J. Wiley & Sons, New York, 1988), pp 199 and 840) and acidic conditions (as described in, for example, Organic Synthesis coll. Vol. V, pp 32 and 373, coll. Vol. III, pp 191 and 513, coll. Vol. II, pp 202, 204 and 363) are suitable for the preparation of oximes used as starting materials in the present application. Nitrous acid is usually generated from sodium nitrite. The alkyl nitrite can be, for example, methyl nitrite, ethyl nitrite, isopropyl nitrite, butyl nitrite, pentyl nitrite or isopentyl nitrite.

[0159]

[0160] The corresponding keto intermediates are prepared, for example, by methods described in the literature, for example in standard chemistry textbooks (J. March. Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992). Furthermore, consecutive Friedel-Crafts reactions are efficient for the synthesis of intermediates. Such reactions are well known to the person skilled in the art.

[0161]

[0162] The corresponding keto intermediates can be synthesized, for example, but not limited to, by the following methods. A reasonable synthesis scheme is described below. Arylation and acylation of [A], and demethylation reaction of [B] give the corresponding keto intermediate [C]. Coupling reaction of [C] with [D] gives the corresponding keto intermediate [E]. Alternatively, [D] can be introduced after subsequent oximation or oxime esterification (Scheme 1).

[0163] Scheme 1

[0164]

[0165] The polymerizable liquid crystal composition comprises a polymerizable liquid crystal compound capable of exhibiting birefringence with reversed wavelength dispersion when the polymerizable liquid crystal compound is in an oriented state.

[0166] A useful parameter for evaluating birefringence with reversed wavelength dispersion in a material is Re 450 value, which represents the retardation of the material at a wavelength of 450 nm, Re 550 value, which represents the retardation of the material at a wavelength of 550 nm, and Re 650 value, which represents the retardation of the material at a wavelength of 650 nm. The retardation Re (in nm) of a material is defined as the product of the birefringence Δn at a given wavelength and the layer thickness d (in nm).

[0167] In a material having birefringence with reversed wavelength dispersion, Re 450 / Re 550 value is lower than 1.0 and Re 650 / Re 550 value is higher than 1.0, which means that the magnitude of the birefringence Δn increases with an increase in the wavelength λ.

[0168] An anisotropic layer formed by uniformly orienting only the polymerizable liquid crystal compound of the polymerizable liquid crystal composition having birefringence with reversed wavelength dispersion satisfies the following relationship: Re 450 / Re 550 value is lower than 1.0 and Re 650 / Re 550 value is higher than 1.0.

[0169] The polymerizable liquid crystal compound having birefringence with reversed wavelength dispersion includes a main chain mesogen and a side chain mesogen bonded to the main chain mesogen in the molecule thereof, and when the polymerizable liquid crystal compound having birefringence with reversed 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.

[0170] The polymerizable liquid crystal compound is preferably at least one anisotropic compound of formula (II)

[0171]

[0172] wherein

[0173] the moieties C and D are each independently selected from the group consisting of phenyl, biphenyl, naphthyl, cycloalkyl, bicycloalkyl,

[0174]

[0175] wherein *1 represents the moiety C and X 2 and the moiety D and X 1*2 indicates the bonding site of moieties C and D to the bonding site of moiety E to the carboxyl group adjacent thereto;

[0176] moiety E is selected from the group consisting of phenyl, biphenyl and naphthyl;

[0177] moiety F is selected from the group consisting of a radical of formula (IIIa), (IIIb) or (IIIc)

[0178]

[0179] wherein * indicates the bonding site of moiety F to the imine nitrogen atom of formula II;

[0180] wherein X 1 and X 2 at least one of which is independently from the other represented by a radical of formula (IV)

[0181]

[0182] wherein n is an integer between 0 and 24, and wherein one or more C atoms can be replaced by -O-, -COO-, -OCO-, -OOC-, -O(CO)O-, -N-, -NR a -, -CON- in which R a is CrC 12 alkyl; and

[0183] PG represents a polymerizable radical selected from the group consisting of CH2=C(Ph)-, CH2=CW-COO-, CH2=CH-COO-Ph-, CH2=CW-CO-NH-, CH2=CH-O-, CH2=CH-OOC-, Ph-CH=CH-, CH2=CH-Ph-, CH2=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 b represents lower alkyl, with the proviso that when R b is attached to a phenylene group (-Ph-), it can also represent hydrogen or lower alkoxy,

[0184] and, if applicable, X 1 and X 2 are selected from the group consisting of hydrogen, CrC 12 substituted or unsubstituted straight-chain or branched alkyl, C3-C 12 substituted or unsubstituted straight-chain or branched alkenyl and CrC 12alkoxy groups, wherein one or more carbon atoms may be via -O-, -COO-, -OCO-, -OOC-, -O(CO)O-, -N-, -NR a -, -CON- are substitutes, where R a For C1-C 12 Alkyl; Y is selected from the group consisting of: H, or substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms;

[0185] R 101 R 102 and R 103 Each can be independently selected from the following groups: hydrogen, C1-C 12 Straight-chain or branched alkyl groups, C3-C 12 alkenyl, C1-C 12 Alkoxy, C3-C 12 Alkenyl group, -(CH2) m -C(CH3)3, NO2, 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, -CF3, and -OCF3; where m is an integer between 0 and 12;

[0186] R 104 Choose from the following groups: hydrogen, C1-C 18 Alkyl groups, C3-C with a double bond at the 3rd position or higher. 18 Alkenyl, -(CH2) P -C-(CF3)3, CN, and unsubstituted or substituted benzene rings, wherein the substituents of the benzene rings are selected from the group consisting of: C1-C6 straight-chain or branched alkyl groups, C1-C6 alkoxy groups, -C-(CH3)3, halogens, -CF3, NO2, CN, COR. 107 -COOR 107 -OCOR 107 -CONR 106 R 107 -NR 106 COR 107 OCOOR 107 -OCONR 106 R 107 -NR106 COOR 107 , -F, -Cl, -CF3, and -OCF3; wherein

[0187] R 106 is selected from the group consisting of hydrogen, lower alkyl, and lower alkenyl;

[0188] R 107 is selected from the group consisting of hydrogen, C1-C 18 alkyl, and C3-C 18 alkenyl having a double bond in the 3-position or higher; p is an integer between 0 and 12;

[0189] 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;

[0190] 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 can be replaced by -O-COO-, -OCO-, -OOC-, -O(CO)O-, -N-, NR a -, -CON-, -CO-R b1 , or -NH-R c , wherein R a is C1-C 12 alkyl, R b1 and R c are independently of each other substituted or unsubstituted alkyl having 1 to 20 carbon atoms, or an organic radical having 2 to 30 carbon atoms comprising at least one aromatic ring, or substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, or substituted or unsubstituted cycloalkyl having 3 to 12 carbon atoms.

[0191] The term "lower alkyl" is to be understood as including C 1-6 branched or straight-chain alkyl groups. Examples of lower alkyl groups include methyl, ethyl, propyl, butyl, pentyl and hexyl.

[0192] The term "lower alkenyl" is to be understood as including C 3-6 branched or straight-chain alkenyl groups in which the double bond is in the 2-position or higher. Examples of lower alkenyl groups include 2-propenyl, 3-butenyl, 3-isopentenyl, 4-pentenyl, 5-hexenyl and 4-isohexenyl.

[0193] The term "lower alkoxy" is to be understood as including C 1-6 non-chiral, branched or straight-chain alkoxy groups. Examples of lower alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy and the like.

[0194] In one particular embodiment, moieties C and D are independently of each other selected from phenyl or cyclohexyl, with the proviso that at least one moiety C or D is phenyl.

[0195] In one preferred particular embodiment, moiety E is a phenyl ring.

[0196] In another particular embodiment, moiety F is a group of formula (IIIb) or (IIIc).

[0197] In one particular embodiment, at least one of moieties C and D is an aromatic ring or contains an aromatic ring and the group of formula (IV) is

[0198]

[0199] wherein n is an integer between 0 and 24.

[0200] Suitable polymerizable liquid crystal compounds are known to the person skilled in the art, for example from WO 2020 / 260621 A1, WO 2021 / 037774 A1. Preferred polymerizable liquid crystal compounds include:

[0201]

[0202]

[0203] 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.

[0204] The polymerizable liquid crystal composition comprises the polymerizable liquid crystal compound and the polymerization initiator of formula (I). In addition, the polymerizable liquid crystal composition can comprise at least one solvent and / or at least one additive.

[0205] Suitable solvents include ketones such as acetone, cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK) and methylethyl ketone (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 cellosolve acetate, ethyl acetate (EA), 1-methoxy-2-propanol acetate (MPA), γ-butyrolactone (BL), propylene glycol monoacetate and propylene glycol diacetate, organic sulphur compounds such as dimethylsulfoxide (DMSO), and aromatic compounds such as toluene. Preferred solvents include ketones, in particular cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK) and methylethyl ketone (MEK), esters, in particular ethyl acetate (EA) and 1-methoxy-2-propanol acetate (MPA), ethers, in particular 1,3-dioxolane (DXG), organic sulphur compounds, in particular dimethylsulfoxide (DMSO), and aromatic compounds, in particular toluene. Suitable solvents include ketones such as acetone, cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK) and methylethyl ketone (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 cellosolve acetate, ethyl acetate (EA), 1-methoxy-2-propanol acetate (MPA), γ-butyrolactone (BL), propylene glycol monoacetate and propylene glycol diacetate, organic sulphur compounds such as dimethylsulfoxide (DMSO), and aromatic compounds such as toluene. Preferred solvents include ketones, in particular cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK) and methylethyl ketone (MEK), esters, in particular ethyl acetate (EA) and 1-methoxy-2-propanol acetate (MPA), ethers, in particular 1,3-dioxolane (DXG), organic sulphur compounds, in particular dimethylsulfoxide (DMSO), and aromatic compounds, in particular toluene. Suitable solvents include ketones such as acetone, cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK) and methylethyl ketone (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 cellosolve acetate, ethyl acetate (EA), 1-methoxy-2-propanol acetate (MPA), γ-butyrolactone (BL), propylene glycol monoacetate and propylene glycol diacetate, organic sulphur compounds such as dimethylsulfoxide (DMSO), and aromatic compounds such as toluene. Preferred solvents include ketones, in particular cyclopentanone (CP), cyclohexanone (CH), methyl isobutyl ketone (MIBK) and methylethyl ketone (MEK), esters, in particular ethyl acetate (EA) and 1-methoxy-2-propanol acetate (MPA), ethers, in particular 1,3-dioxolane (DXG), organic sulphur compounds, in particular dimethylsulfoxide (DMSO), and aromatic compounds, in particular toluene.

[0206] The polymerisable 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 polymerisable liquid crystal composition.

[0207] Suitable additives include antioxidants, accelerators, dyes, polymerization inhibitors, activators, fillers, chain transfer inhibitors, pigments, antistatic agents, flame retardants, thickening agents, thixotropic viscosity reducers, surfactants, viscosity regulators, extender oils, plasticizers, tackifiers, catalysts, sensitizers, stabilizers, lubricants, dispersants, polymeric binders and / or monomeric compounds which can be converted into polymeric binders by polymerization, or in the case of emulsion paints and printing inks, dispersion aids, hydrophobing agents, adhesion agents, flow improvers, levelling agents, antifoams, degassing agents, diluents, auxiliaries, colorants, dyes and pigments, cure inhibitors, chiral additives, isotropic or anisotropic fluorescent and / or non-fluorescent dyes, dichroic dyes and crosslinkers.

[0208] To improve the storage stability, it is preferred to add a polymerization inhibitor in 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), in particular 2,6-di-tert-butyl-4-methylphenol (BHT).

[0209] The crosslinker is a compound containing one or more complementary reactive units such as hydroxyl, thiol or amine groups 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). To maintain the liquid crystal phase, an amount of 0.015 to 10 wt%, preferably 0.25 to 3.0 wt% of the crosslinker relative to the total weight of the polymerizable liquid crystal composition is preferred.

[0210] Preferably, the crosslinker 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.

[0211] Suitable polythiols include monomeric aliphatic polythiols, oligomeric and polymeric polythiols.

[0212] Suitable polymeric polythiols are polypropylene ether glycol bis (beta- mercaptopropionate).

[0213] Preferred aliphatic dithiols include 1,2-ethanedithiol, butanedithiol, 1,3- propanedithiol, 1,5-pentanedithiol, 2,3-dimercapto-1-propanol, dithioerythritol, 3,6- dioxa-1,8-octanedithiol, 1,8-octanedithiol hexanedithiol, dithiodiglycol, pentanedithiol, decanedithiol, 2-methyl-1,4-butanedithiol, bismercaptoethyl phenyl methane, 1,9- nonanedithiol (1,9-dimercaptodecane), ethylene glycol dimercaptoacetate.

[0214] Preferred oligomeric dithiols include difunctional mercapto-functional carboxylic acid ester oligomers derived from the capping moieties of hydroxyethyl mercaptan, hydroxypropyl mercaptan, dimercapto propane, dimercapto ethane, as described in US 5,744,514.

[0215] Preferred tri-thiol functional compounds include trimethylol ethane tris- mercaptopropionate, trimethylol propane tris-mercaptopropionate (TMPTSH), trimethylol ethane tris-mercaptoacetate, and trimethylol propane tris-mercaptoacetate glyceryl (11- mercaptoundecanoate), trimethylol propane tris (11-mercaptoundecanoate).

[0216] Preferred tetra-functional thiols include pentaerythritol tetrakis (3- mercaptopropionate) (PTMP), pentaerythritol tetramercaptoacetate, and pentaerythritol tetra (11- mercaptoundecanoate).

[0217] A particularly preferred polythiol crosslinker is pentaerythritol tetrakis (3- mercaptopropionate) (PTMP).

[0218] 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, palmityl alcohol, and stearyl alcohol), and diallyl ethers and divinyl ethers of difunctional alcohols (e.g., ethylene glycol and 1,4-butanediol).

[0219] Other examples include acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, styrene, core-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylpyrrolidone, vinylsulfonic acid, fatty acid vinyl ester, a,b-vinylidene unsaturated carboxylic acid, alkyl ester of (meth)acrylic acid in which the number of carbon atoms of the alkyl group is 1 to 18, hydroxyalkyl ester of (meth)acrylic acid in which the number of carbon atoms of the hydroxyalkyl group is 1 to 18, amidoalkyl ester of (meth)acrylic acid in which the number of carbon atoms of the amidoalkyl group is 1 to 18, ether oxygen-containing alkyl ester of (meth)acrylic acid in which the number of carbon atoms of the ether oxygen-containing alkyl group is 3 to 18, N-vinylacetamide, vinyl p-tert-butylbenzoate, vinyl N,N-dimethylamino benzoate, vinyl benzoate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylvalerate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, vinyl 2-ethyl-2-methylbutanoate, dicyclopentyl oxyethyl (meth)acrylate, isobornyl oxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, dimethyladamantyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, mono(meth)acrylate, polypropylene glycol having a polymerization degree of 2 to 100 and terminated with di(meth)acrylate or alkyl having 1 to 6 carbons, and mono(meth)acrylate of a copolymer of polyethylene glycol and ethylene oxide and polypropylene oxide, and the like as non-liquid crystalline polymerizable compounds as monofunctional compounds.

[0220] Examples of bifunctional compounds include 1,4-divinyloxybutane (BDDV), 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, dimethylol tricyclodecane diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A EO adduct diacrylate, bisphenol A glycidyl diacrylate, polyethylene glycol diacrylate and methacrylate.

[0221] BDDV is particularly preferred as a crosslinking agent.

[0222] As examples of tri- or higher functional polyfunctional compounds are neopentatryl triacrylate, trimethylolpropane triacrylate, trimethylol EO adduct triacrylate, triacryloyloxyethyl phosphate, tri(acryloyloxyethyl) isocyanurate, alkyl-modified dipentaerythritol triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, neopentatetraacrylate, alkyl-modified dipentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxy pentaacrylate, alkyl-modified dipentaerythritol pentaacrylate, neopentatryl tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylol EO adduct tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate, tri(meth)acryloyloxyethyl isocyanurate, alkyl-modified dipentaerythritol tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate, PO-modified trimethylolpropane tri(meth)acrylate, neopentatetra(meth)acrylate, alkyl-modified dipentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol monohydroxy penta(meth)acrylate, and alkyl-modified dipentaerythritol penta(meth)acrylate. Other examples include dipentaerythritol hexaacrylate, wherein the dipentaerythritol is caprolactone-modified, which is commercially available, for example, from Nippon Kayaku Co., Ltd. as Kayarad DPCA-20, Kayarad DPCA-30, Kayarad DPCA-60, and Kayarad DPCA-120. Kayarad DPCA-20 is a particularly preferred crosslinker.

[0223] In one particular example, the crosslinker 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.

[0224] To reduce film thickness unevenness in forming an optically anisotropic body, an optical film, or the like thin film, it is preferable to add a leveling agent to the polymerizable liquid crystal composition. Suitable leveling agents include polysiloxane agents such as modified polydimethylsiloxane (PDMS), acrylate-based agents such as polyacrylate, fluorocarbon-based agents, and hydrocarbon-based leveling agents, particularly polyacrylate such as Flow.

[0225] The polymerizable liquid crystal composition preferably contains 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.

[0226] In addition to the polymerizable liquid crystal compound (i), other polymerizable compounds can 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 mesogenic. Preferably, the other polymerizable compound is selected from reactive mesogens, most preferably from mono- and di-reactive mesogens.

[0227] The term "mesogenic" means a compound comprising one or more calamitic (rod-shaped or slab-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 itself. It can also only show liquid crystal phase behavior in mixtures with other compounds, or when the mesogenic compound or material or mixtures thereof are polymerized.

[0228] Calamitic mesogenic groups typically comprise a mesogenic core consisting of one or more aromatic or non-aromatic ring systems connected to each other directly or via a linking group, optionally comprising end groups connected to the ends of the mesogenic core, and optionally comprising one or more side groups connected to the long sides of the mesogenic core, wherein such end and side groups can be selected from carbyl or hydrocarbyl groups, polar groups (such as halogen, nitro, hydroxyl, etc.) or polymerizable groups. The term "reactive mesogen" (RM) means a polymerizable mesogenic compound. A polymerizable compound having one polymerizable group is also referred to as a "mono-reactive" compound, a compound having two polymerizable groups is also referred to as a "di-reactive" compound, and a compound having more than two polymerizable groups is referred to as a "multi-reactive" compound. Examples of such compounds are well known to the person skilled in the art and are described in, for example, WO 2018 / 099883. An example of an other polymerizable compound is [3-methyl-4-[4-(6-prop-2-enoyloxyhexyloxy)benzoyl]oxy-phenyl] 4-(6-prop-2-enoyloxyhexyloxy)benzoate (FPC-1), as shown in the following figure.

[0229]

[0230] The present application further relates to a liquid crystal film, which is a cured product of the polymerizable liquid crystal composition.

[0231] The present application also relates to a method for manufacturing a liquid crystal film, 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 laminating the liquid crystal film to a pressure sensitive adhesive coated on a substrate.

[0232] 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 typically comprises a photo-orientable substance in which anisotropic properties can be induced upon exposure to an alignment light. The induced anisotropy suitably provides the polymerizable liquid crystal composition of the present application with alignment ability. The term "alignment direction" refers to the preferred direction induced in the polymerizable liquid crystal composition, i.e. the direction in which the liquid crystal molecules are aligned.

[0233] The photo-orientable substance comprises a photo-orientable moiety which is capable of forming a preferred direction upon exposure to an alignment light and thus generating anisotropic properties. Such photo-orientable moiety preferably has anisotropic absorption properties. Typically, such moiety exhibits an absorption in the wavelength range of 230 to 500 nm. Preferably, the photo-orientable moiety exhibits light absorption in the wavelength range of 300 to 450 nm, more preferably a moiety which exhibits an absorption in the wavelength range of 310 to 380 nm.

[0234] Preferably, the photo-orientable moiety has a carbon-carbon, carbon-nitrogen or nitrogen-nitrogen double bond.

[0235] For example, the photo-orientable moiety is a substituted or unsubstituted azo dye, such as an anthraquinone, a coumarin, a mericyanine, a 2-phenylazothiazole, a 2-phenylazo benzothiazole, a stilbene, a cyanostilbene, a fluorostilbene, a cinnamonic nitrile, a chalcone, a cinnamate, a cyanocinnamate, a stilbazolium, a 1,4-bis(2-phenylethylvinyl)benzene, a 4,4'-bis(arylazo)stilbene, a perylene, a 4,8-diamino-1,5-naphthoquinone dye, an aryloxy carboxylic acid derivative, an aryl ester, an N-aryl amide, a polyimide, and a diaryl ketone having a ketone moiety or a ketone derivative conjugated with two aromatic rings, such as, for example, a substituted diphenyl ketone, a diphenyl ketone imine, a phenylhydrazone and a formamidin urea.

[0236] The preparation of the anisotropic absorbing 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.

[0237] Preferably, the photo-orientable moiety comprises an arylazo group, a poly(arylazo) group, a stilbene, a cyanostilbene, a cinnamate or a chalcone.

[0238] The photo-orientable substance can be, inter alia, a monomer, an oligomer or a polymer. The photo-orientable moiety can be covalently bound within the main chain or within the side chain of, for example, a polymer or oligomer, or it can be a part of a non-polymerizable monomer or other compound. The photo-orientable substance can further be a copolymer comprising different types of photo-orientable moieties, or it can be a copolymer comprising side chains with and without photo-orientable moieties.

[0239] Polymer means, for example, polyacrylates, polymethacrylates, polyimides, polyurethanes, polyamide acids, polymaleimides, poly-2-chloroacrylates, poly-2-phenylacrylates; polyacrylamides, polymethacrylamides, poly-2-chloroacrylamides, poly-2-phenylacrylamides, polyethers, polyvinyl ethers, polyesters, polyvinyl esters, polystyrene derivatives, polysiloxanes, straight-chain or branched alkyl esters of polyacrylic acid or polymethacrylic acid; polyphenoxyalkyl acrylates, polyphenoxyalkyl methacrylates, polyphenylalkyl methacrylates having alkyl residues of 1 to 20 carbon atoms; polyacrylonitriles, polymethacrylonitriles, cycloalkene polymers, polystyrene, poly-4-methylstyrene or mixtures thereof.

[0240] The photo-orientable substance can also comprise a photosensitizer, for example, ketocoumarin and diphenyl ketone.

[0241] Furthermore, preferred photo-orientable monomers or oligomers or polymers are described in U.S. Patents US 5,539,074, US 6,201,087, US 6,107,427, US 6,632,909 and US 7,959,990.

[0242] After the coating, the organic solvent is removed, resulting in a solvent-free liquid crystal layer, wherein the molecules have a predetermined orientation.

[0243] The alignment of the polymerizable liquid crystal composition can also be achieved by other known means for aligning liquid crystals, for example, by coating the polymerizable liquid crystal composition onto a substrate that has been previously treated by rubbing techniques.

[0244] The polymerisable liquid crystal compounds are polymerised to form a network in which the orientation of the liquid crystals is fixed.

[0245] The steps of polymerising the polymerisable liquid crystal composition and exposing to alignment light can be carried out in any order. The polymerisation can be initiated before or after the exposure to alignment light, or the polymerisation and exposure can occur simultaneously.

[0246] The liquid crystal composition can also be applied on a support, and the support can have an alignment surface, which will mean that the surface has the ability to align the liquid crystals. The support can have been provided with an alignment without further treatment. For example, if a plastic substrate is used as a support, it can provide an alignment on the surface due to the manufacturing process, for example extrusion or stretching of the substrate. The support can also be brushed or rubbed or imprinted with a directional microstructure to create the alignment ability.

[0247] The support can be rigid or flexible and can have any form or shape. In principle, it can consist of any material. Preferably, the support comprises a plastic, a glass or a metal or is a silicon wafer. In the case that the support is flexible, preferably the support is a plastic or a metal foil. Preferably, the surface of the support is flat. For some applications, the support can comprise topographical surface structures, such as microstructures like micro-lenses or micro-prisms, or structures exhibiting a shape discontinuity, such as rectangular structures. Preferably, the support is transparent. The support can also be subjected to a treatment before being coated with the polymerisable liquid crystal composition according to the present application.

[0248] The support can be moved during the deposition of the polymerisable liquid crystal composition. For example, the layer of polymerisable liquid crystal composition can be manufactured in a continuous roll-to-roll process by depositing the composition onto a moving flexible foil, preferably a plastic or metal. The resulting film can then be wound on a roll together with the support foil, or the film can be peeled off from the support and then wound as a free-standing film without the support.

[0249] The support can have additional layers, such as organic layers, dielectric layers or metal layers. The layers can have different functions, for example, an organic layer can be coated as a primer layer, which increases the compatibility of the material to be coated with the support. A metal layer can be used as an electrode, for example in an electro-optical device such as a display, or can have the function of a reflector. The support can also be an optical component or device with certain functions, such as a substrate for an LCD, which can comprise for example thin film transistors, electrodes or colour filters. In another example, the support is a device comprising an OLED layer structure. The support can also be a polariser, such as a polarising film or sheet polariser, a reflective polariser, such as the commercially available Vikuity TM DBEF film.

[0250] The polymerizable liquid crystal composition can be applied to the substrate by general coating and printing methods known in the art. Coating methods are, for example, spin coating, blade coating, knife coating, reverse roll coating, transfer roll coating, gravure roll coating, kiss roll coating, cast coating, spray coating, slot-die coating, roll coating, electrodeposition coating, dip coating or die coating. Printing methods include relief printing, such as flexographic printing, inkjet printing, intaglio printing, such as direct or indirect intaglio printing, lithographic printing, such as gravure printing, or stencil printing, such as screen printing. The preferred printing method is inkjet printing.

[0251] The liquid crystal film exhibits a birefringence with an inverted wavelength dispersion.

[0252] The inverted wavelength dispersion of a material can be evaluated via 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 material with a birefringence with an inverted wavelength dispersion, the Re 450 / Re 550 value is below 1.0 and the Re 650 / Re 550 value is above 1.0, indicating that the magnitude of the birefringence (Δn) increases with increasing wavelength λ.

[0253] The present application further provides a use of a liquid crystal film according to the present application for the manufacture of an optical or electro-optical device, such as an optical compensator for viewing angle enhancement in liquid crystal displays, or an achromatic retarder for display applications, including OLED anti-reflection.

[0254] The present application will be described in more detail by means of the accompanying drawings and the following examples.

[0255] Examples

[0256] The following abbreviations are used:

[0257] BDDV 1,4-Diethenyloxybutane

[0258] BHT 2,6-Bis-tert-butyl-4-methylphenol

[0259] CE1 [(E)-1-(4-Phenylsulfenylbenzoyl)heptylideneamino]benzoate

[0260] CE2 [(Z)-1-[9-Ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethylideneamino]acetate

[0261] CE3 [(Z)-[1-[4-[4-(benzofuran-2-carbonyl)phenyl]sulfenylphenyl]-4- methylpentylidene]amino]acetate

[0262] DPCA Kayarad DPCA-20, a di-pentaerythritol multi-functional acrylate wherein the di-pentaerythritol is modified with caprolactone

[0263] FPC-1 [3-methyl-4-[4-(6-prop-2-enoyloxyhexyloxy)benzoyl]oxyphenyl] 4-(6-prop-2- enoyloxyhexyloxy)benzoate

[0264] LPP linear photopolymerisable polymer

[0265] PH1 [4-[6-[(2)-2-acetyloxyiminoheptanoyl]-9-(2-ethylhexyl)carbazole-3- carbonyl]phenyl]acetate

[0266] PH2 [4-[6-[(2)-2-acetyloxyiminohexanoyl]-9-ethyl-carbazole-3-carbonyl]phenyl] hexanoate

[0267] PH3 [1-[9-(2-ethylhexyl)-6-(4-methoxycarbonyloxybenzoyl)carbazole-3-carbonyl] propylideneamino]acetate

[0268] PH4 [1-[9-ethyl-6-(4-propoxycarbonyloxybenzoyl)carbazole-3-carbonyl] pentylideneamino]acetate

[0269] PH5 [1-[6-(4-butoxycarbonyloxybenzoyl)-9-ethyl-carbazole-3-carbonyl] hexylideneamino]acetate

[0270] PH6 [1-[6-(4-ethoxycarbonyloxybenzoyl)-9-ethyl-carbazole-3-carbonyl] hexylideneamino]acetate

[0271] PTMP pentaerythritol tetra(3-mercaptopropionate)

[0272] RWD1 [2-[[1,3-benzothiazol-2-yl(hexyl)hydrazono]methyl]-4-(4-pentylcyclohexanecarbonyl)oxy-phenyl] 4-(6-prop-2-enoyloxyhexyloxy)benzoate

[0273] RWD2 [3-[[1,3-benzothiazol-2-yl(hexyl)hydrazono]methyl]-4-(4-ethylcyclohexanecarbonyl)oxy-phenyl] 4-(6-prop-2-enoyloxyhexyloxy)benzoate

[0274] RWD3 [3-[[1,3-benzothiazol-2-yl(hexyl)hydrazono]methyl]-4-[4-(6-prop-2- enoyloxyhexyloxy)benzoyl]oxy-phenyl] 4-(6-prop-2-enoyloxyhexyloxy) benzoate

[0275] RWD4 3-[[hexyl(quinolin-2-yl)hydrazono]methyl]-4-[4-(6-prop-2- enoyloxyhexyloxy)benzoyl]oxy-phenyl] 4-(6-prop-2-enoyloxyhexyloxy) benzoate

[0276] TAC triacetate cellulose

[0277] Method

[0278] Quality of alignment

[0279] The quality of alignment of the liquid crystals 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 crystals are well aligned, the quality of alignment is defined as very good. If the dark state shows light leakage due to non-uniform alignment of the liquid crystals, the quality of alignment is defined as good. If the dark state shows light leakage and some areas have crystallization, the quality of alignment is defined as medium. If the liquid crystals are not aligned and there is no dark state, the quality of alignment is defined as poor.

[0280] Thermal reliability

[0281] Films of the following compositions 1 to X were laminated to pressure sensitive adhesive PSA OC8171 (3M) coated on 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 ellipsometer was used to determine the retardation before and after thermal stress. The % reliability of the thermal treatment was quantified by the difference in retardation at 550 nm before and after heating at 85°C divided by the retardation before stress.

[0282] The results of the thermal reliability evaluation are summarized in Table 1.

[0283] Preparation of the alignment layer

[0284] A TAC 80 pm (FT TD80ULM from Fujifilm) substrate was spin-coated with a photoalignment composition (LPP polymer with a solid content of 3% in cyclopentanone, as described in WO 2012 / 085048). The coated substrate was 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 linearly polarized UV light at 250 mJ / cm2at 405 nm, using a H-broadband polarizer (from Thorlabs) to obtain a uniform alignment of the liquid crystals. The substrate was then laminated to a pressure sensitive adhesive PSA OC8171 (3M) coated on 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 ellipsometer was used to determine the retardation before and after thermal stress. The % reliability of the thermal treatment was quantified by the difference in retardation at 550 nm before and after heating at 85°C divided by the retardation before stress. 2Collimated and linearly polarized UV (LPUV) light (280-320 nm) at 0° with respect to the reference edge on the substrate.

[0285] Preparation of liquid crystal films

[0286] The polymerizable liquid crystal compounds used in the polymerizable liquid crystal composition are shown below.

[0287] RWD1

[0288] RWD2

[0289] RWD3

[0290] RWD1 and RWD2 were obtained according to the procedure described in WO 2021 / 037774 Al. RWD3 was obtained according to the procedure described in US2014 / 0142266 Al.

[0291] The photopolymerization initiators used in the polymerizable liquid crystal composition are shown below.

[0292]

[0293]

[0294] Example 1

[0295] A 35.0 wt% solution was prepared by mixing 15.050 wt% of RWD1, 12.443 wt% of RWD2, 0.0175 wt% of BHT (obtained from Sigma-Aldrich), 0.7 wt% of BDDV (obtained from BASF), 3.92 wt% of FPC-1 (obtained from Synthon Chemicals), 2.8 wt% of PH1 (obtained from BASF), and 0.070 wt% of Irgacure® 819 (obtained from BASF) in cyclohexanone / toluene 40 / 60. The solution was stirred thoroughly at 40 °C until the solids were 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 at 40 °C and 50 °C, respectively, by irradiating UV light using a high-pressure mercury lamp under a nitrogen atmosphere for about 2 minutes (total UV amount: 2.3 J).

[0296] Example 2

[0297] ​A film was prepared as in Example 1, except that PH2 was used in place of PHI. The film was annealed in an oven at 69 °C for 5 minutes, and then photo-polymerized at 50 °C by irradiating UV light for about 2 minutes (total UV amount: 2.3 J) using a high pressure mercury lamp under a nitrogen atmosphere.

[0298] Example 3

[0299] A film was prepared as in Example 1, except that PH3 was used in place of PHI. The film was annealed in an oven at 69 °C for 5 minutes, and then photo-polymerized at 50 °C by irradiating UV light for about 2 minutes (total UV amount: 2.3 J) using a high pressure mercury lamp under a nitrogen atmosphere.

[0300] Example 4

[0301] A film was prepared as in Example 1, except that PH4 was used in place of PHI. The film was annealed in an oven at 69 °C for 5 minutes, and then photo-polymerized at 50 °C by irradiating UV light for about 2 minutes (total UV amount: 2.3 J) using a high pressure mercury lamp under a nitrogen atmosphere.

[0302] Example 5

[0303] A film was prepared as in Example 1, except that PH5 was used in place of PHI. The film was annealed in an oven at 69 °C for 5 minutes, and then photo-polymerized at 50 °C by irradiating UV light for about 2 minutes (total UV amount: 2.3 J) using a high pressure mercury lamp under a nitrogen atmosphere.

[0304] Example 6

[0305] A film was prepared as in Example 1, except that PH6 was used in place of PHI. The film was annealed in an oven at 69 °C for 5 minutes, and then photo-polymerized at 50 °C by irradiating UV light for about 2 minutes (total UV amount: 2.3 J) using a high pressure mercury lamp under a nitrogen atmosphere.

[0306] Example 7

[0307] A film was prepared as in Example 1, except that PH2 was used in place of PHI. The film was annealed in an oven at 69 °C for 5 minutes, and then photo-polymerized at 50 °C by irradiating UV light for about 2 minutes (total UV amount: 2.3 J) using a high pressure mercury lamp under a nitrogen atmosphere. A 35.0 wt% solution was prepared. The solution was stirred thoroughly at 40 °C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer of a substrate obtained as described above at 800 rpm 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 for about 2 minutes (total UV amount: 2.3 J) at 40 °C and 50 °C, respectively, using a high-pressure mercury lamp under a nitrogen atmosphere.

[0308] Example 8

[0309] A 35.0 wt% solution was prepared. The solution was stirred thoroughly at 40 °C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer of a substrate obtained as described above at 800 rpm 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 for about 2 minutes (total UV amount: 2.3 J) at 40 °C and 50 °C, respectively, using a high-pressure mercury lamp under a nitrogen atmosphere. A 35.0 wt% solution was prepared. The solution was stirred thoroughly at 40 °C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer of a substrate obtained as described above at 800 rpm 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 for about 2 minutes (total UV amount: 2.3 J) at 40 °C and 50 °C, respectively, using a high-pressure mercury lamp under a nitrogen atmosphere.

[0310] Example 9

[0311] A 35.0 wt% solution was prepared. The solution was stirred thoroughly at 40 °C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer of a substrate obtained as described above at 800 rpm 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 for about 2 minutes (total UV amount: 2.3 J) at 40 °C and 50 °C, respectively, using a high-pressure mercury lamp under a nitrogen atmosphere. A 35.0 wt% solution was prepared. The solution was stirred thoroughly at 40 °C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer of a substrate obtained as described above at 800 rpm 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 for about 2 minutes (total UV amount: 2.3 J) at 40 °C and 50 °C, respectively, using a high-pressure mercury lamp under a nitrogen atmosphere.

[0312] Example 10

[0313] A 35.0 wt% solution was prepared. The solution was stirred thoroughly at 40 °C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer of a substrate obtained as described above at 800 rpm 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 for about 2 minutes (total UV amount: 2.3 J) at 40 °C and 50 °C, respectively, using a high-pressure mercury lamp under a nitrogen atmosphere. 819 (obtained from IGM Resins), 0.070 wt% of A 35.0 wt% solution was prepared by Flow 300. The solution was stirred thoroughly at 40 °C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer of the substrate obtained as described above at 800 rpm 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 irradiation of UV light for about 2 minutes (total UV amount: 2.3 J) at 40 °C and 50 °C, respectively, using a high-pressure mercury lamp under a nitrogen atmosphere.

[0314] Example 11

[0315] A 35.0 wt% solution was prepared by Flow 300. The solution was stirred thoroughly at 40 °C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer of the substrate obtained as described above at 800 rpm 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 irradiation of UV light for about 2 minutes (total UV amount: 2.3 J) at 40 °C and 50 °C, respectively, using a high-pressure mercury lamp under a nitrogen atmosphere. 369 (obtained from IGM Resins), 0.070 wt% of A 35.0 wt% solution was prepared by Flow 300. The solution was stirred thoroughly at 40 °C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer of the substrate obtained as described above at 800 rpm 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 irradiation of UV light for about 2 minutes (total UV amount: 2.3 J) at 40 °C and 50 °C, respectively, using a high-pressure mercury lamp under a nitrogen atmosphere.

[0316] Example 12

[0317] A 35.0 wt% solution was prepared by Flow 300. The solution was stirred thoroughly at 40 °C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer of the substrate obtained as described above at 800 rpm 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 irradiation of UV light for about 2 minutes (total UV amount: 2.3 J) at 40 °C and 50 °C, respectively, using a high-pressure mercury lamp under a nitrogen atmosphere. A 35.0 wt% solution was prepared by Flow 300. The solution was stirred thoroughly at 40 °C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer of the substrate obtained as described above at 800 rpm 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 irradiation of UV light for about 2 minutes (total UV amount: 2.3 J) at 40 °C and 50 °C, respectively, using a high-pressure mercury lamp under a nitrogen atmosphere.

[0318] Example 13

[0319] A film was prepared as in Example 12, except that CE4 was substituted for PHI. The film was annealed in an oven at 81 °C for 5 minutes, then photo-polymerized at 50 °C by irradiating UV light for about 2 minutes (total UV amount: 2.3 J) using a high pressure mercury lamp under a nitrogen atmosphere.

[0320] Example 14

[0321] A film was prepared as in Example 12, except that CE2 was substituted for PHI. The film was annealed in an oven at 74 °C for 5 minutes, then photo-polymerized at 50 °C by irradiating UV light for about 2 minutes (total UV amount: 2.3 J) using a high pressure mercury lamp under a nitrogen atmosphere.

[0322] Example 15

[0323] A film was prepared as in Example 12, except that CE1 was substituted for PHI. The film was annealed in an oven at 75 °C for 5 minutes, then photo-polymerized at 50 °C by irradiating UV light for about 2 minutes (total UV amount: 2.3 J) using a high pressure mercury lamp under a nitrogen atmosphere.

[0324] Example 16

[0325] A 35.0 wt% solution was prepared by mixing 15.75 wt% of RWD1, 11.74 wt% of RWD2, 0.0175 wt% of BHT, 0.7 wt% of DPCA (obtained from Nikka Fine), 3.92 wt.% of FPC-1, 2.8 wt.% of PHI, 0.070 wt.% of A 35.0 wt% solution was prepared by mixing 15.75 wt% of RWD1, 11.74 wt% of RWD2, 0.0175 wt% of BHT, 0.7 wt% of DPCA (obtained from Nikka Fine), 3.92 wt.% of FPC-1, 2.8 wt.% of PHI, 0.070 wt.% of

[0326] Example 17

[0327] A film was prepared as in Example 16, except that CE1 was substituted for PHI. The film was annealed in an oven at 75 °C for 5 minutes, then photo-polymerized at 50 °C by irradiating UV light for about 2 minutes (total UV amount: 2.3 J) using a high pressure mercury lamp under a nitrogen atmosphere. 819 was substituted for PHI. The film was annealed in an oven at 60 °C for 5 minutes, then photo-polymerized at 50 °C by irradiating UV light for about 2 minutes (total UV amount: 2.3 J) using a high pressure mercury lamp under a nitrogen atmosphere.

[0328] Example 18

[0329] A film was prepared as in Example 16, except that PTMP (obtained from Sigma-Aldrich) was used instead of DPCA. The film was annealed in an oven at 65°C for 5 minutes, then photo-polymerized at 50°C by irradiation of UV light using a high pressure mercury lamp for about 2 minutes under nitrogen atmosphere (total UV amount: 2.3 J).

[0330] Example 19

[0331] A film was prepared as in Example 16, except that Omnirad 819 was used instead of PH1 and PTMP was used instead of DPCA. The film was annealed in an oven at 60°C for 5 minutes, then photo-polymerized at 50°C by irradiation of UV light using a high pressure mercury lamp for about 2 minutes under nitrogen atmosphere (total UV amount: 2.3 J).

[0332] Example 20

[0333] A film was prepared as in Example 16, except that no DPCA was added. The film was annealed in an oven at 69°C for 5 minutes, then photo-polymerized at 50°C by irradiation of UV light using a high pressure mercury lamp for about 2 minutes under nitrogen atmosphere (total UV amount: 2.3 J).

[0334] Example 21

[0335] A film was prepared as in Example 16, except that Omnirad 819 was used instead of PH1 and no DPCA was added. The film was annealed in an oven at 63°C for 5 minutes, then photo-polymerized at 50°C by irradiation of UV light using a high pressure mercury lamp for about 2 minutes under nitrogen atmosphere (total UV amount: 2.3 J).

[0336] Example 22

[0337] A 35.0 wt% solution was prepared by mixing 31.41 wt% of RWD3, 0.0175 wt% of inhibitor BHT, 0.7 wt% of BDDV, 2.8 wt% of PH1, 0.070 wt% of Omnirad 819, 0.7 wt% of PTMP, and 63.2 wt% of cyclohexanone / toluene 40 / 60 in cyclohexanone / toluene 40 / 60. The solution was stirred well at 40°C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer obtained as described above at 800 rpm to obtain a film. The film was annealed in an oven at 61 °C for 5 minutes. The sample was cooled to room temperature, then photo-polymerized at 50°C by irradiation of UV light using a high pressure mercury lamp for about 2 minutes under nitrogen atmosphere (total UV amount: 2.3 J). Flow 300 to prepare a 35.0 wt% solution. The solution was stirred well at 40°C until the solids were completely dissolved. The solution was spin-coated onto the alignment layer obtained as described above at 800 rpm to obtain a film. The film was annealed in an oven at 61 °C for 5 minutes. The sample was cooled to room temperature, then photo-polymerized at 50°C by irradiation of UV light using a high pressure mercury lamp for about 2 minutes under nitrogen atmosphere (total UV amount: 2.3 J).

[0338] Table 1 - Thermal reliability evaluation

[0339]

[0340]

[0341] Comparative Example

[0342] amount provided relative to the total weight of the polymerizable liquid crystal composition

[0343] The films of the example compositions 1 to 22 all exhibited very good alignment quality. The results shown in Table 1 demonstrate the reliability of the improvement obtained in the examples in which an a-oximino ester photoinitiator according to Formula (I) is used.

Claims

1. A polymerizable liquid crystal composition comprising: (i) a polymerizable liquid crystal compound that, when the polymerizable liquid crystal compound is in an oriented state, exhibits birefringence with reversed wavelength dispersion; and (ii) a polymerization initiator represented by formula (I): in: R 1 Hydrogen, C1-C 20 Alkyl, C 1- C6 alkyl-C3-C6 cycloalkyl, C3-C 20 cycloalkyl or C2-C 12 alkenyl, wherein C3-C 20 cycloalkyl or C2-C 12 The alkenyl group is uninterrupted or via one or more O, S, CO, NR groups. 10 or COOR 4 Interruption; or R 1 For C1-C 20 Alkyl groups, which are unsubstituted or derived from 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 , C3-C8 cycloalkyl substitution, wherein the C3-C8 cycloalkyl group is uninterrupted or via one or more O, S, CO or NR. 10 Interrupted; or via one or more C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein each is unsubstituted or substituted via one or more halogens, phenyl groups, C1-C groups. 20 Alkylphenyl, C1-C8 alkoxyphenyl, C1-C4 haloalkyl, CN, NO2, OR 4 SR 9 NR 10 R 11 PO(OR) 3a )2 or S(O) m -R 3a Replace; or R 1 For C2-C 20 Alkyl groups, which are derived from one or more of O, CO, S, C(O)O, OC(O), SO, SO2, phenyl, naphthyl, or NR. 10 Interruption, of which C2-C is interrupted 20 Alkyl groups that are unsubstituted or derived from one or more halogens, C3-C8 cycloalkyl groups, OH, SH, OR 4 SR 9 COOR 4 O(CO)-R 3a CONR 10 R 11 NR 10 R 11 C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or derived from one or more halogens, C1-C8 alkyl groups, or OR groups. 4 SR 9 or NR 10 R 11 Replace; or R 1 For C6-C 20 Aryl or C3-C 20 heteroaryl groups, each unsubstituted or via one or more C1-C... 20 Alkyl, phenyl, halogen, C1-C4 haloalkyl, CN, NO2, 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 groups Replacement; or via one or more C2-C 20 Alkyl substitution, the C2-C 20 Alkyl groups via one or more O, S, or NR 10 Interrupted; or via one or more C1-C 20 Alkyl substitution, the C1-C 20 Alkyl groups that are unsubstituted or derived from one or more halogens, COOR 4 CONR 10 R 11 , phenyl, C3-C8 cycloalkyl, C3-C 20 heteroaryl, C6-C 20 aryloxycarbonyl, C3-C 20 heteroaryloxycarbonyl, OR 4 SR 9 or NR 10 R 11 Substitution; or substitution with one or more phenyl, naphthyl, benzoyl, or naphthyl groups, each of which is unsubstituted or substituted with OR 4 SR 9 or NR 10 R 11 Replace; or R 1 For C2-C 20 Alkyl or benzoyl groups, which are unsubstituted or derived from one or more C1-C6 alkyl, phenyl, or OR groups. 4 SR 9 or NR 10 R 11 Replace; or R 1 For C2-C 12 An alkoxycarbonyl group, which may be interrupted by one or more -O- groups and / or substituted by one or more hydroxyl groups as needed; or R 1 It is a phenoxycarbonyl group, which is unsubstituted or derived from C1-C6 alkyl, halogen, phenyl, or OR groups. 4 SR 9 or NR 10 R 11 Replace; or R 1 CN, (CO)-R 3a COOR 4 CONR 10 R 11 NO2, PO (OR) 3a )2 or S(O) m -R 3a ; R 1a Hydrogen, C1-C 20 Alkyl, CN, (CO)-R 3a COOR 4a CONR 10a R 11a NO2, PO (OR) 3a )2 or S(O) m -R 3a ;or R 1a For C1-C 20 Alkyl groups, which are derived from 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 C3-C8 cycloalkyl substitution, wherein the C3-C8 cycloalkyl group is uninterrupted or via one or more O, S, CO or NR. 10a Interrupted; or via one or more C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein each is unsubstituted or substituted via one or more halogens, phenyl groups, C1-C groups. 20 Alkylphenyl, C1-C8 alkoxyphenyl, C1-C4 haloalkyl, CN, NO2, OR 4a SR 9a NR 10a R 11a PO(OR) 3a )2 or S(O) m -R 3a Replace; or R 1a For C1-C 20 Alkyl groups, which are derived from one or more O, S, NR atoms 10a Disruptions caused by CO, SO, or SO2, which are unsubstituted or via C3-C8 cycloalkyl groups, OH, SH, O(CO)R 3a COOR 4a CONR 10a R 11a C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or derived from one or more halogens, C1-C8 alkyl groups, or OR groups. 4a SR 9a or NR 10a R 11a Replace; or R 1a For C2-C 12 alkenyl or C3-C 20 cycloalkyl groups, each without interruption or via one or more O, S, CO, NR 10a or COOR 4a Interruption; or R 1a For C6-C 20 Aryl or C3-C 20 Heteroaryl groups, each unsubstituted or mediated by one or more halogens, CN, NO2, 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 Replace; or via one or more C 1- C 20 Alkyl substitution, the C 1- C 20 Alkyl groups that are unsubstituted or derived from one or more halogens, COOR 4a CONR 10a R 11a , phenyl, C3-C8 cycloalkyl, C3-C 20 heteroaryl, OR 4a SR 9a or NR 10a R 11a Replacement; or via one or more C2-C 20 Alkyl substitution, the C2-C 20 Alkyl groups via one or more O, S, or NR 10a Interrupted; or substituted with one or more phenyl, naphthyl, benzoyl, or naphthyl groups, each of which is unsubstituted or substituted with OR 4a SR 9a or NR 10a R 11a replace; R 2 Hydrogen, C1-C 20 Alkyl or C1-C6 alkyl-C3-C6 cycloalkyl, which are unsubstituted or derived from one or more halogens, OR 4 SR 9 COOR 4 CONR 10 R 11 NR 10 R 11 PO(OR) 3a 2. COR 3a Replace, or R 2 For C2-C 20 Alkyl or C1-C6 alkyl-C3-C6 cycloalkyl, wherein the derivative is one or more of O, CO, S, C(O)O, OC(O), SO, SO2, phenyl, naphthyl or NR. 10 Interruption; of which C2-C is interrupted 20 Alkyl groups that are unsubstituted or derived from one or more halogens, OR 4 SR 9 COOR 4 CONR 10 R 11 NR 10 R 11 Replace; or R 2 It is a C2-C4 hydroxyalkyl, C2-C 10 alkoxyalkyl, C3-C5 alkenyl, C3-C8 cycloalkyl, phenyl-C1-C3 alkyl, C2-C8 alkylyl, C3-C 12 Enyl, benzoyl; or R 2 For C6-C 20 Aryl or C3-C 20 heteroaryl groups, each unsubstituted or via one or more C1-C... 12 Alkyl, C1-C4 haloalkyl, phenyl, halogen, CN, NO2, OR 4 SR 9 NR 10 R 11 (CO)-R 3a Replacement, or via C2-C 20 Alkyl substitution, the C2-C 20 Alkyl groups via one or more O, S, or NR 10 Interruption, or each via one or more C1-C 20 Alkyl substitution, the C1-C 20 Alkyl groups that are unsubstituted or derived from one or more halogens, COOR 4 CONR 10 R 11 , phenyl, C3-C8 cycloalkyl, C3-C 20 heteroaryl, C6-C 20 aryloxycarbonyl, C3-C 20 heteroaryloxycarbonyl, OR 4 SR 9 or NR 10 R 11 Replace; or R 2 as a group R 3 It is hydrogen or C1-C 20 Alkyl; or R 3 For C1-C 20 Alkyl groups, which are derived from one or more halogens, OR 4 SR 9 NR 10 R 11 CN, COOR 4 CONR 10 R 11 C3-C8 cycloalkyl substitution, wherein the C3-C8 cycloalkyl group is uninterrupted or via one or more O, S, CO or NR. 10 Interrupted; or via one or more C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein each is unsubstituted or substituted via one or more halogens, phenyl groups, C1-C groups. 20 Alkylphenyl, C1-C8 alkoxyphenyl, C1-C4 haloalkyl, CN, NO2, OR 4 SR 9 or NR 10 R 11 Replace; or R 3 For C1-C 20 Alkyl groups, which are derived from one or more O, S, NR atoms 10 Disruptions involving CO, SO, or SO2, which are unsubstituted or via C3-C8 cycloalkyl groups, OH, SH, or O(CO)-R 3a COOR 4 CONR 10 R 11 C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or via one or more halogens, C1-C8 alkyl groups, or OR groups. 4 SR 9 or NR 10 R 11 Replace; or R 3 For C2-C 12 alkenyl or C3-C 20 cycloalkyl groups, each without interruption or via one or more O, S, CO, NR 10 or COOR 4 Interruption; or R 3 For C6-C 20 Aryl or C3-C 20 Heteroaryl groups, each unsubstituted or via one or more halogens, C1-C 20 Alkyl, C1-C4 haloalkyl, phenyl, C1-C 20 Alkylphenyl, C1-C8 alkoxyphenyl, CN, NO2, OR 4 SR 9 NR 10 R 11 COOR 4 (CO)-R 3a or SO2-R 3a Replace; or R 3 For C1-C 20 Alkyl groups, which are unsubstituted or via one or more C1-C... 10 Alkyl, C1-C4 haloalkyl, halogen, phenyl, C1-C 20 Alkylphenyl or C1-C8 alkoxyphenyl substituted; or R 3 For C1-C 20 Alkyl groups, which are formed by one or more O, S, NR groups 10 Interruption of CO, SO or SO2; or R 3 For C6-C 20 Aryloxy or C3-C 20 Heteroaryl groups, each unsubstituted or via one or more halogens, C1-C 20 Alkyl, C1-C4 haloalkyl, phenyl, C1-C 20 Alkylphenyl, C1-C8 alkoxyphenyl, CN, NO2, OR 4 SR 9 NR 10 R 11 COOR 4 (CO)-R 3a or SO2-R 3a replace; R 3a It is hydrogen or C1-C 20 Alkyl; or R 3a For C1-C 20 Alkyl groups, which are derived from one or more halogens, OR 4a SR 9a NR 10a R 11a CN, COOR 4a CONR 10a R 11a C3-C8 cycloalkyl substitution, wherein the C3-C8 cycloalkyl group is uninterrupted or via one or more O, S, CO or NR. 10a Interrupted; or via one or more C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein each is unsubstituted or substituted via one or more halogens, phenyl groups, C1-C groups. 20 Alkylphenyl, C1-C8 alkoxyphenyl, C1-C4 haloalkyl, CN, NO2, OR 4a SR 9a or NR 10a R 11a Replace; or R 3a For C1-C 20 Alkyl groups, which are derived from one or more O, S, NR atoms 10a Disruptions involving CO, SO, or SO2, which are unsubstituted or derived from C3-C8 cycloalkyl, OH, SH, O(CO)-(C1-C8 alkyl), or COOR 4a CONR 10a R 11a C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or via one or more halogens, C1-C8 alkyl groups, or OR groups. 4a SR 9a or NR 10a R 11a Replace; or R 3a For C2-C 12 alkenyl or C3-C 20 cycloalkyl groups, each without interruption or via one or more O, S, CO, NR 10a or COOR 4a Interruption; or R 3a For C6-C 20 Aryl or C3-C 20 Heteroaryl groups, each unsubstituted or via one or more halogens, C1-C 20 Alkyl, C1-C4 haloalkyl, phenyl, C1-C 20 Alkylphenyl, C1-C8 alkoxyphenyl, CN, NO2, OR 4a SR 9a NR 10a R 11a COOR 4a (CO)-(C1-C8 alkyl) or SO2-(C1-C4 haloalkyl) substitution; or R 3a For C1-C 20 Alkyl groups, which are unsubstituted or via one or more C1-C... 10 Alkyl, C1-C4 haloalkyl, halogen, phenyl, C1-C 20 Alkylphenyl or C1-C8 alkoxyphenyl substituted; or R 3a For C1-C 20 Alkyl groups, which are formed by one or more O, S, NR groups 10a Interruption of CO, SO or SO2; or R 3a For C6-C 20 Aryloxy or C3-C 20 Heteroaryl groups, each unsubstituted or via one or more halogens, C1-C 20 Alkyl, C1-C4 haloalkyl, phenyl, C1-C 20 Alkylphenyl, C1-C8 alkoxyphenyl, CN, NO2, OR 4a SR 9a NR 10a R 11a COOR 4a (CO)-(C1-C8 alkyl) or SO2-(C1-C4 haloalkyl) substitution; or R 3a as a group R 3b It is hydrogen or C1-C 20 Alkyl; or R 3b For C1-C 20 Alkyl groups, which are derived from one or more halogens, OR 4a SR 9a NR 10a R 11a CN, COOR 4a CONR 10a R 11a C3-C8 cycloalkyl substitution, wherein the C3-C8 cycloalkyl group is uninterrupted or via one or more O, S, CO or NR. 10a Interrupted; or via one or more C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein each is unsubstituted or substituted via one or more halogens, phenyl groups, C1-C groups. 20 Alkylphenyl, C1-C8 alkoxyphenyl, C1-C4 haloalkyl, CN, NO2, OR 4a SR 9a or NR 10a R 11a Replace; or R 3b For C1-C 20 Alkyl groups, which are derived from one or more O, S, NR atoms 10a Disruptions involving CO, SO, or SO2, which are unsubstituted or derived from C3-C8 cycloalkyl, OH, SH, O(CO)-(C1-C8 alkyl), or COOR 4a CONR 10a R 11a C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C 3- C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or via one or more halogens, C1-C8 alkyl groups, or OR groups. 4a SR 9a or NR 10a R 11a Replace; or R 3b For C2-C 12 alkenyl or C3-C 20 cycloalkyl groups, each without interruption or via one or more O, S, CO, NR 10a or COOR 4a Interruption; or R 3b For C6-C 20 Aryl or C3-C 20 Heteroaryl groups, each unsubstituted or via one or more halogens, C1-C 20 Alkyl, C1-C4 haloalkyl, phenyl, C1-C 20 Alkylphenyl, C1-C8 alkoxyphenyl, CN, NO2, OR 4a SR 9a NR 10a R 11a COOR 4a (CO)-(C1-C8 alkyl) or SO2-(C1-C4 haloalkyl) substitution; or R 3b For C1-C 20 Alkyl groups, which are unsubstituted or via one or more C1-C... 10 Alkyl, C1-C4 haloalkyl, halogen, phenyl, C1-C 20 Alkylphenyl or C1-C8 alkoxyphenyl substituted; or R 3b For C1-C 20 Alkyl groups, which are formed by one or more O, S, NR groups 10a Interruption of CO, SO or SO2; or R 3b For C6-C 20 Aryloxy or C3-C 20 Heteroaryl groups, each unsubstituted or via one or more halogens, C1-C 20 Alkyl, C1-C4 haloalkyl, phenyl, C1-C 20 Alkylphenyl, C1-C8 alkoxyphenyl, CN, NO2, OR 4a SR 9a NR 10a R 11a COOR 4a (CO)-(C1-C8 alkyl) or SO2-(C1-C4 haloalkyl) substitution; R 4 For hydrogen, (CO)-R 3a COOR 4a CO NR 10a R 11a S(O) m -R 3a or PO (OR) 3a )2; or R 4 For C1-C 20 Alkyl groups, which are derived from one or more halogens, OR 4a SR 9a NR 10a R 11a CN, COOR 4a CONR 10a R 11 a、PO(OR 3a 2. S(O) m -R 3a C3-C8 cycloalkyl substitution, wherein the C3-C8 cycloalkyl group is uninterrupted or via one or more O, S, CO or NR. 10a Interrupted; or via one or more C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein each is unsubstituted or substituted via one or more halogens, phenyl groups, C1-C groups. 20 Alkylphenyl, C1-C8 alkoxyphenyl, C1-C4 haloalkyl, CN, NO2, OR 4a SR 9a NR 10a R 11a PO(OR) 3a )2 or S(O) m -R 3a Replace; or R 4 For C1-C 20 Alkyl groups, which are derived from one or more O, S, NR atoms 10a Disruptions involving CO, SO, or SO2, which are unsubstituted or via C3-C8 cycloalkyl groups, OH, SH, or O(CO)-R 3a COOR 4a CONR 10a R 11a C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or via one or more halogens, C1-C8 alkyl groups, or OR groups. 4a SR 9a or NR 10a R 11a Replace; or R 4 For C2-C 12 alkenyl or C3-C 20 cycloalkyl groups, each without interruption or via one or more O, S, CO, NR 10a or COOR 4a Interruption; or R 4 For C6-C 20 aryl groups, which are derived from one or more halogens, CN, NO2, 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 groups Replacement; or via one or more C1-C 20 Alkyl substitution, the C1-C 20 Alkyl groups that are unsubstituted or derived from one or more halogens, COOR 4a CONR 10a R 11a , phenyl, C3-C8 cycloalkyl, C3-C 20 heteroaryl, OR 4a SR 9a or NR 10a R 11a Replacement; or via one or more C2-C 20 Alkyl substitution, the C2-C 20 Alkyl groups via one or more O, S, or NR 10a Interrupted; or substituted with one or more phenyl, naphthyl, benzoyl, or naphthyl groups, each of which is unsubstituted or substituted with OR 4a SR 9a or NR 10a R 11a Replace; or R 4 For C3-C 20 Heteroaryl groups, each unsubstituted or mediated by one or more halogens, CN, NO2, 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 groups Replacement; or via one or more C1-C 20 Alkyl substitution, the C1-C 20 Alkyl groups that are unsubstituted or derived from one or more halogens, COOR 4a CONR 10a R 11a , phenyl, C3-C8 cycloalkyl, C3-C 20 heteroaryl, OR 4a SR 9a or NR 10a R 11a Replacement; or via one or more C2-C 20 Alkyl substitution, the C2-C 20 Alkyl groups via one or more O, S, or NR 10a Interrupted; or substituted with one or more phenyl, naphthyl, benzoyl, or naphthyl groups, each of which is unsubstituted or substituted with OR 4a SR 9a or NR 10a R 11a Replace; or R 4 With R 1 A 5- or 6-membered saturated or unsaturated ring formed by one of the carbon atoms, which is uninterrupted or via O, S, or NR. 10a The interruption occurs, and the 5- or 6-member saturated or unsaturated ring is not substituted or substituted via one or more C1-C14 rings. 20 Alkyl, OR 4a SR 9a NR 10a R 11a (CO)-R 3a NO2, halogens, C1-C4 haloalkyl groups, CN, phenyl, C1-C 20 Alkylphenyl, C1-C8 alkoxyphenyl, Or C3-C 20 Cycloalkyl substitution, the C3-C 20 cycloalkyl groups are uninterrupted or via one or more O, S, CO, or NR groups. 10a Interruption; R 4a Hydrogen, C1-C 20 Alkyl, (CO)O (C1-C8 alkyl) or CON (C1-C8 alkyl)2; or R 4a For C1-C 20 Alkyl groups substituted with one or more halogens, OH, SH, CN, C3-C8 olefins, OCH2CH2CN, OCH2CH2(CO)O (C1-C8 alkyl), O(CO)-(C1-C8 alkyl), O(CO)-(C2-C4)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O (C1-C8 alkyl), C3-C8 cycloalkyl, SO2-(C1-C4 haloalkyl), O (C1-C4 haloalkyl), phenyl, C1-C8 alkylphenyl, C1-C8 alkoxyphenyl, or C3-C8 cycloalkyl, wherein the C3-C8 cycloalkyl group is interrupted by one or more O atoms; or R 4a For C2-C 20 Alkyl groups interrupted by one or more O, S, N (C1-C8 alkyl), CO, SO, or SO2, which are unsubstituted or interrupted by C3-C8 cycloalkyl, OH, SH, O(CO)(C1-C8 alkyl), (CO)O(C1-C8 alkyl), (CO)N(C1-C8 alkyl)2, C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or substituted with one or more halogens, C1-C8 alkyl groups, C1-C8 alkoxy groups, C1-C8 alkyl thio groups, or N(C1-C8 alkyl)2 groups; or R 4a For C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl groups, each of which is unsubstituted or substituted with one or more halogens, CN, NO2, OH, C1-C8 alkyl, C1-C4 haloalkyl, C1-C8 alkoxy, phenyl-C1-C3 alkoxy, phenoxy, C1-C8 alkyl hydrogen sulfide, phenyl hydrogen sulfide, N(C1-C8 alkyl)2, diphenylamino, (CO)O(C1-C8 alkyl), (CO)-C1-C8 alkyl or (CO)N(C1-C8)2, phenyl or benzoyl; R 4a For C2-C 12 Alkenyl, (CO)O (C1-C8 alkenyl) or C3-C8 cycloalkyl, each uninterrupted or interrupted by one or more O, S, CO, N (C1-C8 alkyl) or COO (C1-C8 alkyl); or R 4a For C1-C 20 Alkyl group, C3-C 12 The enoyl group is unsubstituted or substituted with one or more halogens, phenyl, C1-C8 alkylphenyl, C1-C8 alkoxyphenyl, OH, C1-C8 alkoxy, phenoxy, C1-C8 alkyl hydrogen sulfide, phenyl hydrogen sulfide, N(C1-C8 alkyl)2 or diphenylamino. R 5 R 6 R 7 and R 8 They are independently hydrogen, C1-C 20 Alkyl, C6-C 20 Aryl, C1-C 20 Alkoxy, C6-C 20 Aryl C1-C 20 -alkyl, hydroxy-C1-C 20 Alkyl, hydroxyl -C1-C 20 Alkoxy-C1-C 20 Alkyl, C3-C 10 Cycloalkyl, amino, CN, NO2, hydroxyl (CO)-R 3a OR 4a or COOR 4 ; R 9 It is hydrogen or C1-C 20 Alkyl; or R 9 For C1-C 20 Alkyl groups, which are derived from 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 C3-C8 cycloalkyl substitution, wherein the C3-C8 cycloalkyl group is uninterrupted or via one or more O, S, CO or NR. 10a Interrupted; or via one or more C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein each is unsubstituted or substituted via one or more halogens, phenyl groups, C1-C groups. 20 Alkylphenyl, C1-C8 alkoxyphenyl, C1-C4 haloalkyl, CN, NO2, OR 4a SR 9a NR 10a R 11a PO(OR) 3a )2 or S(O) m -R 3a Replace; or R 9 For C1-C 20 Alkyl groups, which are derived from one or more O, S, NR atoms 10a Disruptions involving CO, SO, or SO2, which are unsubstituted or via C3-C8 cycloalkyl groups, OH, SH, or O(CO)-R 3a COOR 4a CONR 10a R 11a C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or via one or more halogens, C1-C8 alkyl groups, or OR groups. 4a SR 9a or NR 10a R 11a Replace; or R 9 For C2-C 12 alkenyl or C3-C 20 cycloalkyl groups, each without interruption or via one or more O, S, CO, NR 10a or COOR 4a Interruption; or R 9 For C6-C 20 Aryl or C3-C 20 Heteroaryl groups, each unsubstituted or mediated by one or more halogens, CN, NO2, 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 groups Replacement; or via one or more C1-C 20 Alkyl substitution, the C1-C 20 Alkyl groups that are unsubstituted or derived from one or more halogens, COOR 4a CONR 10a R 11a , phenyl, C3-C8 cycloalkyl, C3-C 20 heteroaryl, OR 4a SR 9a or NR 10a R 11a Replacement; or via one or more C2-C 20 Alkyl substitution, the C2-C 20 Alkyl groups via one or more O, S, or NR 10a Interrupted; or substituted with one or more phenyl, naphthyl, benzoyl, or naphthyl groups, each of which is unsubstituted or substituted with OR 4a SR 9a or NR 10a R 11a Replace; or R 9 With R 1 One of the carbon atoms forms a 5- or 6-membered saturated or unsaturated ring, which is uninterrupted or via O, S, or NR. 10a The interruption occurs, and the 5- or 6-member saturated or unsaturated ring is not substituted or substituted via one or more C1-C14 rings. 20 Alkyl, OR 4a SR 9a NR 10a R 11a (CO)-R 3a NO2, halogens, C1-C4 haloalkyl groups, CN, phenyl, C1-C 20 Alkylphenyl, C1-C8 alkoxyphenyl, Or C3-C 20 Cycloalkyl substitution, the C3-C 20 cycloalkyl groups are uninterrupted or via one or more O, S, CO, or NR groups. 10a Interruption; R 9a It is hydrogen or C1-C 20 Alkyl; or R 9a For C1-C 20 Alkyl groups substituted with one or more halogens, OH, SH, CN, C3-C8 olefins, OCH2CH2CN, OCH2CH2(CO)O (C1-C8 alkyl), O(CO)-(C1-C8 alkyl), O(CO)-(C2-C4)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O (C1-C8 alkyl), C3-C8 cycloalkyl, SO2-(C1-C4 haloalkyl), O (C1-C4 haloalkyl), phenyl, C1-C8 alkylphenyl, C1-C8 alkoxyphenyl, or C3-C8 cycloalkyl, wherein the C3-C8 cycloalkyl group is interrupted by one or more O atoms; or R 9a For C2-C 20 Alkyl groups interrupted by one or more O, S, N (C1-C8 alkyl), CO, SO, or SO2, which are unsubstituted or interrupted by C3-C8 cycloalkyl, OH, SH, O(CO)(C1-C8 alkyl), (CO)O(C1-C8 alkyl), (CO)N(C1-C8 alkyl)2, C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or substituted with one or more halogens, C1-C8 alkyl groups, C1-C8 alkoxy groups, C1-C8 alkyl thio groups, or N(C1-C8 alkyl)2 groups; or R 9a For C2-C 12 Alkenyl or C3-C8 cycloalkyl, each uninterrupted or interrupted by one or more O, S, CO, N (C1-C8 alkyl) or COO (C1-C8 alkyl); or R 9a For C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl groups, each unsubstituted or substituted with one or more halogens, CN, NO2, OH, C1-C8 alkyl, C1-C4 haloalkyl, C1-C8 alkoxy, phenyl-C1-C3 alkoxy, phenoxy, C1-C8 alkyl hydrogen sulfide, phenyl hydrogen sulfide, N(C1-C8 alkyl)2, diphenylamino, (CO)O(C1-C8 alkyl), (CO)-C1-C8 alkyl or (CO)N(C1-C8)2, phenyl or benzoyl; or R 9a For C1-C 20 Alkyl group, C3-C 12 The enoyl group is unsubstituted or substituted with one or more halogens, phenyl, C1-C8 alkylphenyl, C1-C8 alkoxyphenyl, OH, C1-C8 alkoxy, phenoxy, C1-C8 alkyl hydrogen sulfide, phenyl hydrogen sulfide, N(C1-C8 alkyl)2 or diphenylamino. R 10 and R 11 They are independently hydrogen, C1-C 20 Alkyl group, S(O) m -R 3a O(CO)-R 3a (CO)-R 3a or CONR 10a R 11a ;or R 10 and R 11 C1-C are independent of each other. 20 Alkyl groups, which are derived from 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 C3-C8 cycloalkyl substitution, wherein the C3-C8 cycloalkyl group is uninterrupted or via one or more O, S, CO or NR. 10a Interrupted; or via one or more C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein each is unsubstituted or substituted via one or more halogens, phenyl groups, C1-C groups. 20 Alkylphenyl, C1-C8 alkoxyphenyl, C1-C4 haloalkyl, CN, NO2, OR 4a SR 9a NR 10a R 11a PO(OR) 3a )2 or S(O) m -R 3a Replace; or R 10 and R 11 C1-C are independent of each other. 20 Alkyl groups, which are derived from one or more O, S, NR atoms 10a Disruptions involving CO, SO, or SO2, which are unsubstituted or via C3-C8 cycloalkyl groups, OH, SH, or O(CO)-R 3a COOR 4a CONR 10a R 11a C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or via one or more halogens, C1-C8 alkyl groups, or OR groups. 4a SR 9a or NR 10a R 11a Replace; or R 10 and R 11 C2-C are independent of each other. 12 alkenyl or C3-C 20 cycloalkyl groups, each without interruption or via one or more O, S, CO, NR 10a or COOR 4a Interruption; or R 10 and R 11 C6-C are independent of each other. 20 Aryl or C3-C 20 Heteroaryl groups, each unsubstituted or mediated by one or more halogens, CN, NO2, 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 groups Replacement; or via one or more C1-C 20 Alkyl substitution, the C1-C 20 Alkyl groups that are unsubstituted or derived from one or more halogens, COOR 4a CONR 10a R 11a , phenyl, C3-C8 cycloalkyl, C3-C 20 heteroaryl, OR 4a SR 9a or NR 10a R 11a Replacement; or via one or more C2-C 20 Alkyl substitution, the C2-C 20 Alkyl groups via one or more O, S, or NR 10a Interrupted; or substituted with one or more phenyl, naphthyl, benzoyl, or naphthyl groups, each of which is unsubstituted or substituted with OR 4a SR 9a or NR 10a R 11a Replace; or R 10 and R 11 C1-C are independent of each other. 20 Alkoxy groups, which are unsubstituted or substituted with one or more halogens, phenyl groups, C1-C8 alkylphenyl groups, or C1-C8 alkoxyphenyl groups; or R 10 and R 11 C1-C are independent of each other. 20 Alkyl groups, which are formed by one or more O, S, NR groups 10a Interruption of CO, SO or SO2; or R 10 and R 11 C6-C are independent of each other. 20 Aryloxy or C3-C 20 Heteroaryl groups, each unsubstituted or oxidized by one or more halogens, C1-C8 alkyl, C1-C4 haloalkyl, phenyl, C1-C8 alkylphenyl, C1-C8 alkoxyphenyl, CN, NO2, OR 4a SR 9a NR 10a R 11a COOR 4a (CO)-R 3a or SO2-R 3a Replace; or R 10 With R 1 One of the carbon atoms forms a 5- or 6-membered saturated or unsaturated ring, which is uninterrupted or via O, S, or NR. 10a The interruption occurs, and the 5- or 6-member saturated or unsaturated ring is not substituted or substituted via one or more C1-C14 rings. 20 Alkyl, OR 4a SR 9a NR 10a R 11a (CO)-R 3a NO2, halogens, C1-C4 haloalkyl groups, CN, phenyl, C1-C 20 Alkylphenyl, C1-C8 alkoxyphenyl, Or C3-C 20 Cycloalkyl substitution, the C3-C 20 cycloalkyl groups are uninterrupted or via one or more O, S, CO, or NR groups. 10a Interruption; or R 10 and R 11 Together with the N atom it is attached to, it forms a 5- or 6-membered saturated or unsaturated ring, which is uninterrupted or via O, S, or NR. 10a The interruption occurs, and the 5- or 6-member saturated or unsaturated ring is not substituted or substituted via one or more C1-C14 rings. 20 Alkyl, OR 4a SR 9a NR 10a R 11a (CO)-R 3a NO2, halogens, C1-C4 haloalkyl groups, CN, phenyl Or C3-C 20 Cycloalkyl substitution, the C3-C 20 cycloalkyl groups are uninterrupted or via one or more O, S, CO, or NR groups. 10a Interruption; R 10a and R 11a They are independently hydrogen, C1-C 20 Alkyl group, S(O) m -(C1-C8 alkyl), O(CO)(C1-C8 alkyl), (CO)(C1-C8 alkyl), (CO)O(C1-C8 alkyl) or CON(C1-C8 alkyl)2; or R 10a and R 11a C1-C are independent of each other. 20 Alkyl groups substituted with one or more halogens, OH, SH, CN, C3-C8 alkenyloxy, OCH2CH2CN, OCH2CH2(CO)O(C1-C8 alkyl), O(CO)(C1-C8 alkyl), O(CO)-(C2-C4)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C1-C8 alkyl), C3-C8 cycloalkyl, SO2-(C1-C4 haloalkyl), O(C1-C4 haloalkyl), phenyl, C1-C8 alkylphenyl, C1-C8 alkoxyphenyl, or C3-C8 cycloalkyl, wherein the C3-C8 cycloalkyl group is interrupted by one or more O atoms; or R 10a and R 11a C2-C are independent of each other. 20 Alkyl groups interrupted by one or more O, S, N (C1-C8 alkyl), CO, SO, or SO2, which are unsubstituted or interrupted by C3-C8 cycloalkyl, OH, SH, O(CO)(C1-C8 alkyl), (CO)O(C1-C8 alkyl), (CO)N(C1-C8 alkyl)2, C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl substitution, wherein C6-C 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 The heteroaryl carbonyl group is unsubstituted or substituted with one or more halogens, C1-C8 alkyl groups, C1-C8 alkoxy groups, C1-C8 alkyl thio groups, or N(C1-C8 alkyl)2 groups; or R 10a and R 11a C2-C are independent of each other. 12 Alkenyl or C3-C8 cycloalkyl, each uninterrupted or interrupted by one or more O, S, CO, N (C1-C8 alkyl) or COO (C1-C8 alkyl); or R 10a and R 11a C6-C are independent of each other. 20 Aryl, C3-C 20 heteroaryl, C6-C 20 Aromatic acyl or C3-C 20 Heteroaryl carbonyl groups, each unsubstituted or substituted with one or more halogens, CN, NO2, OH, C1-C8 alkyl, C1-C4 haloalkyl, C1-C8 alkoxy, phenyl-C1-C3 alkoxy, phenoxy, C1-C8 alkyl hydrogen sulfide, phenyl hydrogen sulfide, N(C1-C8 alkyl)2, diphenylamino, (CO)O(C1-C8 alkyl), (CO)-C1-C8 alkyl or (CO)N(C1-C8 alkyl)2, phenyl or benzoyl; or R 10a and R 11a C1-C are independent of each other. 20 Alkyl group, C3-C 12 The enoyl group, each unsubstituted or substituted with one or more halogens, phenyl, C1-C8 alkylphenyl, C1-C8 alkoxyphenyl, OH, C1-C8 alkoxy, phenoxy, C1-C8 alkylhydrothio, phenylhydrothio, N(C1-C8 alkyl)2, or diphenylamino; or R 10a and R 11a C1-C are independent of each other. 20 Alkoxy groups, which are unsubstituted or substituted with one or more halogens, phenyl groups, C1-C8 alkylphenyl groups, or C1-C8 alkoxyphenyl groups; or R 10a and R 11a C1-C are independent of each other. 20 alkoxy groups, interrupted by one or more O, S, N (C1-C8 alkyl), CO, SO, or SO2; or R 10a and R 11a C6-C are independent of each other. 20 Aryloxy or C3-C 20 Heteroaryl groups, each unsubstituted or substituted with one or more halogens, C1-C8 alkyl, C1-C4 haloalkyl, phenyl, C1-C8 alkylphenyl, C1-C8 alkoxyphenyl, CN, NO2, C1-C8 alkoxy, C1-C8 alkylhydrothioyl, N(C1-C8 alkyl)2, CO(OC1-C8 alkyl), (CO)-(C1-C8 alkyl) or SO2-(C1-C8 alkyl); or R 10a and R 11a Together with the N atom it is attached to, it forms a 5- or 6-membered saturated or unsaturated ring, which is uninterrupted or interrupted by O, S, or N (C1-C8 alkyl), and wherein the 5- or 6-membered saturated or unsaturated ring is unsubstituted or is substituted by one or more C1-C8 alkyl, C1-C8 alkoxy, C1-C8 alkyl thiosulfate, N (C1-C8 alkyl)2, NO2, halogen, C1-C4 haloalkyl, CN, phenyl, or C3-C 20 Cycloalkyl substitution, the C3-C 20 The cycloalkyl group is either uninterrupted or interrupted by one or more O, S, CO, or N (C1-C8 alkyl groups); R 12 and R 13 They are independently hydrogen, C1-C 12 Alkyl, the C1-C 12 Alkyl groups are substituted as needed with one or more halogens, phenyl groups, CN groups, -OH groups, -SH groups, C1-C4 alkoxy groups, (CO)OH groups, or (CO)O groups (C1-C4 alkyl groups); or R 12 and R 13 It is a phenyl group, which, as needed, is esterified by one or more C1-C6 alkyl groups, halogens, CN, OR. 4 SR 9 or NR 10 R 11 Replace; or R 12 and R 13 Halogen, CN, OR 4 SR 9 SOR 9 SO2R 9 or NR 10 R 11 The substituent OR 4 SR 9 or NR 10 R 11 via group R as needed 4 R 9 R 10 and / or R 11 With one of the carbon atoms of phenyl, naphthyl, benzoyl or naphthyl or the substituent R 3a The carbon atoms form 5- or 6-membered rings; or R 12 and R 13 Together as a group Where R 14 R 15 R 16 and R 17 They are independently hydrogen, C1-C 12 Alkyl, the C1-C 12 Alkyl groups are substituted as desired with one or more halogens, phenyl groups, CN groups, -OH groups, -SH groups, C1-C4 alkoxy groups, (CO)OH groups, or (CO)O groups (C1-C4 alkyl groups); or R groups. 14 R 15 R 16 and R 17 It is a phenyl group, which, as needed, is esterified by one or more C1-C6 alkyl groups, halogens, CN, OR. 4 SR 9 or NR 10 R 11 Replace; or R 14 R 15 R 16 and R 17 Halogen, CN, OR 4 SR 9 or NR 10 R 11 ;or R 12 and R 13 Together as a group Where R 18 and R 19 They are independently hydrogen, C1-C 12 Alkyl, the C1-C 12 Alkyl groups are substituted as needed with one or more halogens, phenyl, CN, -OH, -SH, C1-C4 alkoxy, (CO)OH, or (CO)O (C1-C4 alkyl); or R 18 and R 19 It is a phenyl group, which, as needed, is esterified by one or more C1-C6 alkyl groups, halogens, CN, OR. 4 SR 9 or NR 10 R 11 replace; m is 1 or 2; and Q represents a CO bond or a direct bond.

2. The polymerizable liquid crystal composition according to claim 1, characterized in that: R 1 Hydrogen, C1-C 20 Alkyl, C1-C6 alkyl-C3-C6 cycloalkyl, C3-C 20 cycloalkyl or C2-C 12 alkenyl, wherein C3-C 20 cycloalkyl or C2-C 12 The alkenyl group is uninterrupted or via one or more O, S, CO, NR groups. 10 or COOR 4 Interruption; R 2 Hydrogen, C1-C 20 Alkyl or C1-C6 alkyl-C3-C6 cycloalkyl, which are unsubstituted or derived from one or more halogens, OR 4 SR 9 COOR 4 CONR 10 R 11 NR 10 R 11 PO(OR) 3a 2. COR 3a replace; R 3 It is hydrogen or C1-C 20 alkyl; R 3a It is hydrogen or C1-C 20 alkyl; R 4 For hydrogen, (CO)-R 3a COOR 4a CO NR 10a R 11a S(O) m -R 3a or PO (OR) 3a )2; R 4a Hydrogen, C1-C 20 Alkyl, (CO)O (C1-C8 alkyl) or CON (C1-C8 alkyl)2; R 5 R 6 R 7 and R 8 They are independently hydrogen, C1-C 20 Alkyl, C6-C 20 Aryl, C1-C 20 Alkoxy, C6-C 20 Aryl, C1-C 20 Alkyl, hydroxyl -C1-C 20 Alkyl, hydroxyl -C1-C 20 Alkoxy-C1-C 20 Alkyl, C3-C 10 Cycloalkyl, amino, CN, NO2, hydroxyl (CO)-R 3a OR 4a or COOR 4 ; R 9 It is hydrogen or C1-C 20 alkyl; R 10 and R 11 They are independently hydrogen, C1-C 20 Alkyl group, S(O) m -R 3a O(CO)R 3a (CO)-R 3a or CONR 10a R 11a ;and R 10a and R 11a They are independently hydrogen, C1-C 20 Alkyl group, S(O) m -(C1-C8 alkyl), O(CO)(C1-C8 alkyl), (CO)(C1-C8 alkyl), (CO)O(C1-C8 alkyl) or CON(C1-C8 alkyl)2; and Q represents a CO bond or a direct bond.

3. The polymerizable liquid crystal composition according to claim 1 or 2, characterized in that, The polymerization initiator of formula (I) is a compound of formula (Ia) or (Ib): in R 1 They are straight-chain C1-C8 alkyl groups, especially C2-C6 alkyl groups; R 20 and R 21 C1-C are independent of each other. 20 Alkyl, C6-C 20 Aryl or C3-C 20 Heteroaryl groups, especially C1-C8 alkyl groups.

4. The polymerizable liquid crystal composition according to claim 3, characterized in that... The polymerization initiator of formula (Ia) is a compound of formula (Ia-1):

5. The polymerizable liquid crystal composition according to any one of the preceding claims, characterized in that, The polymerizable liquid crystal compound is at least one anisotropic compound of formula (II). in C and D are selected independently from the following groups: phenyl, biphenyl, naphthyl, cycloalkyl, bicycloalkyl, Where *1 represents parts of C and X respectively. 2 and some D and X 1 The *2 indicates the bonding sites of C and D with the carboxyl groups adjacent to and partially bonded to E; Part of E is selected from the following groups: phenyl, biphenyl, and naphthyl; Part of F is selected from the group consisting of: groups of formula (IIIa), (IIIb) or (IIIc). Where * indicates the bonding site between part of F and the imine nitrogen atom of formula II; Where X 1 and X 2 At least one of them is independently represented by a group of formula (IV). Where n is an integer between 0 and 24, and one or more C atoms can be substituted with -O-, -COO-, -OCO-, -OOC-, -O(CO)O-, -N-, or -NR-. a -, -CON- are substitutes, where R a For C1-C 12 Alkyl groups; and PG represents polymerizable groups selected from the following groups: CH2=C(Ph)-, CH2=CW-COO-, CH2=CH-COO-Ph-, CH2=CW-CO-NH-, CH2=CH-O-, CH2=CH-OOC-, Ph-CH=CH-, CH2=CH-Ph-, CH2=CH-Ph-O-, R b -Ph-CH=CH-COO-、R b -OOC-CH=CH-Ph-O- and 2-W-epoxyethyl; where W represents H, Cl, Ph or a lower alkyl group and R b To indicate a lower alkyl group, the restriction condition is that when R b When linked to a phenyl group (-Ph-), it can also represent hydrogen or a lower alkoxy group. Furthermore, if applicable, X not represented by the group of formula (IV) 1 and X 2 Choose from the following groups: hydrogen, C1-C 12 Substituted or unsubstituted straight-chain or branched alkyl groups, C3-C 12 Substituted or unsubstituted straight-chain or branched alkenyl groups and C1-C 12 alkoxy groups, wherein one or more carbon atoms may be via -O-, -COO-, -OCO-, -OOC-, -O(CO)O-, -N-, -NR a -, -CON- are substitutes, where R a For C1-C 12 Alkyl; Y is selected from the group consisting of: H, or substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms; R 101 R 102 and R 103 Each can be independently selected from the following groups: hydrogen, C1-C 12 Straight-chain or branched alkyl groups, C3-C 12 alkenyl, C1-C 12 Alkoxy, C3-C 12 Alkenyl group, -(CH2) m -C(CH3)3, NO2, 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, -CF3, and -OCF3; where m is an integer between 0 and 12; R 104 Choose from the following groups: hydrogen, C1-C 18 Alkyl groups, C3-C with a double bond at the 3rd position or higher. 18 Alkenyl, -(CH2) P -C-(CF3)3, CN, and unsubstituted or substituted benzene rings, wherein the substituents of the benzene rings are selected from the group consisting of: C1-C6 straight-chain or branched alkyl groups, C1-C6 alkoxy groups, -C-(CH3)3, halogens, -CF3, NO2, CN, COR. 107 -COOR 107 -OCOR 107 -CONR 106 R 107 -NR 106 COR 107 OCOOR 107 -OCONR 106 R 107 -NR 106 COOR 107 -F, -Cl, -CF3 and -OCF3; among which R 106 Selected from the following groups: hydrogen, lower alkyl and lower alkenyl; R 107 Choose from the following groups: hydrogen, C1-C 18 Alkyl groups and C3-C groups having a double bond at the 3 position or higher. 18 Alkenyl; p is an integer between 0 and 12; R 105 It 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 groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 12 carbon atoms, and substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, wherein one or more carbon atoms may be substituted with -O-COO-, -OCO-, -OOC-, -O(CO)O-, -N-, NR-. a -、-CON-、-CO-R b1 or -NH-R c Replacement, where R a For C1-C 12 Alkyl, R b1 and R c Each of the following is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or an organic group having 2 to 30 carbon atoms including at least one aromatic ring, or 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.

6. The polymerizable liquid crystal composition according to claims 5 and 6, characterized in that, In some cases, F is a group of formula (IIIb) or (IIIc).

7. The polymerizable liquid crystal composition according to claims 5 and 6, characterized in that, The C and D portions are independently selected from phenyl or cyclohexyl groups, with the limitation that at least one C or D portion is phenyl.

8. The polymerizable liquid crystal composition according to claims 5 to 7, characterized in that, Part of E is a benzene ring.

9. The polymerizable liquid crystal composition according to claims 5 to 8, characterized in that, At least one of 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.

10. The polymerizable liquid crystal composition according to claims 5 to 9, characterized in that, R 101 R 102 and R 103 Each can be independently selected from the following groups: hydrogen, and C1-C. 12 Straight chain or C3-C 12 Branched alkyl groups.

11. The polymerizable liquid crystal composition according to any one of the preceding claims, further comprising a polymerization inhibitor.

12. The polymerizable liquid crystal composition according to any one of the preceding claims, further comprising a crosslinking agent selected from the group consisting of monofunctional, difunctional, and polyfunctional compounds containing at least one olefinic double bond, and polythiols having two or more thiol groups per molecule.

13. A liquid crystal film, which is a cured product of a polymerizable liquid crystal composition according to any one of the preceding claims.

14. A method for manufacturing a liquid crystal film according to claim 13, comprising: aligning a polymerizable liquid crystal compound to obtain a polymerizable liquid crystal layer having a predetermined orientation of the polymerizable liquid crystal compound; polymerizing the polymerizable liquid crystal compound to form a network in which the orientation of the liquid crystal is fixed; and laminating the liquid crystal film onto a pressure-sensitive adhesive coated on a substrate.

15. Use of a liquid crystal film according to claim 13 or a liquid crystal film obtained by the method according to claim 14, for manufacturing an optical device or an electro-optical device.

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