TW202140754A - Polymerizable liquid crystal composition, retardation film, elliptical polarizer and optical display - Google Patents

Abstract

Provided is a polymerizable liquid crystal composition which contains at least two types of polymerizable liquid crystal compound which have the same molecular weights but have different molecular structures and which are represented by formula (1). As the polymerizable liquid crystal compounds, the composition contains a polymerizable liquid crystal compound (1-1) in which G1 and G2 in formula (1) are 1,4-trans-cyclohexanediyl groups and a polymerizable liquid crystal compound (1-2) which differs in terms of molecular structure from the polymerizable liquid crystal compound (1-1) only in that at least one of G1 and G2 in formula (1) is a 1,4-cis-cyclohexanediyl group. The ratio of the peak area of the polymerizable liquid crystal compound (1-2) relative to the total peak area of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), as measured by liquid chromatography, is 0.01-10%.

Description

Polymerizable liquid crystal composition, retardation film, elliptical polarizing plate and optical display

The present invention relates to a polymerizable liquid crystal composition, a retardation film containing the cured product of the polymerizable liquid crystal composition, and an elliptical polarizing plate and an optical display including the retardation film.

As an optical film such as a retardation film used in a flat panel display device (FPD), for example, there is an optical film in which a polymerizable liquid crystal compound is dissolved in a solvent to obtain a coating liquid, and the obtained coating liquid is applied to After supporting the base material, it is obtained by polymerization. As the polymerizable liquid crystal compound used to form such an optical film, for example, a nematic liquid crystal compound having a rod-like structure connected with 2 to 4 six-membered rings is known.

On the other hand, for the retardation film, it is required to be able to perform uniform polarization conversion in the entire wavelength region as one of its characteristics. For example, it is known that the retardation value Re(λ) at a certain wavelength λ divided by the retardation at 550 nm The value of Re(550) [Re(λ)/Re(550)] is close to the wavelength range of 1, and the wavelength range that shows the reverse wavelength dispersion of [Re(450)/Re(550)]<1, theoretically It can perform uniform polarization conversion. The polymerizable liquid crystal compound that can constitute such a retardation film is disclosed in, for example, Japanese Patent Laid-Open No. 2011-207765 and Japanese Patent Laid-Open No. 2015-143788.

In a solution (coating liquid) for manufacturing an optical film obtained by dissolving a polymerizable liquid crystal compound in a solvent, the solubility in various solvents may be insufficient due to the molecular structure of the polymerizable liquid crystal compound. The polymerizable liquid crystal compound with low solubility may precipitate or crystallize in the coating solution. The precipitation and precipitation of the polymerizable liquid crystal compound may reduce the film forming ability and produce the obtained optical film. Causes of alignment defects. Therefore, it is expected to develop a polymerizable liquid crystal composition containing a polymerizable liquid crystal showing a further improved solubility to a solvent.

The object of the present invention is to provide a polymerizable liquid crystal composition having excellent solubility in a solvent.

The present invention provides the following suitable forms.

[式(1)中， Ar表示可具有取代基之二價芳香族烴基或二價芳香族雜環基， D¹ 、D² 、E¹ 、E² 、B¹ 及B² 分別獨立地表示-CR¹¹ R¹² -、-CH₂ -CH₂ -、-O-、-S-、-CO-O-、-O-CO-、-O-CO-O-、-C(=S)-O-、-O-C(=S)-、-O-C(=S)-O-、-CO-NR¹¹ -、-NR¹¹ -CO-、-O-CH₂ -、-CH₂ -O-、-S-CH₂ -、-CH₂ -S-或單鍵，R¹¹ 及R¹² 分別獨立地表示氫原子、氟原子或碳數1～4之烷基， G¹ 及G² 分別表示1,4-環己二基， A¹ 及A² 分別獨立地表示碳數3～16之二價脂環式烴基或碳數6～20之二價芳香族烴基，該脂環式烴基及該芳香族烴基中包含之氫原子可經鹵素原子、-R¹³ 、-OR¹³ 、氰基或硝基取代，R¹³ 表示碳數1～4之烷基，該烷基中包含之氫原子可被取代為氟原子， F¹ 及F² 分別獨立地表示碳數1～12之烷二基，該烷二基中包含之氫原子可經-OR¹⁴ 或鹵素原子取代，R¹⁴ 表示碳數1～4之烷基，該烷基中包含之氫原子可被取代為氟原子，該烷二基中包含之-CH₂ -可被取代為-O-或-CO-， P¹ 及P² 分別獨立地表示氫原子或聚合性基(其中，P¹ 及P² 中之至少1個為聚合性基)]， 作為上述聚合性液晶化合物，包含：式(1)中之G¹ 及G² 分別為1,4-反式-環己二基之聚合性液晶化合物(1-1)、及僅於式(1)中之G¹ 及G² 之至少一者為1,4-順式-環己二基之情況下分子結構與上述聚合性液晶化合物(1-1)不同之聚合性液晶化合物(1-2)； 藉由液相層析法測定之聚合性液晶化合物(1-2)之峰面積相對於聚合性液晶化合物(1-1)與聚合性液晶化合物(1-2)之總峰面積之比率為0.01%以上10%以下。 [2]如上述[1]中記載之聚合性液晶組合物，其中聚合性液晶化合物(1-2)包含式(1)中之G¹ 及G² 之任一者為1,4-順式-環己二基之聚合性液晶化合物(1-2a)、及式(1)中之G¹ 及G² 均為1,4-順式-環己二基之聚合性液晶化合物(1-2b)。 [3]如上述[1]或[2]中記載之聚合性液晶組合物，其中式(1)中之Ar為式(2-1)～(2-5)之任一者所表示之基

[式中， ＊表示與D¹ 或D² 之鍵結部； Q¹ 表示-S-、-O-或-NR¹⁵ -，R¹⁵ 表示氫原子或可具有取代基之碳數1～6之烷基， Q² 表示氫原子或可具有取代基之碳數1～6之烷基； W¹ 及W² 分別獨立地表示-O-、-S-、-CO-、-NR¹⁵ -，R¹⁵ 表示氫原子或可具有取代基之碳數1～6之烷基； Y¹ 表示碳數1～6之烷基、可具有取代基之芳香族烴基或芳香族雜環基，該烷基、該芳香族烴基或該芳香族雜環基中包含之氫原子可經鹵素原子取代，該烷基中包含之-CH₂ -可被取代為-O-、-CO-、-O-CO-或-CO-O-， Y² 表示CN基或可具有取代基之碳數1～12之烷基，該烷基中包含之氫原子可經鹵素原子取代，該烷基中包含之-CH₂ -可被取代為-O-、-CO-、-O-CO-或-CO-O-； Z¹ 、Z² 及Z³ 分別獨立地表示氫原子或碳數1～20之脂肪族烴基或烷氧基、碳數3～20之脂環式烴基、碳數6～20之一價芳香族烴基、鹵素原子、氰基、硝基、-NR¹⁵ R¹⁶ 或-SR¹⁵ ，Z¹ 及Z² 亦可相互鍵結而形成芳香環或芳香族雜環，R¹⁵ 及R¹⁶ 分別獨立地表示氫原子或碳數1～6之烷基； Ax表示具有選自由芳香族烴環及芳香族雜環所組成之群中之至少1個芳香族環的碳數2～30之有機基，Ay表示氫原子、可具有取代基之碳數1～6之烷基、或具有選自由芳香族烴環及芳香族雜環所組成之群中之至少1個芳香族環的碳數2～30之有機基，Ax與Ay亦可鍵結而形成環； Y³ 及Y⁴ 分別獨立地表示選自下述式(Y-1)中之基：

[式(Y-1)中， M¹ 表示氫原子或碳數1～6之烷基，該烷基可經1個以上之取代基X³ 取代，取代基X³ 表示氟原子、氯原子、溴原子、碘原子、五氟硫基、硝基、氰基、異氰基、胺基、羥基、巰基、甲基胺基、二甲基胺基、二乙基胺基、二異丙基胺基、三甲基矽烷基、二甲基矽烷基、異硫氰基、或者1個-CH₂ -或不相鄰之2個以上-CH₂ -可分別獨立地被取代為-O-、-S-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-O-CO-O-、-CO-NH-、-NH-CO-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-CH=CH-、-CF=CF-或-C≡C-之碳數1～20之直鏈狀或支鏈狀烷基，該烷基中之任意之氫原子可被取代為氟原子，或者亦可為-B¹¹ -F¹¹ -P¹¹ 所表示之基，B¹¹ 、F¹¹ 及P¹¹ 分別與上述式(1)中之B¹ 、F¹ 及P¹ 被同樣地定義，分別可與上述B¹ 、F¹ 及P¹ 相同，亦可不同； U¹ 表示具有芳香族烴基之碳數2～30之有機基，該芳香族烴基之任意之碳原子可被取代為雜原子，芳香族烴基可經1個以上之上述取代基X³ 取代； T¹ 表示-O-、-S-、-COO-、-OCO-、-OCO-O-、-NU² -、-N=CU² -、-CO-NU² -、-OCO-NU² -或-O-NU² -，U² 表示氫原子、碳數1～20之烷基、碳數3～12之環烷基、碳數3～12之環烯基、具有芳香族烴基(該芳香族烴基之任意之碳原子可被取代為雜原子)之碳數2～30之有機基、或(E¹¹ -A¹¹ )_q -B¹² -F¹² -P¹² ，該烷基、環烷基、環烯基及芳香族烴基分別未經取代或可經1個以上之取代基X³ 取代，該烷基亦可經該環烷基或環烯基取代，該烷基中之1個-CH₂ -或不相鄰之2個以上-CH₂ -可分別獨立地被取代為-O-、-S-、-CO-、-COO-、-OCO-、-CO-S-、-S-CO-、-SO₂ -、-O-CO-O-、-CO-NH-、-NH-CO-、-CH=CH-COO-、-CH=CH-OCO-、-COO-CH=CH-、-OCO-CH=CH-、-CH=CH-、-CF=CF-或-C≡C-，該環烷基或環烯基中之1個-CH₂ -或不相鄰之2個以上-CH₂ -可分別獨立地被取代為-O-、-CO-、-COO-、-OCO-或-O-CO-O-，E¹¹ 、A¹¹ 、B¹² 、F¹² 及P¹² 分別與式(1)中之E¹ 、A¹ 、B¹ 、F¹ 及P¹ 被同樣地定義，分別可與上述E¹ 、A¹ 、B¹ 、F¹ 及P¹ 相同，亦可不同，q表示0～4之整數，於存在複數個E¹¹ 及/或A¹¹ 之情形時，分別可相同亦可不同，U¹ 與U² 亦可鍵結而構成環]]。 [4]如上述[1]～[3]中任一項中記載之聚合性液晶組合物，其中式(1)中之A¹ 及A² 分別獨立地為1,4-環己二基或1,4-伸苯基二基。 [5]如上述[1]～[4]中任一項中記載之聚合性液晶組合物，其中式(1)中之P¹ 及P² 分別為丙烯醯基。 [6]如上述[1]～[5]中任一項中記載之聚合性液晶組合物，其進而包含光聚合起始劑。 [7]如上述[1]～[6]中任一項中記載之聚合性液晶組合物，其進而包含有機溶劑。 [8]一種相位差膜，其包含作為如上述[1]～[7]中任一項中記載之聚合性液晶組合物之硬化物之液晶硬化膜。 [9]如上述[8]中記載之相位差膜，其中 液晶硬化膜滿足式(i)： 0.75≦Re(450)/Re(550)＜1.00     (i) [式(i)中，Re(λ)表示液晶硬化膜於波長λ nm下之面內相位差值]。 [10]一種橢圓偏光板，其包含如上述[8]或[9]中記載之相位差膜。 [11]一種光學顯示器，其包含如上述[10]中記載之橢圓偏光板。 [12]一種可撓性圖像顯示裝置，其包含如上述[10]中記載之橢圓偏光板。[1] A polymerizable liquid crystal composition comprising at least two polymerizable liquid crystal compounds represented by formula (1) having the same molecular weight but different molecular structures

[In formula (1), Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent, and D ¹ , D ² , E ¹ , E ² , B ¹ and B ² each independently represent- CR ¹¹ R ¹² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O -, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S -CH ₂ -, -CH ₂ -S- or a single bond, R ¹¹ and R ¹² each independently represent a hydrogen atom, a fluorine atom or an alkyl group with 1 to 4 carbon atoms, and G ¹ and G ² each represent 1,4- Cyclohexanediyl, A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group with 3 to 16 carbons or a divalent aromatic hydrocarbon group with 6 to 20 carbons, in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The hydrogen atoms contained can be substituted by halogen atoms, -R ¹³ , -OR ¹³ , cyano or nitro groups, R ¹³ represents an alkyl group with 1 to 4 carbon atoms, and the hydrogen atoms contained in the alkyl group can be substituted with fluorine atoms , F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbons. The hydrogen atom contained in the alkanediyl group may be ^{substituted by -OR 14} or a halogen atom. R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms. , The hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, the -CH ₂ -contained in the alkanediyl group may be substituted with -O- or -CO-, P ¹ and P ² each independently represent a hydrogen atom Or a polymerizable group (wherein, ^{at least one of P 1} and P ² is a polymerizable group)], as the polymerizable liquid crystal compound, includes: G ¹ and G ² in formula (1) are 1,4- The polymerizable liquid crystal compound (1-1) of trans-cyclohexanediyl, and the case where only ^{at least one of G 1} and G ² in formula (1) is 1,4-cis-cyclohexanediyl The lower molecular structure of the polymerizable liquid crystal compound (1-2) is different from the above-mentioned polymerizable liquid crystal compound (1-1); the peak area of the polymerizable liquid crystal compound (1-2) measured by liquid chromatography is relative to the polymerization The ratio of the total peak area of the liquid crystal compound (1-1) to the polymerizable liquid crystal compound (1-2) is 0.01% or more and 10% or less. [2] The polymerizable liquid crystal composition as described in [1] above, wherein the polymerizable liquid crystal compound (1-2) includes ^{any one of G 1} and G ² in the formula (1), which is 1,4-cis -Cyclohexanediyl polymerizable liquid crystal compound (1-2a), and formula (1) G ¹ and G ² are both 1,4-cis-cyclohexanediyl polymerizable liquid crystal compound (1-2b ). [3] The polymerizable liquid crystal composition as described in [1] or [2] above, wherein Ar in formula (1) is a group represented by any one of formulas (2-1) to (2-5)

[In the formula, * represents the bonding part ^{with D 1} or D ^{2 ; Q 1} represents -S-, -O- or -NR ¹⁵ -, R ¹⁵ represents a hydrogen atom or a carbon number of 1 to 6 which may have a substituent Alkyl group, Q ² represents a hydrogen atom or an optionally substituted alkyl group with 1 to 6 carbons; W ¹ and W ² each independently represent -O-, -S-, -CO-, -NR ¹⁵ -, R ¹⁵ represents a hydrogen atom or an ^{alkyl group having 1 to 6 carbons which may have a substituent; Y 1} represents an alkyl group having 1 to 6 carbons, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and the alkyl group, The hydrogen atom contained in the aromatic hydrocarbon group or the aromatic heterocyclic group may be substituted by a halogen atom, and the -CH ₂ -contained in the alkyl group may be substituted with -O-, -CO-, -O-CO- or -CO-O-, Y ² represents a CN group or a C1-C12 alkyl group which may have a substituent, the hydrogen atom contained in the alkyl group may be substituted by a halogen atom, and the alkyl group contains -CH _2- Can be substituted with -O-, -CO-, -O-CO- or -CO-O-; Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom or an aliphatic hydrocarbon group or alkane with 1 to 20 carbon atoms Oxy group, alicyclic hydrocarbon group with 3 to 20 carbons, monovalent aromatic hydrocarbon group with 6 to 20 carbons, halogen atom, cyano, nitro, -NR ¹⁵ R ¹⁶ or -SR ¹⁵ , Z ¹ and Z ² They may also be bonded to each other to form an aromatic ring or an aromatic heterocyclic ring. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms; Ax represents an aromatic hydrocarbon ring and an aromatic heterocyclic ring At least one aromatic ring in the group consisting of an organic group with 2 to 30 carbons, Ay represents a hydrogen atom, an alkyl group with 1 to 6 carbons which may have a substituent, or has an aromatic hydrocarbon ring and At least one aromatic ring in the group consisting of aromatic heterocycles has an organic group of 2 to 30 carbon atoms, Ax and Ay may also be bonded to form a ring; Y ³ and Y ⁴ are each independently selected from the following The base in formula (Y-1):

[In formula (Y-1), M ¹ represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, and the alkyl group may be substituted with one or more substituents X ³ , and the substituent X ³ represents a fluorine atom, a chlorine atom, Bromine atom, iodine atom, pentafluorothio, nitro, cyano, isocyano, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamine Group, trimethylsilyl group, dimethylsilyl group, isothiocyano group, or one -CH ₂ -or two or more non-adjacent -CH ₂ -can be independently substituted with -O-,- S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH= CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- carbon number 1 -20 linear or branched alkyl groups, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or may be a group represented by ^{-B 11} -F ¹¹ -P ^{11 , B 11} , F ¹¹ and P ^{11 are defined in the same way as B 1} , F ¹ and P ¹ in the above formula (1), respectively, and can be the same as or different ^{from the above B 1} , F ¹ and P ^{1 respectively ; U 1} represents aromatic An organic group with 2 to 30 carbon atoms in the aromatic hydrocarbon group, any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and the aromatic hydrocarbon group may be substituted by one or more of the above-mentioned substituents X ³ ; T ¹ represents -O- , -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO-NU ² -, -OCO-NU ² -or -O-NU ² -, U ² represents a hydrogen atom, an alkyl group with 1 to 20 carbons, a cycloalkyl group with 3 to 12 carbons, a cycloalkenyl group with 3 to 12 carbons, and an aromatic hydrocarbon group (any carbon of the aromatic hydrocarbon group) Atoms may be substituted with heteroatoms) organic groups with 2 to 30 carbons, or (E ¹¹ -A ¹¹ ) _q -B ¹² -F ¹² -P ¹² , the alkyl, cycloalkyl, cycloalkenyl and aromatic groups The group hydrocarbyl groups are respectively unsubstituted or can be substituted by more than one substituent X ³ , the alkyl group can also be substituted by the cycloalkyl or cycloalkenyl group, and one -CH ₂ -in the alkyl group may not be adjacent Two or more of -CH ₂ -can be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO ₂ -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH =CH-, -CH=CH-, -CF=CF- or -C≡C-, one of the cycloalkyl or cycloalkenyl groups -CH ₂ -or two or more non-adjacent ones -CH _2- Can be independently Replaced with -O-, -CO-, -COO-, -OCO- or -O-CO-O-, E ¹¹ , A ¹¹ , B ¹² , F ¹² and P ¹² are respectively the same as E ^{1 in formula (1)} , A ¹ , B ¹ , F ¹ and P ¹ are defined in the same way, and may be the ^{same as or different from the above E 1} , A ¹ , B ¹ , F ¹ and P ^{1 respectively} . q represents an integer from 0 to 4, in When there are a plurality of E ¹¹ and/or A ¹¹ , they may be the same or different, and U ¹ and U ² may also be bonded to form a ring]]. [4] The polymerizable liquid crystal composition as described in any one of [1] to [3] above, wherein A ¹ and A ² in formula (1) are each independently 1,4-cyclohexanediyl or 1,4-Phenylenediyl. [5] The polymerizable liquid crystal composition as described in any one of [1] to [4] above, wherein P ¹ and P ² in the formula (1) are each an acryloyl group. [6] The polymerizable liquid crystal composition as described in any one of [1] to [5] above, which further contains a photopolymerization initiator. [7] The polymerizable liquid crystal composition as described in any one of [1] to [6] above, which further contains an organic solvent. [8] A retardation film comprising a liquid crystal cured film as a cured product of the polymerizable liquid crystal composition as described in any one of [1] to [7] above. [9] The retardation film as described in [8] above, wherein the liquid crystal cured film satisfies the formula (i): 0.75≦Re(450)/Re(550)<1.00 (i) [In the formula (i), Re( λ) represents the in-plane retardation value of the liquid crystal cured film at the wavelength λ nm]. [10] An elliptically polarizing plate comprising the retardation film as described in [8] or [9] above. [11] An optical display comprising the elliptically polarizing plate as described in [10] above. [12] A flexible image display device comprising the elliptical polarizing plate as described in [10] above.

According to the present invention, a polymerizable liquid crystal composition having excellent solubility in a solvent can be provided.

Hereinafter, embodiments of the present invention will be described in detail. Furthermore, the scope of the present invention is not limited to the embodiments described here, and various changes can be made within a range that does not impair the gist of the present invention.

[式(1)中， Ar表示可具有取代基之二價芳香族烴基或二價芳香族雜環基， D¹ 、D² 、E¹ 、E² 、B¹ 及B² 分別獨立地表示-CR¹¹ R¹² -、-CH₂ -CH₂ -、-O-、-S-、-CO-O-、-O-CO-、-O-CO-O-、-C(=S)-O-、-O-C(=S)-、-O-C(=S)-O-、-CO-NR¹¹ -、-NR¹¹ -CO-、-O-CH₂ -、-CH₂ -O-、-S-CH₂ -、-CH₂ -S-或單鍵，R¹¹ 及R¹² 分別獨立地表示氫原子、氟原子或碳數1～4之烷基， G¹ 及G² 分別表示1,4-環己二基， A¹ 及A² 分別獨立地表示碳數3～16之二價脂環式烴基或碳數6～20之二價芳香族烴基，該脂環式烴基及該芳香族烴基中包含之氫原子可經鹵素原子、-R¹³ 、-OR¹³ 、氰基或硝基取代，R¹³ 表示碳數1～4之烷基，該烷基中包含之氫原子可被取代為氟原子， F¹ 及F² 分別獨立地表示碳數1～12之烷二基，該烷二基中包含之氫原子可經-OR¹⁴ 或鹵素原子取代，R¹⁴ 表示碳數1～4之烷基，該烷基中包含之氫原子可經氟原子取代，該烷二基中包含之-CH₂ -可被取代為-O-或-CO-， P¹ 及P² 分別獨立地表示氫原子或聚合性基(其中，P¹ 及P² 中之至少1個為聚合性基)]。<Polymerizable liquid crystal composition> The polymerizable liquid crystal composition of the present invention contains at least two polymerizable liquid crystal compounds having the same molecular weight represented by the formula (1) but different molecular structures from each other. By including at least two polymerizable liquid crystal compounds whose molecular structures are different from each other but the molecular weights are the same, and the molecular structures represented by formula (1) are similar to each other, high solubility in solvents can be ensured.

[In formula (1), Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent, and D ¹ , D ² , E ¹ , E ² , B ¹ and B ² each independently represent- CR ¹¹ R ¹² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O -, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S -CH ₂ -, -CH ₂ -S- or a single bond, R ¹¹ and R ¹² each independently represent a hydrogen atom, a fluorine atom or an alkyl group with 1 to 4 carbon atoms, and G ¹ and G ² each represent 1,4- Cyclohexanediyl, A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group with 3 to 16 carbons or a divalent aromatic hydrocarbon group with 6 to 20 carbons, in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The hydrogen atoms contained can be substituted by halogen atoms, -R ¹³ , -OR ¹³ , cyano or nitro groups, R ¹³ represents an alkyl group with 1 to 4 carbon atoms, and the hydrogen atoms contained in the alkyl group can be substituted with fluorine atoms , F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbons. The hydrogen atom contained in the alkanediyl group may be ^{substituted by -OR 14} or a halogen atom. R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms. , The hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, the -CH ₂ -contained in the alkanediyl group may be substituted with -O- or -CO-, and P ¹ and P ² each independently represent a hydrogen atom or Polymerizable group (wherein, ^{at least one of P 1} and P ² is a polymerizable group)].

Regarding the polymerizable liquid crystal composition of the present invention, as the above-mentioned at least two kinds of polymerizable liquid crystal compounds, include a polymerizable liquid crystal compound in which G ¹ and G ² in formula (1) are 1,4-trans-cyclohexanediyl groups, respectively (1-1) (hereinafter also referred to as "polymerizable liquid crystal compound (1-1)"), and only ^{at least one of G 1} and G ² in formula (1) is 1,4-cis-ring In the case of hexamethylenediyl, a polymerizable liquid crystal compound (1-2) having a molecular structure different from the above-mentioned polymerizable liquid crystal compound (1-1) (hereinafter also referred to as "polymerizable liquid crystal compound (1-2)"). In the present invention, the polymerizable liquid crystal composition may include only one type of polymerizable liquid crystal compound (1-1), or may include two or more types. In the case of containing a plurality of polymerizable liquid crystal compounds (1-1), the polymerizable liquid crystal composition of the present invention contains polymerizable liquid crystal compounds (1-2) corresponding to at least one of the polymerizable liquid crystal compounds (1-1) ), and the polymerizable liquid crystal compound (1-2) corresponding to the plurality of polymerizable liquid crystal compounds (1-1) constituting the polymerizable liquid crystal composition may be included.

By dividing the polymerizable liquid crystal compound (1-1) and only in ^{the case where at least one of G 1} and G ² in formula (1) is 1,4-cis-cyclohexanediyl, the molecular structure is different, namely The polymerizable liquid crystal compound (1-2) is included as a combination of isomers, and the solubility of the polymerizable liquid crystal compound (1-1) in a solvent can be improved. That is, when the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) are included in combination, compared with the case where the polymerizable liquid crystal compound (1-1) is dissolved in a solvent alone, it can be More polymerizable liquid crystal compound (1-1) can be easily dissolved in the same amount or a smaller amount of solvent. Thereby, the undissolved polymerizable liquid crystal compound is unlikely to remain in the coating liquid, and the precipitation, precipitation, and stacking of the polymerizable liquid crystal compound in the coating liquid can be suppressed. The improvement of the solubility of the polymerizable liquid crystal compound (1-1) in the solvent is related to the suppression of alignment defects caused by the undissolved polymerizable liquid crystal compound and precipitates, and the improvement of storage stability.

所表示之聚合性液晶化合物。具有式(1)所表示之結構之化合物通常為於沿一個方向配向之狀態下聚合時顯示逆波長分散性雙折射之聚合性液晶化合物，能夠於較寬之波長區域進行均勻之偏光轉換。因此，藉由使用式(1)所表示之聚合性液晶化合物，可獲得將由該聚合性液晶化合物形成之相位差膜及橢圓偏光板用於顯示裝置等光學顯示器時可賦予良好之顯示特性之聚合性液晶組合物。The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) are respectively the formula (1):

The polymerizable liquid crystal compound represented. The compound having the structure represented by formula (1) is usually a polymerizable liquid crystal compound that exhibits reverse wavelength dispersive birefringence when polymerized in a state aligned in one direction, and can perform uniform polarization conversion in a wide wavelength region. Therefore, by using the polymerizable liquid crystal compound represented by formula (1), it is possible to obtain a polymer that can impart good display characteristics when the retardation film and elliptically polarizing plate formed from the polymerizable liquid crystal compound are used in optical displays such as display devices. Sexual liquid crystal composition.

In formula (1), G ¹ and G ² each independently represent 1,4-cyclohexadiyl. The two types of polymerizable liquid crystal compound (1-1) and polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention have structures represented by ^{G 1} and G ^{2 in formula (1) are all 1} , 4-trans-cyclohexadiyl, or ^{the case where any or all of G 1} and G ² are 1,4-cis-cyclohexadiyl are different from each other.

In formula (1), D ¹ , D ² , E ¹ , E ² , B ¹ and B ² independently represent -CR ¹¹ R ¹² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO -NR ¹¹ -, -NR ¹¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S- or a single bond. Here, R ¹¹ and R ¹² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, a methyl group, or an ethyl group.

In formula (1), D ¹ and D ² are each independently preferably -CO-O-, -O-CO-, -C(=S)-O-, -OC(=S)-, -O- CH ₂ -, -CH ₂ -O-, -CO-NR ¹¹ -or -NR ¹¹ -CO-, more preferably -CO-O-, -O-CO-, -CO-NR ¹¹ -or -NR ¹¹ -CO-, particularly preferably -CO-O-, -O-CO-. R ^{11 is} preferably a hydrogen atom, a methyl group or an ethyl group. In formula (1), D ¹ and D ² may be the same or different from each other. Furthermore, D ¹ and D ^{2 being identical to each other means that the structures of D 1} and D ² when viewed with Ar as the center are identical to each other. Hereinafter, the relationship between E ¹ and E ² , A ¹ and A ² , B ¹ and B ² , and F ¹ and F ² is also the same.

In formula (1), E ¹ , E ² , B ¹ and B ² are each independently preferably -O-, -S-, -CO-O-, -O-CO-, -O-CO-O- , -CO-NR ¹¹ -, -NR ¹¹ -CO- or a single bond, more preferably -O-, -O-CO- or -CO-O-. R ^{11 is} preferably a hydrogen atom, a methyl group or an ethyl group. In the formula (1), E ¹ and E ² and B ¹ and B ² may be the same or different from each other.

In formula (1), A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group having 3 to 16 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Here, the hydrogen atom contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a halogen atom, -R ¹³ , -OR ¹³ , cyano group or nitro group, and R ¹³ represents an alkyl group with 1 to 4 carbon atoms, The hydrogen atom contained in the alkyl group may be substituted with a fluorine atom.

In the formula (1), A ¹ and A ² are each independently preferably a 1,4-alkylene which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms. Phenyldiyl, 1,4-cyclohexanediyl which may be substituted with at least one substituent selected from the group consisting of halogen atoms and alkyl groups with 1 to 4 carbon atoms, more preferably substituted by methyl 1,4-phenylenediyl, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-cyclohexanediyl, particularly preferably unsubstituted 1,4-phenylenediyl Phenyldiyl or unsubstituted 1,4-cyclohexadiyl, particularly preferably unsubstituted 1,4-phenylenediyl. In the formula (1), A ¹ and A ² may be the same or different from each other.

In the formula (1), F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbon atoms. Here, the hydrogen atom contained in the alkanediyl group may be ^{substituted by -OR 14} or a halogen atom, R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a fluorine atom. _{In addition, -CH 2} -contained in the alkanediyl group may be substituted with -O- or -CO- (wherein, when there are a plurality of -O-s, they are not adjacent to each other).

In the formula (1), F ¹ and F ² are each independently preferably a substituted alkanediyl group having 4 to 12 carbon atoms. In formula (1), F ¹ and F ² may be the same or different from each other.

Examples of the polymerizable group represented by P ¹ or P ² include epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, propylene group, methyl group Alkyl propenyl, oxirane, oxetanyl, etc. Among them, acryloyl group, methacryloyl group, vinyl group and ethyleneoxy group are preferable, acryloyl group and methacryloyl group are more preferable, and acryloyl group is still more preferable. Formula (1), P ¹ and P ² as long as any one of a polymerizable group, may be the same as each other or may be different, but is preferably P ¹ and P ² are a polymerizable group, and more preferably ¹ to P P ² is all acryloyl group.

In formula (1), Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent. In the present invention, a divalent aromatic hydrocarbon group which may have a substituent refers to a divalent linking group containing at least one aromatic hydrocarbon ring, and a divalent aromatic heterocyclic group which may have a substituent refers to a divalent linking group containing at least one aromatic A divalent linking group of a heterocyclic ring. The aromatic hydrocarbon ring and aromatic heterocyclic ring mentioned here refer to those having the ring structure with the number of π electrons according to Shocker’s rule of [4n+2] (n represents an integer) (in the case of an aromatic heterocyclic ring, Including non-shared bonding electron pairs on heteroatoms such as -N= and -S- to satisfy Shocker's rule). Ar may include one aromatic hydrocarbon ring or aromatic heterocyclic ring, or two or more. When including one aromatic hydrocarbon ring or aromatic heterocyclic ring, Ar may be a divalent aromatic hydrocarbon group which may have a substituent, or may be a divalent aromatic heterocyclic group which may have a substituent. When two or more aromatic hydrocarbon rings or aromatic heterocycles are included, it may include only a plurality of aromatic hydrocarbon rings, or only a plurality of aromatic heterocycles, or may include more than one aromatic hydrocarbon ring and Aromatic heterocyclic ring. Two or more aromatic hydrocarbon rings and/or aromatic heterocyclic rings may be bonded to each other via a single bond, divalent bonding groups such as -CO-O- and -O-.

As the aromatic hydrocarbon ring that Ar may contain, for example, a benzene ring, a naphthalene ring, an anthracene ring, etc. may be mentioned, and a benzene ring and a naphthalene ring are preferable. Examples of aromatic heterocyclic rings include furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyridine ring, pyrimidine ring, triazole ring, triazole ring , Pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thiophenthiazole ring, azole ring, benzoazole ring, and phenanthroline ring. When Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

Among them, Ar preferably has an aromatic heterocyclic ring containing at least 2 heteroatoms selected from the group consisting of nitrogen atoms, oxygen atoms and sulfur atoms, and more preferably has a thiazole ring, a benzothiazole ring or a benzofuran The ring further preferably has a benzothiazole ring. Furthermore, when Ar has an aromatic heterocyclic ring containing at least two heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom, the above-mentioned aromatic heterocyclic ring may be the same as in the formula (1) D ¹ and D ^{2 are} directly bonded to form a divalent linking group, and can also be included as a ^{substituent of the divalent linking group directly bonded to D 1} and D ² , but preferably includes the above-mentioned aromatic heterocyclic ring The entire Ar group is configured in a three-dimensional configuration in a direction substantially orthogonal to the molecular alignment direction.

In formula (1), the total number of π electrons contained in the divalent aromatic hydrocarbon group or the divalent aromatic heterocyclic group represented by Ar, which may have a substituent, N _{π is} preferably 8 or more, more preferably 12 or more, Particularly preferred is 16 or more, and particularly preferred is 20 or more. Furthermore, it is preferably 36 or less, more preferably 32 or less, still more preferably 30 or less, particularly preferably 26 or less, and particularly preferably 24 or less.

As the divalent aromatic hydrocarbon group or the divalent aromatic heterocyclic group which may have a substituent represented by Ar in the formula (1), the groups represented by the following formulas (2-1) to (2-5) can be exemplified .

In the formulas (2-1) to (2-5), * represents the bonding part ^{with D 1} or D ^2.

In the formula (2-1), Q ¹ represents -S-, -O- or -NR ¹⁵ -, and R ¹⁵ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbons. In the formulas (2-3) and (2-4), Q ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

In the formula (2-2), W ¹ and W ² each independently represent -O-, -S-, -CO-, -NR ¹⁵ -, and R ¹⁵ represents a hydrogen atom or an optionally substituted carbon number of 1 to 6的alkyl.

In formula (2-1), Y ¹ represents an alkyl group having 1 to 6 carbons, an optionally substituted aromatic hydrocarbon group or an aromatic heterocyclic group, preferably an optionally substituted aromatic hydrocarbon group having 6 to 12 carbons The aromatic hydrocarbon group and the aromatic heterocyclic group having 3 to 12 carbons are more preferably the aromatic hydrocarbon group having 6 to 12 carbons and the aromatic heterocyclic group having 3 to 12 carbons. In the formula (2-2), Y ² represents a CN group or an optionally substituted alkyl group having 1 to 12 carbons. Here, the hydrogen atom contained in the alkyl group, the aromatic heterocyclic group or the aromatic heterocyclic group may be substituted with a halogen atom, and the -CH ₂ -contained in the alkyl group may be substituted with -O-, -CO- , -O-CO- or -CO-O-.

In formulas (2-1) to (2-5), Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom or an aliphatic hydrocarbon group or alkoxy group with 1 to 20 carbons, and a fat with 3 to 20 carbons Cyclic hydrocarbon group, monovalent aromatic hydrocarbon group with 6 to 20 carbon atoms, halogen atom, cyano group, nitro group, -NR ¹⁵ R ¹⁶ or -SR ¹⁵ , Z ¹ and Z ² can also be bonded to each other to form an aromatic ring or Aromatic heterocyclic ring. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In formulas (2-3) and (2-4), Ax represents an organic group with 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocyclic rings, Ay represents a hydrogen atom, an alkyl group having 1 to 6 carbons which may have a substituent, or a carbon number of 2 to 30 having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring The organic group, Ax and Ay can also be bonded to form a ring.

The bases represented by formulas (2-1) to (2-4) are not particularly limited. Specific examples include Japanese Patent Laid-Open No. 2011-207765, Japanese Patent Laid-Open No. 2008-107767, and WO2014/010325 The basis recorded in the bulletin, etc.

所表示之基。In formula (2-5), Y ³ and Y ⁴ are each independently selected from the following formula (Y-1):

The base expressed.

In the formula (Y-1), M ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The alkyl group may be substituted by one or more substituents X ³ .

Substituent X ³ represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorothio group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, Diethylamino, diisopropylamino, trimethylsilyl, dimethylsilyl, isothiocyano, or one -CH ₂ -or two or more non-adjacent -CH _2- They are independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH -, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF -Or -C≡C- is a linear or branched alkyl group having 1 to 20 carbon atoms, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or may be -B ¹¹ -F ¹¹ The base represented by -P ^{11 , B 11} , F ^11, and P ^{11 are defined in the same way as B 1} , F ¹ and P ¹ in the above formula (1), respectively, and can be defined as the same as the above B ¹ , F ¹ and P ^{1 respectively} The same can be different.

The substituent X ^{3 is} preferably a fluorine atom, a chlorine atom, -CF ₃ , -OCF ₃ or a cyano group. M ^{1 is} preferably unsubstituted, or a hydrogen atom or an alkyl group with 1 to 6 carbon atoms substituted with one or more fluorine atoms, more preferably a hydrogen atom.

U ¹ represents an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group. Any carbon atom of the aromatic hydrocarbon group can be substituted with a heteroatom, and U ¹ is an organic group with 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring . The aromatic hydrocarbon group may be substituted with one or more of the above-mentioned substituents X ³ .

In order to improve the wavelength dispersibility, U ^{1 is} preferably an organic group having an aromatic heterocyclic ring in which one or more carbon atoms are substituted by heteroatoms. In order to have good wavelength dispersion and high birefringence, U ^{1 is more} preferably an organic group having an aromatic heterocyclic ring which is a condensed ring of a five-membered ring and a six-membered ring.

Specifically, as U ¹ , it is preferable to have a group represented by the following formula. Furthermore, in the following formula, these groups have a bonding bond ^{with T 1 at any position.}

T ¹ means -O-, -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO-NU ² -, -OCO-NU ^2- Or -O-NU ² -, U ² represents a hydrogen atom, an alkyl group with 1 to 20 carbons, a cycloalkyl group with 3 to 12 carbons, a cycloalkenyl group with 3 to 12 carbons, and an aromatic hydrocarbon group (the aromatic Any carbon atom of the group hydrocarbon group may be substituted with a heteroatom) an organic group with 2 to 30 carbon atoms, or (E ¹¹ -A ¹¹ ) _q -B ¹² -F ¹² -P ¹² . The above-mentioned alkyl group, cycloalkyl group, cycloalkenyl group and aromatic hydrocarbon group are respectively unsubstituted or may be substituted by one or more substituents X ³ , and the above-mentioned alkyl group may be substituted by the above-mentioned cycloalkyl group or the above-mentioned cycloalkenyl group. Of 1 in the alkyl -CH ₂ - or more of the two non-adjacent -CH ₂ - may each independently be substituted with -O -, - S -, - CO -, - COO -, - OCO-, -CO-S-, -S-CO-, -SO ₂ -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH- OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C-, one of the above-mentioned cycloalkyl or cycloalkenyl- CH ₂ -or two or more non-adjacent -CH ₂ -s may be independently substituted with -O-, -CO-, -COO-, -OCO- or O-CO-O-. E ¹¹ , A ¹¹ , B ¹² , F ¹² and P ^{12 are defined in the same way as E 1} , A ¹ , B ¹ , F ¹ and P ¹ in the above formula (1), respectively, and can be defined as the same as the above E ¹ , A ¹ , B ¹ , F ¹ and P ^{1 are the} same or different. q represents an integer from 0 to 4, and when there are a plurality of E ¹¹ and/or A ¹¹ , they may be the same or different.

To make the birefringence good and easy to synthesize, T ^{1 is} preferably -O-, -S-, -N=CU ² -or -NU ² -. To easily improve the wavelength dispersion and birefringence, it is more preferable -O-, -S- or -NU ² -.

U ^{2 is} preferably a group that can be substituted by one or more of the above-mentioned substituents X ³ , and one -CH ₂ -or two or more non-adjacent -CH ₂ -can be independently substituted into -O- , -CO-, -COO-, -OCO- or -O-CO-O- C 1-20 alkyl or alkenyl, C 3-12 cycloalkyl, or C 3-12 The cycloalkenyl group, or the above-mentioned alkyl or alkenyl group which may be substituted by the cycloalkyl, cycloalkenyl, or aryl group.

Among them, in terms of birefringence and solvent solubility, U ^{2 is more} preferably that a hydrogen atom can be substituted with a fluorine atom, and one -CH ₂ -or two or more non-adjacent -CH ₂ -s can be independent of each other Ground is substituted with -O-, -CO-, -COO- or -OCO- with a linear alkyl group having 1 to 20 carbon atoms.

U ¹ and U ² may also be bonded to form a ring. In this case, for example ^{, a cyclic group represented by -NU 1} U ² or a cyclic group represented by -N=CU ¹ U ² can be exemplified.

In order to easily obtain raw materials, have good solubility and show high birefringence, Y ³ and Y ^{4 are} particularly preferably selected from the following formula (Y-1') ~ formula (Y-47') base.

From the viewpoints of making the polymerizable liquid crystal compound (1) good in alignment, easy to industrially manufacture, and improving productivity, the molecular structure of the polymerizable liquid crystal compound (1) is preferably symmetrical. Specific examples of the group represented by formula (2-5) include the following groups. * In the following (2-5a) to (2-5t) represents the bonding part ^{with D 1} or D ^2.

Among the formulas (2-1) to (2-5), the formula (2-1), the formula (2-3), the formula (2-4) and the formula (2-5) are preferred, and the formula ( 2-1) and formula (2-5), especially formula (2-1).

In the present invention, as the polymerizable liquid crystal compound represented by formula (1), for example, the compounds described in Japanese Patent Laid-Open No. 2019-003177, Japanese Patent Laid-Open No. 2019-073496, and the like are exemplified.

The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention are only represented by G ¹ and G ^{2 in the structure represented by the above formula (1)} The structure of 1,4-cyclohexadiyl is different from each other. Regarding the polymerizable liquid crystal compound (1-1), both G ¹ and G ² in the formula (1) are 1,4-trans-cyclohexanediyl groups. Regarding the polymerizable liquid crystal compound (1-2), based on the polymerization The structure of the liquid crystal compound (1-1) is different from the polymerizable liquid crystal compound (1-1) ^{only when at least one of G 1} and G ^{2 is 1,4-cis-cyclohexanediyl.}

In the present invention, the polymerizable liquid crystal compound (1-2) can be that one of G ¹ and G ² in the formula (1) is 1,4-trans-cyclohexanediyl, and the other is 1, 4-cis-cyclohexanediyl polymerizable liquid crystal compound (1-2a) (hereinafter also referred to as "polymerizable liquid crystal compound (1-2a)), and may also be G ¹ and G ^{2 in formula (1)} All are 1,4-cis-cyclohexanediyl polymerizable liquid crystal compound (1-2b) (hereinafter also referred to as "polymerizable liquid crystal compound (1-2b)). The polymerizable liquid crystal composition of the present invention can only Either one of the polymerizable liquid crystal compound (1-2a) and the polymerizable liquid crystal compound (1-2b) is included, and both may be included.

In the polymerizable liquid crystal composition of the present invention, the peak area of the polymerizable liquid crystal compound (1-2) measured by liquid chromatography is relative to the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2). The ratio of the total peak area of) (hereinafter also referred to as "area percentage value") becomes 0.01% or more and 10% or less, including the polymerizable liquid crystal composition (1-1) and the polymerizable liquid crystal compound (1-2). Regarding the polymerizable liquid crystal compound represented by formula (1) having a so-called T-shaped structure in which constituent molecules are arranged in the long axis direction of the main chain of the compound and the direction intersecting the long axis direction, in the formula (1 When G ¹ and G ^{2 in)} are both 1,4-trans-cyclohexanediyl groups (ie, polymerizable liquid crystal compound (1-1)), it is usually the same as G ¹ and G in formula (1) ^{Compared with the polymerizable liquid crystal compound (1-2) in which at least one of 2} is 1,4-cis-cyclohexanediyl, the molecular structure is stable and it is easy to align in the desired direction. Therefore, it can be manufactured with fewer alignment defects的optical film. Therefore, from the viewpoint of alignment and optical properties, it is considered that the polymerizable liquid crystal compound (1-1) is more advantageous as the polymerizable liquid crystal compound represented by formula (1). In the present invention, by setting the amount of the polymerizable liquid crystal compound (1-2) relative to the polymerizable liquid crystal compound (1-1) within a specific range, the alignment of the polymerizable liquid crystal compound (1-1) can be avoided. Under the influence of the properties, the solubility of the polymerizable liquid crystal compound (1-1) in the solvent is sufficiently improved.

If the area percentage value of the polymerizable liquid crystal compound (1-2) does not reach the above lower limit, it is difficult to improve the solubility of the polymerizable liquid crystal compound (1-1) in the solvent. If the polymerizable liquid crystal compound (1-2) If the area percentage value is more than the above lower limit, the solubility of the polymerizable liquid crystal compound (1-1) in the solvent tends to be sufficiently improved. In addition, if the area percentage value of the polymerizable liquid crystal compound (1-2) is less than the above upper limit, the liquid crystal alignment when an optical film such as a retardation film is produced from a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound The state is maintained well, and therefore, an optical film with excellent optical properties can be obtained while suppressing alignment defects. In the present invention, the area percentage value of the polymerizable liquid crystal compound (1-2) is more preferably 9% or less, still more preferably 8% or less, particularly preferably 7% or less, and particularly preferably 6% or less. In the present invention, the area percentage value of the polymerizable liquid crystal compound (1-2) is preferably 0.1% or more, more preferably 0.5%, and still more preferably 2.5% or more. On the other hand, in the present invention, even when the polymerizable liquid crystal compound (1-2) is contained in a small amount, the effect of greatly improving the solubility of the polymerizable liquid crystal compound (1-1) in the solvent is excellent. Therefore, In one aspect of the present invention, the area percentage value of the polymerizable liquid crystal compound (1-2) may not reach 1.0%, for example, 0.5% or less or 0.1% or less. In this case, it is easy to fully obtain the above-mentioned advantages of the present invention. Effect. Furthermore, when a plurality of types of polymerizable liquid crystal compounds corresponding to the polymerizable liquid crystal compound (1-1) and/or the polymerizable liquid crystal compound (1-2) are included, the area of the polymerizable liquid crystal compound (1-2) The percentage value is calculated with respect to the total peak area of all polymerizable liquid crystal compounds (1-2) and all polymerizable liquid crystal compounds (1-1). The area percentage value can be calculated based on the peak area measured by liquid chromatography. Specifically, it can be measured and calculated by the method described in the following examples.

The method for producing the polymerizable liquid crystal compound (1-1) and polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention is not particularly limited. According to its structure, the well-known organic synthesis reactions described in Methoden der Organischen Chemie, Organic Reactions, Organic Synthesis, Comprehensive Organic Synthesis, New Experimental Chemistry Lectures, etc. (for example, condensation reaction, esterification reaction, Williamson reaction, Ur Mann reaction, Witti reaction, Schiff base formation reaction, benzylation reaction, Sawtou reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Fred -Crafts reaction, Heck reaction, aldol reaction, etc.) are appropriately combined and manufactured.

所表示之聚合性液晶化合物(1-1)，可藉由進行 式(B)： HO-Ar-OH   (B) 所表示之醇化合物(B)與 式(C)：

所表示之羧酸化合物(C)之酯化反應而製造。再者，上述式(A-1)、式(B)及式(C)中之Ar、E¹ 、E² 、A¹ 、A² 、B¹ 、B² 、F¹ 、F² 、P¹ 及P² 與上述式(1)中規定者相同，對應式(A-1)所表示之聚合性液晶化合物(1-1)之結構來確定。For example, in formula (1), D ¹ and D ² are *-O-CO- (* represents the bonding part with Ar), and G ¹ and G ² are 1,4-trans-cyclohexadiyl groups, And has a symmetrical structure centered on Ar (ie, E ¹ and E ² , A ¹ and A ² , B ¹ and B ² , F ¹ and F ² , P ¹ and P ² are the same respectively) of the following formula (A -1):

The represented polymerizable liquid crystal compound (1-1) can be represented by the formula (B): HO-Ar-OH (B) represented by the alcohol compound (B) and formula (C):

It is produced by the esterification reaction of the carboxylic acid compound (C) shown. ^{Furthermore, Ar, E 1} , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ^{1 in the} above formula (A-1), formula (B) and formula (C) And P ² are the same as those specified in the above formula (1), and are determined corresponding to the structure of the polymerizable liquid crystal compound (1-1) represented by the formula (A-1).

As the alcohol compound (B), it is sufficient if it is a compound in which two hydroxyl groups are bonded to the aromatic group Ar of the desired polymerizable liquid crystal compound (1-1), and the aromatic group Ar corresponds to the formula (1) The aromatic group Ar. The aromatic group Ar is the same as defined above, and examples include compounds in which two * moieties in the above formulas (2-1) to (2-5) are hydroxyl groups.

As the carboxylic acid compound (C), as long as it corresponds to the P ¹ -F ¹ -B ¹ -A ¹ -E ¹ -G ¹ -in the formula (1) for the desired polymerizable liquid crystal compound (1-1) In the structure, ^{the 1,4-trans-cyclohexanediyl group to which G 1} is bonded may be a compound in which a carboxyl group is bonded.

所表示之化合物，藉由使該化合物與下述式(C')：

所表示之羧酸化合物(C')反應。再者，上述式(C')及(D)中之Ar、E¹ 、E² 、A¹ 、A² 、B¹ 、B² 、F¹ 、F² 、P¹ 及P² 與上述式(1)中規定者相同，對應式(A-1)所表示之聚合性液晶化合物(1-1)之結構來確定。 ^{The polymerizable liquid crystal compound (1-2a) in which any one of G 1} and G ² in the formula (1) is 1,4-cis-cyclohexanediyl can be produced, for example, by the following method: (B) reacts with the above-mentioned carboxylic acid compound (C) to obtain the following formula (D):

The compound represented by combining the compound with the following formula (C'):

The indicated carboxylic acid compound (C') reacts. ^{Furthermore, Ar, E 1} , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ² in the above formula (C') and (D) are the same as the above formula ( The same as those specified in 1) are determined corresponding to the structure of the polymerizable liquid crystal compound (1-1) represented by the formula (A-1).

^{In addition, the polymerizable liquid crystal compound (1-2b) in which G 1} and G ² in the formula (1) are both 1,4-cis-cyclohexanediyl groups can be used as the polymerizable liquid crystal compound (1-1 In the method exemplified in the manufacturing method of ), the carboxylic acid compound (C') is used instead of the carboxylic acid compound (C).

The esterification reaction of the alcohol compound (B) and the carboxylic acid compound (C) and/or the carboxylic acid compound (C′) is preferably carried out in the presence of a condensing agent. By carrying out the esterification reaction in the presence of the condensing agent, the esterification reaction can be carried out efficiently and quickly.

As the condensing agent, for example, 1-cyclohexyl-3-(2-𠰌lineethyl)carbodiimide methyl p-toluenesulfonate, dicyclohexylcarbodiimide, diisopropyl Carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Amine hydrochloride (water-soluble carbodiimide: commercially available as WSC), bis(2,6-diisopropylphenyl)carbodiimide, and bis(trimethylsilyl)carbodiimide Carbodiimide compounds such as imines, 2-methyl-6-nitrobenzoic anhydride, 2,2'-carbonylbis-1H-imidazole, 1,1'-oxadiimidazole, diphenyl azide Phosphoryl, 1(4-nitrobenzenesulfonyl)-1H-1, 2, 4-triazole, hexafluorophosphate 1H-benzotriazol-1-yl-oxytripyrrolidinylphosphonium, six Fluorophosphate 1H-benzotriazol-1-yl-oxytris(dimethylamino)phosphonium, tetrafluoroborate N,N,N',N'-tetramethyl-O-(N-butanedioic acid) Amino) uronium, N-(1,2,2,2-tetrachloroethoxycarbonyloxy) succinimide, N-benzyloxycarbonyl succinimide, tetrafluoroborate O-(6- Chlorobenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium, hexafluorophosphate O-(6-chlorobenzotriazol-1-yl)-N,N, N',N'-tetramethyluronium, 2-bromo-1-ethylpyridinium tetrafluoroborate, 2-chloro-1,3-dimethylimidazolinium chloride, 2-chloro-hexafluorophosphate 1,3-Dimethylimidazolium, 2-chloro-1-methylpyridinium iodide, 2-chloro-1-methylpyridinium p-toluenesulfonate, 2-fluoro-1-methyl p-toluenesulfonate Base pyridinium and pentachlorophenyl trichloroacetate, etc.

[式中，R¹ 及R² 相互獨立地表示反應性基， Ar、E¹ 、E² 、A¹ 、A² 、B¹ 、B² 、F¹ 、F² 、P¹ 及P² 表示與式(1)中之Ar、E¹ 、E² 、A¹ 、A² 、B¹ 、B² 、F¹ 、F² 、P¹ 及P² 相同之含義] 若為前者之方法，則容易控制聚合性液晶組合物中之聚合性液晶化合物(1-1)與聚合性液晶化合物(1-2)之含量，若為後者之方法，則具有合成簡便，可更有效率地製造聚合性液晶組合物之優點。The polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) constituting the polymerizable liquid crystal composition of the present invention can be used as a liquid crystal mixture by being separately prepared and then mixed. Further, by reaction of a compound of the reactive group R comprises reacting a compound of the following formula (I) represented by the ^2, of formula (II) represented by the sum of the group represented by R ² in the formula (III) R ¹ Reaction of compound It is also possible to prepare a liquid crystal mixture containing the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2a) and/or the polymerizable liquid crystal compound (1-2b).

[In the formula, R ¹ and R ² independently represent a reactive group, and Ar, E ¹ , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ² represent the same ^{Ar, E 1} , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ^{2 in} formula (1) have the same meaning] If it is the former method, it is easy to control If the content of the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) in the polymerizable liquid crystal composition is the latter method, the synthesis is simple and the polymerizable liquid crystal composition can be produced more efficiently The advantages of things.

^{Ar, E 1} , E ² , A ¹ , A ² , B ¹ , B ² , F ¹ , F ² , P ¹ and P ^{2 in} formula (I), formula (II) and formula (III) are based on and The molecular structure corresponding to the required polymerizable liquid crystal compound (1-1) and polymerizable liquid crystal compound (1-2) is determined.

In the middle of the formula (III) R ¹ in the formula (I) and formula (II) R ² may react with each other to form a long polymerizable liquid crystal compound represented by (1-1) and the polymerizable liquid crystal compound (1-2) of the formula (1) The structure represented by ^{D 1} and D ² in (1) is sufficient. For example, ^{the reactive group represented by R 1} and/or R ² may, for example, be a hydroxyl group, a carboxyl group, an amino group, etc., as long as the groups represented by R ¹ and R ^{2 are selected according to the reaction used in the production of the polymerizable liquid crystal compound} The reactive group is sufficient.

From the viewpoints of ease of reaction, operability of materials, and ease of acquisition, it is typical to use, for example, ^{an alcohol compound in which R 1} in formula (III) is a hydroxyl group as the compound represented by formula (III) , And as the compound represented by the formula (I) and the compound represented by the formula (II), the ^{carboxylic acid compound in which R 2} in the formula (I) and the formula (II) are each a carboxyl group undergoes an esterification reaction, whereby The polymerizable liquid crystal compound (liquid crystal mixture) constituting the polymerizable liquid crystal composition of the present invention is produced. The esterification reaction can be carried out according to the same method as the esterification reaction that can be used to produce the polymerizable liquid crystal compound represented by formula (I), etc., for example, the method described above, or the method described in Japanese Patent Laid-Open No. 2019-003177, etc. Methods and conditions.

By adjusting the amount of the compound represented by the formula (I) and the compound represented by the formula (II) used in the preparation, it is possible to control the polymerizable liquid crystal compound (1-1) and polymerization in the obtained liquid crystal mixture. The content ratio of the liquid crystal compound (1-2a) and the polymerizable liquid crystal compound (1-2b). By using a plurality of carboxylic acid compounds in the above-mentioned ^{method of reacting R 1} and R ² , a large number of compounds can be synthesized at the same time.

The polymerizable liquid crystal composition of the present invention may contain polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) as long as it does not affect the effects of the present invention. Examples of polymerizable liquid crystal compounds other than polymerizable liquid crystal compound (1-1) and polymerizable liquid crystal compound (1-2) include: polymerizable liquid crystal compounds that do not have the molecular structure represented by formula (1), For example, polymerizable liquid crystal compounds that usually exhibit positive wavelength dispersion when polymerized by alignment, such as the Liquid Crystal Handbook (Edited by the Liquid Crystal Handbook Editorial Committee, issued by Maruzen Co., Ltd. on October 30, 2012) "3.8.6 Network ( Fully crosslinked type)", "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material" among the compounds described in the compound having a polymerizable group, etc.

When the polymerizable liquid crystal composition of the present invention contains polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), a higher degree of alignment order is obtained. From the viewpoint of the liquid crystal cured film, the ratio of the polymerizable liquid crystal compound (1) to the total mass of all polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition is preferably 51% by mass or more, more preferably 70% by mass or more , More preferably 90% by mass or more, and may also be 100% by mass.

When two or more types of polymerizable liquid crystal compounds (1-1) are included, the polymerizable liquid crystal compound (1-2) corresponding to at least one of the polymerizable liquid crystal compounds (1-1) may be included. The content of the liquid crystal compound (1-1) (there is a corresponding polymerizable liquid crystal compound (1-2)) and the corresponding polymerizable liquid crystal compound (1-2) relative to the total mass of all polymerizable liquid crystal compounds, preferably It is 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition (the total amount of all polymerizable liquid crystal compounds) relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition is, for example, 70-99.5 parts by mass, preferably 80 -99 parts by mass, more preferably 85-98 parts by mass, and still more preferably 90-95 parts by mass. If the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film. In addition, in this specification, the solid component of the polymerizable liquid crystal composition refers to all the components after removing volatile components such as organic solvents from the polymerizable liquid crystal mixture.

In addition to the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2), the polymerizable liquid crystal composition of the present invention may further include a photopolymerization initiator, an organic solvent, a polymerization inhibitor, and photosensitization. Additives such as agents, leveling agents, etc. These components may be used individually by only 1 type, and may be used in combination of 2 or more types.

The polymerizable liquid crystal composition of the present invention preferably contains a polymerization initiator. The polymerization initiator is a compound that can generate reactive species and start a polymerization reaction such as polymerizable liquid crystal by the contribution of heat or light. The reactive species may, for example, be free radicals, cations, or anions. Among them, from the viewpoint of easy control of the reaction, a photopolymerization initiator that generates radicals by light irradiation is preferred.

As the photopolymerization initiator, for example, a benzoin compound, a benzophenone compound, a benzyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, a triacetin compound, an iodonium salt, a phosphonium salt, etc. . Specifically, examples include: Irgacure (registered trademark) 907, Irgacure184, Irgacure651, Irgacure819, Irgacure250, Irgacure369, Irgacure379, Irgacure127, Irgacure2959, Irgacureku754, Irgacure379ol B (above, made by Sei Japan Co., Ltd.) , Seikuol BEE (manufactured by Seiko Chemical Co., Ltd. above), kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), kayacure UVI-6992 (manufactured by Dow), Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Arkles NCI-831, Adeka Arkles NCI-930 (above manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (above manufactured by Nihon SiberHegner) and TAZ-104 (Manufactured by Sanwa Chemical Company). In the present invention, the polymerizable liquid crystal composition preferably contains at least one photopolymerization initiator, and may also contain two or more photopolymerization initiators.

The photopolymerization initiator can fully utilize the energy emitted from the light source and has excellent productivity. Therefore, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and among them, α- Acetophenone-based polymerization initiator, oxime-based photopolymerization initiator.

Examples of the α-acetophenone-based polymerization initiator include: 2-methyl-2-𠰌line-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamine 1-(4-𠰌olinylphenyl)-2-benzylbutan-1-one and 2-dimethylamino-1-(4-𠰌olinylphenyl)-2-(4- Methylphenylmethyl)butan-1-one, etc., more preferably 2-methyl-2-𠰌line-1-(4-methylthiophenyl)propan-1-one and 2 -Dimethylamino-1-(4-𠰌olinylphenyl)-2-benzylbutan-1-one. As commercial products of the α-acetophenone compound, Irgacure369, 379EG, 907 (manufactured by BASF Japan Co., Ltd. above), Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.), and the like can be mentioned.

The oxime-based photopolymerization initiator generates methyl radicals by irradiating light. With this methyl radical, the polymerizable liquid crystal compound is appropriately polymerized in the deep part of the formed liquid crystal cured film. In addition, from the viewpoint of more efficiently proceeding the polymerization reaction of the deep portion of the formed liquid crystal cured film, it is preferable to use a photopolymerization initiator capable of efficiently using ultraviolet rays with a wavelength of 350 nm or more. As a photopolymerization initiator capable of efficiently using ultraviolet rays with a wavelength of 350 nm or more, tris compounds and oxime ester carbazole compounds are preferred, and from the viewpoint of sensitivity, oxime ester carbazole compounds are more preferred. The oxime ester type carbazole compound may, for example, be 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzyl oxime)], ethyl ketone, 1-[9 -Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-1-(O-acetoxime) and the like. Commercial products of the oxime ester type carbazole compound include: Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (the above are made by BASF Japan Co., Ltd.), Adeka Optomer N-1919, Adeka Arkles NCI -831 (the above are manufactured by ADEKA Co., Ltd.), etc.

The addition amount of the photopolymerization initiator relative to 100 parts by mass of the polymerizable liquid crystal compound is usually 0.1 part by mass or more and 30 parts by mass or less, preferably 0.5 part by mass or more, more preferably 1 part by mass or more, and preferably 20 Parts by mass or less, more preferably 15 parts by mass or less. If it is in the above range, the reaction of the polymerizable group proceeds sufficiently, and it is difficult to disturb the alignment of the polymerizable liquid crystal compound.

In the present invention, the polymerizable liquid crystal composition is usually applied to a substrate or the like in a state of being dissolved in a solvent, and therefore preferably contains a solvent. As the solvent, a solvent that can dissolve the polymerizable liquid crystal compound constituting the polymerizable liquid crystal composition such as the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) is preferred. The polymerization reaction of liquid crystal compounds is an inert solvent. As the solvent, for example, water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butanol Alcohol solvents such as oxyethanol and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone , Methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone and other ketone solvents; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; ethyl cyclohexane, etc. Alicyclic hydrocarbon solvents; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; Amine-based solvents such as methylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used alone or in combination of two or more kinds. Among them, organic solvents are preferred, and alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide-based solvents, and aromatic hydrocarbon solvents are more preferred.

The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal composition. Therefore, in 100 parts by mass of the polymerizable liquid crystal composition, the solid content is preferably 2-50 parts by mass, more preferably 5-30 parts by mass. If the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition tends to be lowered, the thickness of the film becomes approximately uniform, and unevenness tends not to occur easily. The above-mentioned solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.

By compounding a polymerization inhibitor, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. Examples of polymerization inhibitors include hydroquinone and hydroquinones having substituents such as alkyl ethers; catechols having substituents such as alkyl ethers, such as butylcatechol; o Free radical scavengers such as benzene triphenols, 2,2,6,6-tetramethyl-1-piperidinoxy radicals; thiophenols; β-naphthylamines and β-naphthols. In order to polymerize the polymerizable liquid crystal compound without disturbing the alignment, the content of the polymerization inhibitor is usually 0.01-10 parts by mass, preferably 0.1-5 parts by mass, and more preferably, relative to 100 parts by mass of the polymerizable liquid crystal compound. It is 0.1 to 3 parts by mass.

等𠮿酮類；蒽及具有烷基醚等取代基之蒽類；啡噻𠯤；紅螢烯。作為光增感劑，例如可例舉：𠮿酮、9-氧硫𠮿

等𠮿酮類；蒽及具有烷基醚等取代基之蒽類；啡噻𠯤；紅螢烯。光增感劑之含量相對於聚合性液晶化合物100質量份，通常為0.01～10質量份，較佳為0.05～5質量份，進而較佳為0.1～3質量份。Furthermore, by using a sensitizer, the photopolymerization initiator can be highly sensitive. As a photosensitizer, for example, ketone, 9-oxysulfur 𠮿

And other ketones; anthracene and anthracene with alkyl ether and other substituents; phenanthrene; red fluorene. As a photosensitizer, for example, ketone, 9-oxysulfur 𠮿

And other ketones; anthracene and anthracene with alkyl ether and other substituents; phenanthrene; red fluorene. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound.

Furthermore, the polymerizable liquid crystal composition of this invention may contain a leveling agent. The leveling agent is an additive that has the function of adjusting the fluidity of the polymerizable liquid crystal composition and making the film obtained by coating the polymerizable liquid crystal composition flatter, for example: polysiloxane series, polyacrylate series and Perfluoroalkyl type leveling agent. Specifically, examples include: DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of which are manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (the above are all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (the above are all Momentive Advanced Materials Japan Co., Ltd.), fluorinert (registered trademark) FC-72, fluorinert FC-40, fluorinert FC-43, fluorinert FC-3283 (all the above are manufactured by Sumitomo 3M (stock)), Megafac (registered trademark) R-08, Megafac R-30, Megafac R-90, Megafac F-410, Megafac F-411, Megafac F-443, Megafac F-445, Megafac F-470, Megafac F-477, Megafac F-479, Megafac F-482, Megafac F-483 (all of the above are manufactured by DIC (Stock)), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (all of the above are manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S -381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, SA-100 (all above are manufactured by AGC Seimi Chemical Co., Ltd.), trade name E1830, trade name E5844 (manufactured by Daikin Institute of Fine Chemicals Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353, BYK-361N (all trade names: manufactured by BM Chemie), etc. Among them, polyacrylate-based leveling agents and perfluoroalkyl-based leveling agents are preferred.

The content of the leveling agent in the polymerizable liquid crystal composition is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. If the content of the leveling agent is within the above range, it is easy to align the polymerizable liquid crystal compound, and the obtained liquid crystal cured film tends to be smooth, which is preferable. The polymerizable liquid crystal composition may have two or more types of leveling agents.

The polymerizable liquid crystal composition of the present invention can be prepared by adding a solvent, a photopolymerization initiator, and a polymerization inhibitor to the polymerizable liquid crystal compound (1-1) and the polymerizable liquid crystal compound (1-2) as necessary , Additives such as photosensitizer or leveling agent, stir and mix at the specified temperature.

＜Retardation film＞ Regarding the polymerizable liquid crystal composition of the present invention, the solubility of the polymerizable liquid crystal compound in the solvent is relatively high. Therefore, the alignment defects caused by the precipitation and precipitation of the undissolved polymerizable liquid crystal compound and the polymerizable liquid crystal compound in storage are suppressed The result is excellent. Therefore, by using the polymerizable liquid crystal composition of the present invention, it is possible to form a film without reducing the optical properties that the polymerizable liquid crystal compound can originally exhibit, and a liquid crystal cured film with excellent optical properties can be obtained. Therefore, the present invention also relates to a retardation film comprising a liquid crystal cured film, which is a cured product (liquid crystal cured film) of the polymerizable liquid crystal composition of the present invention, and the polymerizability in the polymerizable liquid crystal composition The liquid crystal compound is hardened in the aligned state. The retardation film containing the above-mentioned liquid crystal cured film can fully exhibit the optical properties that the polymerizable liquid crystal compound used originally can exert, and can become a retardation film with higher optical performance.

The liquid crystal cured film constituting the retardation film of the present invention may also include a homopolymer of the polymerizable liquid crystal compound (1-1) in an aligned state and a homopolymer of the polymerizable liquid crystal compound (1-2), and may also A copolymer comprising a mixture of polymerizable liquid crystal compound (1-1) and polymerizable liquid crystal compound (1-2) in an aligned state. Since the polymerization reaction is relatively easy and it is easy to obtain a uniform liquid crystal cured film, the liquid crystal cured film constituting the retardation film of the present invention preferably contains a polymerizable liquid crystal compound (1-1) and a polymerizable liquid crystal compound (1-2). The mixture is a copolymer in the aligned state.

In one aspect of the present invention, the retardation film of the present invention includes a liquid crystal cured film that is a cured product of the polymerizable liquid crystal composition of the present invention, and the liquid crystal cured film preferably has an optics represented by the following formula (i) characteristic: 0.75≦Re(450)/Re(550)＜1.0 (i) [In formula (i), Re(λ) represents the in-plane retardation value of the liquid crystal cured film at the wavelength λ nm]. When the liquid crystal cured film satisfies the formula (i), it exhibits so-called reverse wavelength dispersion, that is, the in-plane retardation value of the liquid crystal cured film at short wavelengths is smaller than the in-plane retardation value at long wavelengths. In order to improve the reverse wavelength dispersion and further improve the optical properties of the retardation film, Re(450)/Re(550) is more preferably 0.76 or more, more preferably 0.78 or more, more preferably 0.92 or less, and more It is preferably 0.90 or less, particularly preferably 0.87 or less, more preferably 0.86 or less, and particularly preferably 0.85 or less.

In one aspect of the present invention, the retardation film of the present invention preferably includes a liquid crystal cured film having an optical characteristic represented by the following formula (ii): 1.00≦Re(650)/Re(550) (ii) [In formula (ii), Re(λ) represents the in-plane retardation value of the retardation film at the wavelength λ nm]. From the viewpoint of the optical characteristics of the retardation film, Re(650)/Re(550) is more preferably 1.01 or more, and still more preferably 1.02 or more.

In addition, in one aspect of the present invention, the retardation film of the present invention preferably includes a liquid crystal cured film having an optical characteristic represented by the following formula (iii): 100 nm≦Re(550)≦180 nm (iii) [In formula (iii), Re(λ) represents the in-plane retardation value of the retardation film at the wavelength λ nm]. The liquid crystal cured film that satisfies the above formula (iii) functions as a λ/4 plate, and when an elliptical polarizing plate equipped with a retardation film including the liquid crystal cured film is applied to an optical display, the improvement effect of the front reflection hue (inhibition of coloring) The effect) is excellent. A more preferable range of the in-plane retardation value is 120 nm≦Re(550)≦170 nm, and a more preferable range is 130 nm≦Re(550)≦150 nm.

The above-mentioned in-plane retardation value can be adjusted according to the thickness d of the liquid crystal cured film. The in-plane retardation value is determined by the above formula Re(λ)=(nx(λ)-ny(λ))×d. Therefore, in order to obtain the required in-plane retardation value (Re(λ): The in-plane retardation value of the cured liquid crystal film at the wavelength λ (nm)), as long as the three-dimensional refractive index and the film thickness d are adjusted. Furthermore, in the above formula, d represents the thickness of the target liquid crystal cured film, and nx represents the principal refractive index at the wavelength λ nm in the direction parallel to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film Ny represents the refractive index at a wavelength λ nm in a direction parallel to the plane of the liquid crystal cured film and orthogonal to the direction of nx in the refractive index ellipsoid formed by the liquid crystal cured film.

The retardation film of the present invention can be manufactured, for example, by a method including the following steps: The step of forming the coating film of the polymerizable liquid crystal composition of the present invention, drying the coating film, and aligning the polymerizable liquid crystal compound in the polymerizable liquid crystal composition; and While maintaining the alignment state, the step of polymerizing the polymerizable liquid crystal compound by light irradiation to form a liquid crystal cured film.

The coating film of the polymerizable liquid crystal composition can be formed by coating the polymerizable liquid crystal composition on a substrate or an alignment film described below. As the base material, for example, a glass base material, a film base material, etc. may be mentioned, and from the viewpoint of processability, a resin film base material is preferred. As the resin constituting the film substrate, for example, polyolefins such as polyethylene, polypropylene, and norene-based polymers; cycloolefin-based resins; polyvinyl alcohol; polyethylene terephthalate; Polymethacrylate; polyacrylate; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfide; Polyether stubble; polyether ketone; polyphenylene sulfide and polyphenylene ether and other plastics. Such a resin can be formed into a film by a known method such as a solvent casting method and a melt extrusion method to form a substrate. The surface of the substrate can also have a protective layer formed of acrylic resin, methacrylic resin, epoxy resin, oxetane resin, polyurethane resin, melamine resin, etc., and it can also be subjected to mold release treatment such as silicone treatment , Corona treatment, plasma treatment and other surface treatments.

Commercially available products can also be used as substrates. Examples of commercially available cellulose ester substrates include: cellulose ester substrates manufactured by FUJI FILM Co., Ltd. such as Fujitac Film; Konica Minolta such as "KC8UX2M", "KC8UY", and "KC4UY" Cellulose ester substrate manufactured by Opto Co., Ltd., etc. As commercially available cycloolefin resins, for example, cycloolefin resins manufactured by Ticona (independent) such as "Topas (registered trademark)"; JSR Co., Ltd. such as "ARTON (registered trademark)" Cycloolefin resins manufactured; "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)" Cycloolefin resins manufactured by Zeon Corporation; "APEL" (registered trademark) such as Mitsui Cycloolefin resin manufactured by Chemical Co., Ltd. Commercially available cycloolefin resin substrates can also be used. Examples of commercially available cycloolefin resin substrates include: "S-SINA (registered trademark)" and "SCA40 (registered trademark)" cycloolefin resin substrates manufactured by Sekisui Chemical Industry Co., Ltd.; "ZEONOR Film (registered trademark)" such as the cycloolefin resin base material manufactured by Optes Co., Ltd.; "ARTON Film (registered trademark)" such as the cycloolefin resin base material manufactured by JSR Co., Ltd.

From the viewpoints of the thickness reduction of the retardation film, the ease of peeling of the substrate, and the rationality of the substrate, the thickness of the substrate is usually 5 to 300 μm, preferably 10 to 150 μm.

As a method of applying the polymerizable liquid crystal composition to a substrate or the like, for example, spin coating method, extrusion coating method, gravure coating method, die nozzle coating method, bar coating method, application Coating methods such as coating method; printing methods such as flexographic printing method and other well-known methods.

Then, the solvent is removed by drying or the like, thereby forming a dry coating film. The drying method may, for example, be a natural drying method, a ventilation drying method, a heat drying method, and a reduced pressure drying method. At this time, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent can be dried and removed from the coating film, and the polymerizable liquid crystal compound can be aligned in a desired direction (for example, horizontally) with respect to the plane of the coating film. Or vertical direction). The heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound used and the material of the substrate forming the coating film, etc. However, in order to make the polymerizable liquid crystal compound phase transition into the liquid crystal phase state, the liquid crystal phase transition temperature is usually required The above temperature. In order to remove the solvent contained in the polymerizable liquid crystal composition and make the polymerizable liquid crystal compound in a desired alignment state, for example, it can be heated to the liquid crystal phase transition temperature of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition (smearization). Phase transition temperature or nematic phase transition temperature) above the temperature. In addition, the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature adjustment stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analysis device (TG-DTA), and the like. The above-mentioned phase transition temperature of the polymerizable liquid crystal composition of the present invention containing at least two polymerizable liquid crystal compounds refers to the use of all polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition so as to have the same composition as the polymerizable liquid crystal composition The measured temperature of a mixture of polymerizable liquid crystal compounds mixed in a ratio.

The polymerizable liquid crystal composition of the present invention contains at least two types of polymerizable liquid crystal compound (1-1) and polymerizable liquid crystal compound (1-2), and generally can be lower than the single polymerizable liquid crystal compound (1-1) or The polymerizable liquid crystal compound (1-2) undergoes liquid crystal phase transition at a temperature at which the liquid crystal phase transitions. Therefore, in the production of the retardation film using the polymerizable liquid crystal composition of the present invention, the excessive consumption of thermal energy can be suppressed, and the production efficiency can be improved. In addition, the liquid crystal phase transition is performed by heating at a relatively low temperature, thereby, there is also an advantage that there are more options for coating the support substrate of the polymerizable liquid crystal composition.

The heating time can be appropriately determined according to the heating temperature, the type of polymerizable liquid crystal compound used, the type of solvent, and the boiling point and amount of the solvent, etc., but it is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.

Regarding the removal of the solvent from the coating film, it may be performed while heating to a temperature higher than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound, or may be performed separately, but from the viewpoint of improving productivity, it is preferably performed simultaneously. A pre-drying step can also be provided before heating to a temperature above the liquid crystal phase transition temperature of the polymerizable liquid crystal compound. This step is appropriately used under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize. Remove the solvent in the coating film. The drying method in the pre-drying step may, for example, be a natural drying method, a vent drying method, a heat drying method, a reduced pressure drying method, etc. The drying temperature (heating temperature) in the drying step can be based on the polymerizable liquid crystal used The type of compound, the type of solvent, and the boiling point and amount of the solvent are appropriately determined.

Then, in the obtained dry coating film, in the aligned state of the polymerizable liquid crystal compound, the polymerizable liquid crystal compound is polymerized by light irradiation to form a polymer as the polymerizable liquid crystal compound existing in the desired aligned state The liquid crystal hardened film. The polymerizable liquid crystal composition of the present invention can suppress damage to the polymerizable liquid crystal compound, and is highly polymerized by light irradiation such as high-intensity ultraviolet rays. Therefore, as a polymerization method, a photopolymerization method is generally used. In the photopolymerization, the light irradiated to the dry coating film is appropriately selected according to the type of polymerization initiator contained in the dry coating film, the type and amount of the polymerizable liquid crystal compound. As a specific example, one or more types of light and active electron beams selected from the group consisting of visible light, ultraviolet light, infrared light, X-ray, α-ray, β-ray, and γ-ray can be mentioned. Among them, in terms of easy control of the progress of the polymerization reaction, and in terms of being able to use a wide range of users in the field as a photopolymerization device, ultraviolet light is preferred, and a method capable of photopolymerization by ultraviolet light is preferred. Select the type of polymerizable liquid crystal compound and polymerization initiator contained in the polymerizable liquid crystal composition. In addition, during polymerization, the dry coating film is cooled by an appropriate cooling method and light is irradiated, thereby controlling the polymerization temperature. If the polymerization of the polymerizable liquid crystal compound is performed at a lower temperature by adopting such a cooling method, even if a relatively low heat resistance is used as a base material, a liquid crystal cured film can be appropriately formed. In addition, by increasing the polymerization temperature within a range that does not generate defects (deformation caused by the heat of the substrate, etc.) caused by heat during light irradiation, the polymerization reaction can also be promoted. During photopolymerization, a patterned cured film can also be obtained by masking and developing.

As the light source of the above-mentioned active energy rays, for example, low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, halogen lamp, carbon arc lamp, tungsten filament lamp, gallium lamp, excimer laser, emission Light Emitting Diode (Light Emitting Diode) light source, chemical lamp, black light lamp, microwave excited mercury lamp, metal halide lamp, etc. for light with a wavelength range of 380 ~ 440 nm.

The intensity of ultraviolet radiation is usually 10 to 3,000 mW/cm ² . The intensity of ultraviolet irradiation is preferably the intensity in the wavelength region effective for the activation of the photopolymerization initiator. The light irradiation time is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and still more preferably 0.1 second to 1 minute. If irradiated with such ultraviolet radiation intensity once or multiple times, the cumulative light intensity is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , and more preferably 100 to 1,000 mJ/cm ² .

The thickness of the liquid crystal cured film can be appropriately selected according to the applied optical display, etc. It is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm.

The coating film of the polymerizable liquid crystal composition can also be formed on the alignment film. The alignment film has an alignment restricting force for aligning the liquid crystal of the polymerizable liquid crystal compound in a desired direction. For example, there are horizontal alignment films for the alignment film having the alignment restricting force for aligning the polymerizable liquid crystal compound in the horizontal direction, and the vertical alignment film for the alignment film having the alignment restricting force for the vertical direction. The alignment restriction force can be arbitrarily adjusted according to the type, surface state, and friction conditions of the alignment film. When the alignment film is formed of a photo-alignment polymer, it can be arbitrarily adjusted according to polarized light irradiation conditions.

As an alignment film, it is preferable to have solvent resistance which does not dissolve by coating etc. of a polymerizable liquid crystal composition, and to have heat resistance in the heat treatment for removing a solvent and aligning a polymerizable liquid crystal compound mentioned later. As the alignment film, for example, an alignment film containing an alignment polymer, a photo-alignment film, a groove alignment film with a concave-convex pattern and a plurality of grooves on the surface, a stretched film extending in the alignment direction, etc., are related to the accuracy of the alignment angle. From the viewpoint of quality and quality, a photo-alignment film is preferred.

As the alignment polymer, for example, polyamides and gelatins having an amide bond in the molecule, polyimines having an amide bond in the molecule, and polyamides and polyethylene as hydrolysates thereof can be mentioned. Alcohol, alkyl modified polyvinyl alcohol, polyacrylamide, polyazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylates. Among them, polyvinyl alcohol is preferred. The alignment polymer can be used alone or in combination of two or more kinds.

The alignment film containing the alignment polymer is usually obtained by the following method: a composition (hereinafter sometimes referred to as "alignment polymer composition") formed by dissolving the alignment polymer in a solvent is applied to the substrate, Remove the solvent; or apply the aligning polymer composition to the substrate, remove the solvent and rub (rubbing method). The solvent may be the same as the solvent exemplified above as the solvent that can be used in the polymerizable liquid crystal composition.

Regarding the concentration of the aligning polymer in the aligning polymer composition, as long as the aligning polymer material can be completely dissolved in the solvent, it is preferably 0.1 to 0.1 in terms of solid content relative to the solution. 20%, more preferably about 0.1 to 10%.

As the alignment polymer composition, a commercially available alignment film material can also be used as it is. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industry Co., Ltd.), Optomer (registered trademark, manufactured by JSR (Stock)), and the like.

As the method of applying the aligning polymer composition to the substrate, the same as those exemplified as the method of applying the polymerizable liquid crystal composition to the substrate can be exemplified.

As a method of removing the solvent contained in the aligning polymer composition, a natural drying method, a ventilation drying method, a heat drying method, a reduced pressure drying method, etc. may be mentioned.

In order to impart an alignment restriction force to the alignment film, a rubbing treatment (rubbing method) may be performed as necessary. As a method of imparting the alignment restriction force by the rubbing method, the following method can be exemplified: a rubbing roller wound with a rubbing cloth in rotation is brought into contact with a film of an alignment polymer formed on the surface of the substrate, and the film of the alignment polymer It is formed by coating the aligning polymer composition on the substrate and annealing. If masking is performed during the rubbing treatment, a plurality of regions (patterns) with different alignment directions may also be formed on the alignment film.

The photo-alignment film is usually obtained by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as "the composition for forming a photo-alignment film") on a substrate to remove After the solvent is irradiated with polarized light (preferably polarized UV). The optical alignment film is also advantageous in that the direction of the alignment restriction force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarization.

The photoreactive group refers to a group that produces liquid crystal alignment ability by light irradiation. Specifically, it can be exemplified to participate in the molecular alignment induced by light irradiation or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photolysis reaction, etc., which become the base of the photoreaction originating the alignment ability of the liquid crystal. Among them, the group participating in the dimerization reaction or the photocrosslinking reaction is preferable in terms of excellent alignment. The photoreactive group is preferably a group having an unsaturated bond, especially a double bond, and particularly preferably a group having a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), At least one group of nitrogen-nitrogen double bond (N=N bond) and carbon-oxygen double bond (C=O bond).

Examples of the photoreactive group having a C=C bond include vinyl, polyalkenyl, stilbene, styrylpyridyl, styrylpyridinium, chalcone and cinnamyl Wait. The photoreactive group having a C=N bond may, for example, be a group having a structure such as an aromatic Schiff base and an aromatic hydrazone. Examples of photoreactive groups having N=N bonds include: azophenyl, azonaphthyl, aromatic heterocyclic azo, bisazo, formazan, and oxyazobenzene structure The base and so on. The photoreactive group having a C=O bond may, for example, be a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group, and the like. These groups may also have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

Among them, the photoreactive group that participates in the photodimerization reaction is preferable. In terms of the relatively small amount of polarized light irradiation required for photoalignment, and it is easier to obtain a photoalignment film with excellent thermal stability and stability over time, it is more Preferred are cinnamon base and chalcone base. As a polymer having a photoreactive group, a cinnamyl group having a cinnamic acid structure at the end of the polymer side chain is particularly preferred.

By coating the composition for forming a photo-alignment film on a substrate, a photo-alignment inducing layer can be formed on the substrate. As the solvent contained in the composition, the same solvents as those exemplified as the solvents that can be used in the polymerizable liquid crystal composition can be exemplified, and it can be appropriately determined according to the solubility of the polymer or monomer having a photoreactive group. choose.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted according to the type of polymer or monomer and the thickness of the target photo-alignment film, preferably relative to the photo-alignment film The mass of the forming composition is at least 0.2% by mass, more preferably in the range of 0.3-10% by mass. The composition for forming the photo-alignment film may also contain polymer materials such as polyvinyl alcohol or polyimide, or a photosensitizer within the range that does not significantly impair the characteristics of the photo-alignment film.

As a method of applying the composition for forming a photo-alignment film to the substrate, the same method as the method of applying the aligning polymer composition to the substrate can be exemplified. As a method of removing the solvent from the coated composition for forming a photo-alignment film, for example, a natural drying method, an air drying method, a heat drying method, and a reduced-pressure drying method may be mentioned.

Regarding the irradiation of polarized light, either of the following two forms is possible, that is, the form of directly irradiating the polarized light UV from the photo-alignment film forming composition coated on the substrate by removing the solvent, and irradiating the polarized light from the substrate side to transmit the polarized light And the form of irradiation. Moreover, the polarized light is particularly preferably substantially parallel light. The wavelength of the polarized light irradiated may be in the wavelength region where the photoreactive group of the polymer or monomer having the photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) with a wavelength in the range of 250 to 400 nm is particularly preferred. As the light source used for the polarized light irradiation, for example, xenon lamp, high pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, KrF, ArF and other ultraviolet lasers, etc., more preferably high pressure mercury lamp, ultra high pressure mercury lamp and metal halide lamp . Among them, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferred because of the higher luminous intensity of ultraviolet light with a wavelength of 313 nm. Polarized UV can be irradiated by irradiating light from the above-mentioned light source through an appropriate polarizing element. As the polarizing element, a polarizer, a polarizing element such as Gülen-Thompson and Gülen-Taylor, and a wire grid type polarizing element can be used.

Furthermore, when rubbing or polarized light irradiation is performed, if shielding is performed, a plurality of regions (patterns) with different liquid crystal alignment directions can also be formed.

The groove alignment film has a concave-convex pattern or a plurality of grooves (grooves) on the surface of the film. When the polymerizable liquid crystal compound is coated on a film with a plurality of linear grooves arranged at equal intervals, the liquid crystal molecules are aligned in a direction along the grooves.

As a method of obtaining the groove alignment film, the following method can be exemplified: after exposing the surface of the photosensitive polyimide film through an exposure mask having a pattern shape, the surface of the photosensitive polyimide film is developed and rinsed to form a concave-convex pattern. Method; forming a UV-curing resin layer before hardening on a plate-shaped master with grooves on the surface, and then moving the formed resin layer to the base material and then hardening; and pressing the roll master with multiple grooves A method of forming unevenness against the UV-curing resin film formed before the hardening of the base material, and then curing.

The thickness of the alignment film (alignment film or photo-alignment film containing an alignment polymer) is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 1000 nm, more preferably 10 to 500 nm or less, and more preferably 10-300 nm, particularly preferably in the range of 50-250 nm.

＜Elliptical polarizing plate＞ The present invention includes an elliptical polarizing plate including the retardation film of the present invention. The elliptically polarizing plate of the present invention includes the retardation film and the polarizing film of the present invention. The polarizing film is a film having a polarization function, and examples thereof include a stretched film adsorbed with a pigment having absorption anisotropy, and a film coated with a pigment having absorption anisotropy as a polarizing element. As a dye having absorption anisotropy, for example, a dichroic dye may be mentioned.

The film containing the stretched film adsorbed with the pigment with absorption anisotropy as the polarizing element is usually produced by sandwiching the polarizing element with a transparent protective film through an adhesive on at least one side of the polarizing element. The polarizing element is produced through the following steps: The step of uniaxially stretching the polyvinyl alcohol-based resin film, the step of adsorbing the dichroic pigment by dyeing the polyvinyl alcohol-based resin film with a dichroic pigment, the step of adsorbing the dichroic pigment with an aqueous solution of boric acid The step of treating the polyvinyl alcohol resin film, and the step of washing with water after treatment with an aqueous solution of boric acid.

The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and other monomers copolymerizable therewith can be used. Examples of other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

The degree of saponification of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may also be modified, for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, preferably in the range of 1,500 to 5,000.

A film made of such a polyvinyl alcohol-based resin is used as a blank film of a polarizing film. The method of forming a polyvinyl alcohol-based resin into a film is not particularly limited, and the film can be formed by a known method. The film thickness of the polyvinyl alcohol-based green film can be about 10 to 150 μm, for example.

The uniaxial stretching of the polyvinyl alcohol-based resin film may be performed before, at the same time, or after dyeing with the dichroic dye. When uniaxial stretching is performed after dyeing, the uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment. Moreover, it is also possible to perform uniaxial extension in these plural stages. In uniaxial extension, uniaxial extension can be performed between rollers with different peripheral speeds, or a heated roller can be used for uniaxial extension. In addition, the uniaxial stretching may be dry stretching in the atmosphere, or wet stretching in a state where the polyvinyl alcohol-based resin film is swollen with a solvent. The stretching ratio is usually about 3 to 8 times.

The dyeing of the polyvinyl alcohol-based resin film with a dichroic dye is performed by, for example, immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye.

As the dichroic dye, specifically, iodine or a dichroic organic dye is used. Examples of dichroic organic dyes include C.I. DIRECT RED 39 and other dichroic direct dyes containing bisazo compounds, and dichroic direct dyes containing compounds such as trisazo and tetrasazo. The polyvinyl alcohol resin film is preferably subjected to an immersion treatment in water before the dyeing treatment.

When iodine is used as a dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide for dyeing is usually adopted. The content of iodine in the aqueous solution is usually about 0.01 to 1 part by mass relative to 100 parts by mass of water. In addition, the content of potassium iodide is usually about 0.5 to 20 parts by mass relative to 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is usually around 20-40°C. In addition, the immersion time (dyeing time) in the aqueous solution is usually about 20 to 1,800 seconds.

On the other hand, when a dichroic organic dye is used as a dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye for dyeing is usually adopted. The content of the dichroic organic dye in the aqueous solution is usually about 1×10 ^-4 to 10 parts by mass relative to 100 parts by mass of water, preferably 1×10 ^-3 to 1 part by mass, and more preferably 1× 10 ^-3 ～1×10 ^-2 parts by mass. The aqueous solution may also contain inorganic salts such as sodium sulfate as a dyeing auxiliary. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80°C. In addition, the immersion time (dyeing time) in the aqueous solution is usually about 10 to 1,800 seconds.

The boric acid treatment after dyeing with a dichroic dye can usually be performed by immersing the dyed polyvinyl alcohol resin film in an aqueous solution of boric acid. The content of boric acid in the boric acid aqueous solution is usually about 2 to 15 parts by mass relative to 100 parts by mass of water, and preferably 5 to 12 parts by mass. When iodine is used as a dichroic pigment, the boric acid aqueous solution preferably contains potassium iodide. The content of potassium iodide is usually about 0.1-15 parts by mass, preferably 5-12 parts by mass relative to 100 parts by mass of water. share. The immersion time in the boric acid aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid treatment is usually 50°C or higher, preferably 50 to 85°C, and more preferably 60 to 80°C.

The polyvinyl alcohol resin film after boric acid treatment is usually washed with water. The water washing treatment can be performed, for example, by a method of immersing a polyvinyl alcohol-based resin film treated with boric acid in water. The temperature of the water in the washing treatment is usually about 5-40°C. In addition, the immersion time is usually about 1 to 120 seconds.

After washing with water, a drying process was performed to obtain a polarizing element. The drying treatment can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying treatment is usually about 30 to 100°C, preferably 50 to 80°C. The drying treatment time is usually about 60 to 600 seconds, preferably 120 to 600 seconds. Through the drying process, the moisture content of the polarizing element is reduced to a practical level. The water content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. If the moisture content is in the above range, it is easy to obtain a polarizing element having appropriate flexibility and excellent thermal stability.

The thickness of the polarizing element obtained by uniaxially stretching the polyvinyl alcohol resin film, dyeing with dichroic pigment, boric acid treatment, washing with water, and drying in this way is preferably 5-40 μm.

As a film coated with a pigment having absorption anisotropy, a film obtained by coating a composition containing a dichroic pigment with liquid crystallinity, or a composition containing a dichroic pigment and a polymerizable liquid crystal compound can be mentioned. Wait. The film preferably has a protective film on one or both sides. The protective film may be the same as the resin film exemplified as the base material that can be used in the production of the liquid crystal cured film.

The film coated with a pigment having absorption anisotropy is preferably thin, but from the viewpoint of strength and processability, the thickness of the film is usually 20 μm or less, preferably 5 μm or less, more preferably 0.5 to 3 μm.

As the film coated with a dye having absorption anisotropy, specifically, a film described in JP 2013-33249 A and the like can be mentioned.

On at least one side of the polarizing element obtained in this way, a transparent protective film is laminated via an adhesive, thereby obtaining a polarizing film. As the transparent protective film, the same transparent film as the resin film exemplified as the base material that can be used in the production of the liquid crystal cured film constituting the retardation film is preferably used.

The elliptically polarizing plate of the present invention includes the retardation film and the polarizing film of the present invention. For example, the elliptically polarizing plate of the present invention can be obtained by laminating the retardation film and the polarizing film of the present invention through an adhesive layer or an adhesive layer. .

In one aspect of the present invention, when the retardation film and the polarizing film of the present invention including the liquid crystal cured film are laminated, it is preferable to make the retardation axis (optical axis) of the liquid crystal cured film constituting the retardation film and The angle formed by the absorption axis of the polarizing film becomes 45±5°.

The elliptical polarizing plate of the present invention may have the structure of the conventional elliptical polarizing plate, or the polarizing film and the retardation film. Examples of such a structure include: bonding an ellipsoidal polarizing plate to an adhesive layer (sheet) that constitutes a display element of an optical display, and protecting the surface of the polarizing film and retardation film from damage and contamination. And the use of protective film and so on.

The elliptically polarizing plate of the present invention can be used in various display devices, especially optical displays. A display device refers to a device with a display element, which includes a light-emitting element or a light-emitting device as a light-emitting source. The display device may, for example, be a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a flexible image display device, a touch panel display device, an electron emission display device (E.g. field emission display device (FED), surface field emission display device (SED)), electronic paper (display device using electronic ink or electrophoresis element), plasma display device, projection type display device (e.g. grating light valve imaging System (GLV) display device, display device with digital micro-mirror device (DMD), piezoelectric ceramic display, etc. The liquid crystal display device includes any of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection liquid crystal display device. The display devices can be display devices that display two-dimensional images, or stereoscopic display devices that display three-dimensional images. In particular, the elliptically polarizing plate of the present invention is suitable for use in organic electroluminescence (EL) display devices and inorganic electroluminescence (EL) display devices. These display devices (optical displays) can exhibit good image display characteristics by having the elliptically polarizing plate of the present invention with excellent optical characteristics.

The flexible image display device with the elliptical polarizer of the present invention preferably further has a window and a touch panel touch sensor. The flexible image display device includes, for example, a laminate for a flexible image display device and an organic EL display panel. The laminate for a flexible image display device is arranged on the visible side of the organic EL display panel and can be bent. The way of folding is constituted. As a laminate for a flexible image display device, in addition to the above-mentioned elliptically polarizing plate of the present invention, a window, a touch panel touch sensor, and the like may be included. The order of these layers is arbitrary, but it is better to follow the order of window, elliptical polarizer, touch sensor or window, touch sensor, elliptical polarizer from the viewing side Buildup.

When there is an elliptical polarizer on the visual recognition side of the touch panel touch sensor, it is difficult to visualize the pattern of the touch panel touch sensor, and the visibility of the displayed image becomes better, which is better. Each member can be laminated using adhesives, adhesives, etc. In addition, the laminated body for a flexible image display device may have a light-shielding pattern formed on at least one surface of any one of the window, the elliptical polarizer, and the touch sensor of the touch panel.

The window is arranged on the visual recognition side of the flexible image display device, and plays a role of protecting other components from external impact or environmental changes such as temperature and humidity. Previously, glass was used as such a protective layer, but the window of a flexible image display device is not as rigid and hard as glass, but has the characteristics of flexibility. The window includes a flexible transparent substrate, and may also include a hard coat layer on at least one side.

The above-mentioned transparent substrate preferably has a visible light transmittance of 70% or more, and more preferably has a visible light transmittance of 80% or more. As the above-mentioned transparent substrate, any polymer film having transparency can be used. Among them, a polyamide film, a polyimide film or a polyimide film, a polyester film, an olefin film, an acrylic film, and a cellulose film, which are excellent in transparency and heat resistance, are preferred. It is also preferable to disperse inorganic particles such as silicon dioxide, organic microparticles, colloidal particles, etc. in the polymer film.

The thickness of the above-mentioned transparent substrate is preferably 5 to 200 μm, more preferably 20 to 100 μm.

It is also possible to provide a hard coat layer on at least one side of the transparent substrate constituting the above-mentioned window. The thickness of the hard coat layer is not particularly limited, and may be, for example, 2 to 100 μm. If the thickness of the hard coat layer is within the above range, it is easy to ensure sufficient impact resistance, scratch resistance, and bending resistance.

The above-mentioned hard coat layer can be formed by curing a composition for forming a hard coat layer containing a reactive material that forms a cross-linked structure by irradiating active energy rays or thermal energy, but is preferably obtained by curing by active energy rays . The definition of active energy ray is the energy ray that can decompose the compound that produces the active species to produce the active species. Examples of the active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, and electron beams, and ultraviolet rays are particularly preferred. The composition for forming a hard coat layer generally contains at least one compound of a radical polymerizable compound and a cation polymerizable compound, and a polymerization initiator. The radically polymerizable compound, the cationically polymerizable compound, and the polymerization initiator are not particularly limited, and those previously known may be mentioned. The said hard coat composition may further contain 1 or more types chosen from the group which consists of a solvent and an additive. As long as the above-mentioned solvent can dissolve or disperse the above-mentioned polymerizable compound and polymerization initiator, those known as solvents for the composition for forming a hard coat layer in the field of optical films can be used without limitation. Examples of the above-mentioned additives include inorganic particles, leveling agents, stabilizers, surfactants, antistatic agents, lubricants, antifouling agents, and the like.

The touch panel touch sensor is used as the output mechanism. As a touch panel touch sensor, various styles such as a resistive film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, and an electrostatic capacitance method are disclosed, and any method is acceptable. Among them, the electrostatic capacitance method is preferred. The capacitive touch panel touch sensor is divided into an active area and an inactive area located outside the active area. The active area is the area corresponding to the area of the display screen (display part) in the display panel, and is the area that perceives the user's contact, and the inactive area is the area corresponding to the area (non-display part) of the display device that does not display the picture . The touch panel touch sensor may include: a substrate, which has the characteristic of flexibility; a sensing pattern, which is formed on the active area of the substrate; and each sensing line, which is formed on the inactive area of the substrate, is used It is connected to an external driving circuit via the sensing pattern and the pad part.

There are no special restrictions on the substrate, the sensing pattern, and each sensing line with flexible characteristics, and materials applicable in the technical field can be selected respectively.

As the substrate having the characteristic of flexibility, for example, a substrate containing the same material as the transparent substrate of the above-mentioned window can be used. Regarding the substrate of the touch panel touch sensor, in terms of suppressing the cracking of the touch panel touch sensor, the toughness is preferably 2,000 MPa% or more, and more preferably the toughness is 2,000 MPa%~ 30,000 MPa%. Here, the definition of toughness is the area under the curve up to the breaking point in the stress-strain curve (MPa)-strain (%) obtained by the tensile experiment of the polymer material.

The various layers (windows, ellipsoidal polarizers, touch panel touch sensors) and the film members (polarizing films, retardation films, etc.) constituting each layer that form the above-mentioned laminated body for flexible image display devices can be adhered by Agent and formed. As the adhesive, water-based adhesives, organic solvent-based adhesives, solvent-free adhesives, solid adhesives, solvent sublimation type adhesives, moisture curing type adhesives, heat curing type adhesives, anaerobic curing type can be used , Active energy ray hardening type adhesive, hardening agent mixed type adhesive, hot melt type adhesive, pressure sensitive type adhesive (adhesive), rewetting type adhesive, etc. for general users. Among them, it is preferable to use an aqueous solvent sublimation type adhesive, an active energy ray hardening type adhesive, and an adhesive. The thickness of the adhesive layer can be appropriately adjusted according to the required adhesive force, etc., but is usually 0.01 μm to 500 μm, preferably 0.1 μm to 300 μm. When there are a plurality of adhesive layers in the above-mentioned laminate for flexible image display devices, the types and thicknesses of the adhesives constituting each adhesive layer may be the same or different. [Example]

Hereinafter, the present invention will be described in more detail with examples. Furthermore, unless otherwise specified, the "%" and "parts" in the examples refer to mass% and mass parts, respectively.

1. Preparation of polymerizable liquid crystal compound and liquid crystal mixture Production example 1: Production of polymerizable liquid crystal compound represented by formula (A-1) According to the following procedure, the polymerizable liquid crystal compound represented by formula (A-1) ( Hereinafter, it is referred to as "polymerizable liquid crystal compound (A-1)").

A 100 mL four-necked flask equipped with a Dai’s condenser and a thermometer was set in a nitrogen atmosphere, and 11.02 g of compound (E-1) synthesized by referring to the patent document (Japanese Patent Laid-Open No. 2010-31223) was added, and the reference patent document ( Japanese Patent Publication 2011-207765) synthesized compound (D-1) 4.00 g, DMAP (manufactured by Wako Pure Chemical Industries Co., Ltd.) 0.02 g, BHT (manufactured by Wako Pure Chemical Industries Co., Ltd.) 0.20 g, and chloroform After 58 g (manufactured by Kanto Chemical Co., Ltd.) and mixed, 4.05 g of IPC (manufactured by Wako Pure Chemical Industries Co., Ltd.) was further added using a dropping funnel, and the reaction was kept at 0°C overnight. After the reaction, the insoluble components were removed by filtration. The obtained chloroform solution was added dropwise to 3 times the weight of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.) with respect to the weight of chloroform contained in the solution to precipitate a solid. Then, the precipitated solid was taken out by filtration, washed three times with 20 g of acetonitrile, and dried under reduced pressure at 30°C to obtain 11.43 g of a polymerizable liquid crystal compound (A-1). The yield of the polymerizable liquid crystal compound (A-1) was 80% based on the compound (D-1).

參考專利文獻(日本專利特開2010-31223)，將反式-1,4-環己烷二羧酸變更為順式-1,4-環己烷二羧酸，合成化合物(E-2)所表示之混合物27.02 g。使用將所獲得之化合物(E-2)與化合物(E-1)以10/90混合所得者，將製造例1之化合物(E-1)變更為化合物(E-2)與化合物(E-1)之上述混合物，進行合成，藉此，獲得液晶混合物(A')10.57 g。利用HPLC(high performance liquid chromatography，高效液相層析)測定對所獲得之液晶混合物(A')進行分析，結果，該液晶混合物包含上述化合物(A-1)、化合物(A-2)及化合物(A-3)，上述化合物(A-2)及化合物(A-3)之合計峰面積相對於化合物(A-1)、化合物(A-2)及化合物(A-3)之總峰面積100%為3.00%。Production Example 2: Production of Liquid Crystal Mixture (A') According to the following process, a liquid crystal mixture containing polymerizable liquid crystal compounds represented by the following formulas (A-1) to (A-3) (hereinafter also referred to as "liquid crystal mixture ( A')").

With reference to the patent document (Japanese Patent Laid-Open No. 2010-31223), trans-1,4-cyclohexanedicarboxylic acid was changed to cis-1,4-cyclohexanedicarboxylic acid, and compound (E-2) was synthesized The indicated mixture is 27.02 g. The compound (E-1) of Production Example 1 was changed to compound (E-2) and compound (E- 1) The above-mentioned mixture was synthesized, thereby obtaining 10.57 g of a liquid crystal mixture (A'). The liquid crystal mixture (A') obtained was analyzed by HPLC (high performance liquid chromatography). As a result, the liquid crystal mixture contained the above-mentioned compound (A-1), compound (A-2) and compound (A-3), the total peak area of the above compound (A-2) and compound (A-3) relative to the total peak area of compound (A-1), compound (A-2) and compound (A-3) 100% is 3.00%.

[HLPC determination] The HPLC measurement can be performed under any conditions as long as the peak derived from the polymerizable liquid crystal compound can be separated. The HPLC measurement conditions used in the analysis in the Examples and Comparative Examples of the present invention are shown below. (Measurement conditions) Measuring device: HPLC LC-10AT (manufactured by Shimadzu Corporation) Column: L-Column ODS (inner diameter 3.0 mm, length 150 mm, particle size 3 μm) Temperature: 40℃ Mobile phase A: 0.1%(v/v)-TFA/water Mobile phase B: 0.1%(v/v)-TFA/acetonitrile Gradient: 0 min 70%-B 30 min 100%-B 60 min 100%-B 60.01 min 70%-B 75 min 70%-B Flow rate: 0.5 mL/min Injection volume: 5 μL Detection wavelength: 254 nm

Production Example 3: Production of the polymerizable liquid crystal compound represented by the formula (B-1) The polymerizable liquid crystal compound represented by the following formula (B-1) (hereinafter referred to as "polymerizable liquid crystal compound (B- 1)").

Except for changing the compound (D-2) to 4.22 g, the reaction was carried out in the same manner as the method described in Production Example 1 to obtain 11.75 g of a polymerizable liquid crystal compound (B-1). The yield of the polymerizable liquid crystal compound (B-1) was 81% based on the compound (D-2).

Production Example 4: Production of Liquid Crystal Mixture (B') According to the following process, a liquid crystal mixture containing polymerizable liquid crystal compounds represented by the following formulas (B-1) to (B-3) (hereinafter also referred to as "liquid crystal mixture ( B')”).

Except for changing the compound (D-2) to 4.22 g, the reaction was carried out in the same manner as the method described in Production Example 2 to obtain 10.88 g of a liquid crystal mixture (B'). The obtained liquid crystal mixture (B') was analyzed under the above-mentioned HPLC measurement conditions. As a result, the liquid crystal mixture contained the above-mentioned compound (B-1), compound (B-2) and compound (B-3), and the above-mentioned compound (B- 2) The total peak area of compound (B-3) is 5.23% with respect to 100% of the total peak area of compound (B-1), compound (B-2), and compound (B-3).

Production Example 5: Production of Liquid Crystal Mixture (C') Except that the mixing ratio of compound (E-2) and compound (E-1) used in Production Example 4 was changed to 20/80, all the reactions were carried out in the same manner as the method described in Production Example 4 to obtain a liquid crystal mixture (C') 10.44 g. The obtained liquid crystal mixture (C') was analyzed under the above-mentioned HPLC measurement conditions. As a result, the liquid crystal mixture contained the above-mentioned compound (B-1), compound (B-2) and compound (B-3), and the above-mentioned compound (B- 2) The total peak area of compound (B-3) is 12.3% with respect to 100% of the total peak area of compound (B-1), compound (B-2), and compound (B-3). Furthermore, in the above-mentioned production examples 1 to 5, compound (A-1) and compound (B-1) correspond to the polymerizable liquid crystal compound (1-1), compound (A-2) and compound ( B-2) respectively correspond to the polymerizable liquid crystal compound (1-2a) of the present invention, and the compound (A-3) and the compound (B-3) respectively correspond to the polymerizable liquid crystal compound (1-2b) of the present invention.

2. Polymerizable liquid crystal compounds/mixtures of Examples and Comparative Examples (1) Example 1: Preparation of liquid crystal mixture (1) Under the above HPLC measurement conditions, the peak area of compound (A-2) and compound (A-3) is relative to the total peak area of compound (A-1), compound (A-2) and compound (A-3) In such a way that 100% becomes 0.1%, the liquid crystal mixture (A') obtained in the above-mentioned Production Example 2 and the polymerizable liquid crystal compound (A-1) obtained in the above-mentioned Production Example 1 were mixed to obtain a liquid crystal mixture (1).

(2) Example 2: The liquid crystal mixture (A') obtained in the above-mentioned Production Example 2 was used as the liquid crystal mixture (2).

(3) Example 3: Preparation of liquid crystal mixture (4) Under the above HPLC measurement conditions, the peak area of compound (B-2) and compound (B-3) is relative to the total peak area of compound (B-1), compound (B-2) and compound (B-3) In such a way that 100% becomes 0.4%, the liquid crystal mixture (B') obtained in Production Example 4 and the polymerizable liquid crystal compound (B-1) obtained in Production Example 3 are mixed to obtain a liquid crystal mixture (3).

(4) Example 4: The liquid crystal mixture (B') obtained in the above-mentioned Production Example 4 was used as the liquid crystal mixture (4).

(5) Comparative Example 1: The polymerizable liquid crystal compound (A-1) obtained in Production Example 1 was referred to as the liquid crystal compound (1).

(6) Comparative Example 2: The polymerizable liquid crystal compound (B-1) obtained in Production Example 3 was referred to as the liquid crystal compound (2).

(7) Comparative Example 3: The liquid crystal mixture (C') obtained in Production Example 5 was referred to as the liquid crystal mixture (5).

3. Solubility evaluation Put N-methylpyrrolidone (NMP) and a stirrer into the bottle, stir with a magnetic stirrer (HS-30DN, AS ONE), and put them into the above-mentioned Examples 1 to 4 and Comparative Example 1 respectively The liquid crystal mixtures (1) to (5), liquid crystal compounds (1) and (2) prepared in ~3 were not dissolved until visually confirmed. When it is confirmed that it is not dissolved, calculate each liquid crystal mixture and polymerizable liquid crystal compound by weight percentage based on (weight of each liquid crystal mixture and polymerizable liquid crystal compound)/(weight of each liquid crystal mixture and polymerizable liquid crystal compound + weight of NMP) Solubility in NMP. The results are shown in Table 2.

溶劑(95份)：環戊酮4. Evaluation of alignment defects (1) Production of optical film (retardation film) The optical film (retardation film) was produced according to the following procedure. (i) Preparation of the composition for forming a photo-alignment film The following components were mixed, and the obtained mixture was stirred at 80° C. for 1 hour, thereby obtaining a composition for forming a photo-alignment film. The photo-alignment material represented by the following formula (5 parts) (number average molecular weight is about 28,000):

Solvent (95 parts): cyclopentanone

(ii) The preparation of the polymerizable liquid crystal composition uses a corona treatment device (AGF-B10, manufactured by Kasuga Electric Co., Ltd.) to treat the cycloolefin polymer film (COP) at an output of 0.3 kW and a processing speed of 3 m/min. ) (ZF-14, manufactured by Zeon Co., Ltd., Japan) for one treatment. The above-mentioned photo-alignment film-forming composition was coated on the corona-treated surface by a bar coater, dried at 80°C for 1 minute, and polarized UV irradiation equipment (SPOT CURE SP-7; Ushio Electric Co., Ltd. (Manufactured by the company) Polarized UV exposure is carried out with a cumulative light quantity of ^{100 mJ/cm 2.} When the film thickness of the obtained photo-alignment film was measured by a laser microscope (LEXT, manufactured by Olympus Co., Ltd.), it was 100 nm. Then, the liquid crystal mixture (1) prepared in Example 1 above was put into the bottle tube, and the photopolymerization initiator, leveling agent, polymerization inhibitor and solvent were added according to the composition described in Table 1, and the rotating material rack was used for 80 It stirred for 30 minutes at degreeC, and obtained the polymerizable liquid crystal composition. Furthermore, the blending amount of the solvent is set so that the mass% of the liquid crystal mixture is 13% with respect to the total amount of the polymerizable liquid crystal composition (solution).

[Table 1] Liquid crystal mixture/liquid crystal compound Types of polymerizable liquid crystal compounds (1-1) Addition amount (parts by mass) relative to 100 parts by mass of liquid crystal mixture/liquid crystal compound Photopolymerization initiator Leveling agent Polymerization inhibitor Example 1 Liquid crystal mixture (1) (A-1) 6 0.1 0.2 Example 2 Liquid crystal mixture (2) (A-1) 6 0.1 0.2 Example 3 Liquid crystal mixture (3) (B-1) 6 0.1 0.2 Example 4 Liquid crystal mixture (4) (B-1) 6 0.1 0.2 Comparative example 1 Liquid crystal compound (1) (A-1) 6 0.1 0.2 Comparative example 2 Liquid crystal compound (2) (B-1) 6 0.1 0.2 Comparative example 3 Liquid crystal mixture (5) (B-1) 6 0.1 0.2

Polymerization initiator: 2-benzyl-2-dimethylamino-1-(4-𠰌linephenyl)butan-1-one (Irgacure369; manufactured by BASF Japan) Leveling agent: polyacrylate compound (BYK-361N; manufactured by BYK-Chemie Japan) Polymerization inhibitor: BHT (manufactured by Wako Pure Chemical Industries, Ltd.) Solvent: N-methylpyrrolidone (NMP; manufactured by Kanto Chemical Co., Ltd.)

(iii) Production of optical film Use a bar coater to coat the obtained polymerizable liquid crystal composition on the alignment film, and after drying at 120°C for 1 minute, use a high-pressure mercury lamp (uniQureVB-15201BY-A, Oxtail Motor Co., Ltd.) irradiate (under nitrogen atmosphere, wavelength: 365 nm, cumulative light intensity at wavelength of 365 nm: 1000 mJ/cm ² ) ultraviolet light to form an optical film. In addition, the liquid crystal mixtures (2) to (5), liquid crystal compounds (1) and (2) prepared in Examples 2 to 5 and Comparative Examples 1 to 3 were used instead of the above liquid crystal mixture (1), as described in Table 1. A photopolymerization initiator, a leveling agent, a polymerization inhibitor, and a solvent are added to the composition, except for this, a polymerizable liquid crystal composition and an optical film are produced in the same manner as described above.

(2) Evaluation of alignment defects Cut out the obtained optical film with a 10 cm square, use a polarizing microscope (LEXT, manufactured by Olympus), visually confirm the number of alignment defects on the screen, and evaluate it according to the following evaluation criteria. The results are shown in Table 1. (Assessment criteria for alignment defects) 1: Alignment defects on the entire surface (>100) 2: 11～100 3: 1～10 4: No defects

[Table 2] Liquid crystal mixture/liquid crystal compound Types of polymerizable liquid crystal compounds (1-1) Area percentage value of polymerizable liquid crystal compound (1-2) (%) Alignment defect assessment Solubility in NMP Example 1 Liquid crystal mixture (1) (A-1) 0.1 4 4.2 Example 2 Liquid crystal mixture (2) (A-1) 3 4 6.6 Example 3 Liquid crystal mixture (3) (B-1) 0.4 4 6.1 Example 4 Liquid crystal mixture (4) (B-1) 5.23 4 8.4 Comparative example 1 Liquid crystal compound (1) (A-1) 0 4 3.0 Comparative example 2 Liquid crystal compound (2) (B-1) 0 4 5.8 Comparative example 3 Liquid crystal mixture (3) (B-1) 12.3 2 8.8

As shown in Table 1, it can be confirmed that the polymerizable liquid crystal composition (Examples 1 to 4) according to the present invention contains a specific amount of the polymerizable liquid crystal compound (1-2) relative to the polymerizable liquid crystal compound (1-1). ), can suppress the alignment defect, and improve the solubility of the polymerizable liquid crystal compound (1-1) in the solvent.

Claims (12)

A polymerizable liquid crystal composition comprising at least two polymerizable liquid crystal compounds represented by formula (1) with the same molecular weight but different molecular structures,

[In formula (1), Ar represents a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group which may have a substituent, and D ¹ , D ² , E ¹ , E ² , B ¹ and B ² each independently represent- CR ¹¹ R ¹² -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O -, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S -CH ₂ -, -CH ₂ -S- or a single bond, R ¹¹ and R ¹² each independently represent a hydrogen atom, a fluorine atom or an alkyl group with 1 to 4 carbon atoms, and G ¹ and G ² each represent 1,4- Cyclohexanediyl, A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group with 3 to 16 carbons or a divalent aromatic hydrocarbon group with 6 to 20 carbons, in the alicyclic hydrocarbon group and the aromatic hydrocarbon group The hydrogen atoms contained can be substituted by halogen atoms, -R ¹³ , -OR ¹³ , cyano or nitro groups, R ¹³ represents an alkyl group with 1 to 4 carbon atoms, and the hydrogen atoms contained in the alkyl group can be substituted by fluorine atoms, F ¹ and F ² each independently represent an alkanediyl group having 1 to 12 carbons. The hydrogen atom contained in the alkanediyl group may be ^{substituted by -OR 14} or a halogen atom. R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms. The hydrogen atom contained in the alkyl group may be substituted with a fluorine atom, and the -CH ₂ -contained in the alkanediyl group may be substituted with -O- or -CO-, and P ¹ and P ² each independently represent a hydrogen atom or polymerization (Wherein, ^{at least one of P 1} and P ² is a polymerizable group)], as the polymerizable liquid crystal compound, include: G ¹ and G ² in formula (1) are 1,4-trans -Cyclohexanediyl polymerizable liquid crystal compound (1-1), and only when ^{at least one of G 1} and G ² in formula (1) is 1,4-cis-cyclohexadiyl molecule The polymerizable liquid crystal compound (1-2) having a structure different from the above-mentioned polymerizable liquid crystal compound (1-1); the peak area of the polymerizable liquid crystal compound (1-2) measured by liquid chromatography is relative to that of the polymerizable liquid crystal The ratio of the total peak area of the compound (1-1) to the polymerizable liquid crystal compound (1-2) is 0.01% or more and 10% or less. The polymerizable liquid crystal composition of claim 1, wherein the polymerizable liquid crystal compound (1-2) includes one of G ¹ and G ² in the formula (1), which is 1,4-cis-cyclohexanediyl The polymerizable liquid crystal compound (1-2a) and the G ¹ and G ² in the formula (1) are both 1,4-cis-cyclohexanediyl polymerizable liquid crystal compound (1-2b). The polymerizable liquid crystal composition of claim 1 or 2, wherein Ar in formula (1) is a base represented by any one of formulas (2-1) to (2-5),

[In the formula, * represents the bonding part ^{with D 1} or D ^{2 ; Q 1} represents -S-, -O- or -NR ¹⁵ -, R ¹⁵ represents a hydrogen atom or a carbon number of 1 to 6 which may have a substituent Alkyl group, Q ² represents a hydrogen atom or an optionally substituted alkyl group with 1 to 6 carbons; W ¹ and W ² each independently represent -O-, -S-, -CO-, -NR ¹⁵ -, R ¹⁵ represents a hydrogen atom or an ^{alkyl group having 1 to 6 carbons which may have a substituent; Y 1} represents an alkyl group having 1 to 6 carbons, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and the alkyl group, The hydrogen atom contained in the aromatic hydrocarbon group or the aromatic heterocyclic group may be substituted by a halogen atom, and the -CH ₂ -contained in the alkyl group may be substituted with -O-, -CO-, -O-CO- or -CO-O-, Y ² represents a CN group or a C1-C12 alkyl group which may have a substituent, the hydrogen atom contained in the alkyl group may be substituted by a halogen atom, and the alkyl group contains -CH _2- Can be substituted with -O-, -CO-, -O-CO- or -CO-O-; Z ¹ , Z ² and Z ³ each independently represent a hydrogen atom or an aliphatic hydrocarbon group or alkane with 1 to 20 carbon atoms Oxy group, alicyclic hydrocarbon group with 3 to 20 carbons, monovalent aromatic hydrocarbon group with 6 to 20 carbons, halogen atom, cyano, nitro, -NR ¹⁵ R ¹⁶ or -SR ¹⁵ , Z ¹ and Z ² They may also be bonded to each other to form an aromatic ring or an aromatic heterocyclic ring. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms; Ax represents an aromatic hydrocarbon ring and an aromatic heterocyclic ring At least one aromatic ring in the group consisting of an organic group with 2 to 30 carbons, Ay represents a hydrogen atom, an alkyl group with 1 to 6 carbons which may have a substituent, or has an aromatic hydrocarbon ring and At least one aromatic ring in the group consisting of aromatic heterocycles has an organic group of 2 to 30 carbon atoms, Ax and Ay may also be bonded to form a ring; Y ³ and Y ⁴ are each independently selected from the following The base in formula (Y-1):

[In formula (Y-1), M ¹ represents a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, and the alkyl group may be substituted with one or more substituents X ³ , and the substituent X ³ represents a fluorine atom, a chlorine atom, Bromine atom, iodine atom, pentafluorothio, nitro, cyano, isocyano, amino, hydroxyl, mercapto, methylamino, dimethylamino, diethylamino, diisopropylamine Group, trimethylsilyl group, dimethylsilyl group, isothiocyano group, or one -CH ₂ -or two or more non-adjacent -CH ₂ -can be independently substituted with -O-,- S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH= CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF- or -C≡C- carbon number 1 -20 linear or branched alkyl groups, any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or may be a group represented by ^{-B 11} -F ¹¹ -P ^{11 , B 11} , F ¹¹ and P ^{11 are defined in the same way as B 1} , F ¹ and P ¹ in the above formula (1), respectively, and can be the same as or different ^{from the above B 1} , F ¹ and P ^{1 respectively ; U 1} represents aromatic An organic group with 2 to 30 carbon atoms in the aromatic hydrocarbon group, any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and the aromatic hydrocarbon group may be substituted by one or more of the above-mentioned substituents X ³ ; T ¹ represents -O- , -S-, -COO-, -OCO-, -OCO-O-, -NU ² -, -N=CU ² -, -CO-NU ² -, -OCO-NU ² -or -O-NU ² -, U ² represents a hydrogen atom, an alkyl group with 1 to 20 carbons, a cycloalkyl group with 3 to 12 carbons, a cycloalkenyl group with 3 to 12 carbons, and an aromatic hydrocarbon group (any carbon of the aromatic hydrocarbon group) Atoms may be substituted with heteroatoms) organic groups with 2 to 30 carbons, or (E ¹¹ -A ¹¹ ) _q -B ¹² -F ¹² -P ¹² , the alkyl, cycloalkyl, cycloalkenyl and aromatic groups The group hydrocarbyl groups are respectively unsubstituted or can be substituted by more than one substituent X ³ , the alkyl group can also be substituted by the cycloalkyl or cycloalkenyl group, and one -CH ₂ -in the alkyl group may not be adjacent Two or more of -CH ₂ -can be independently replaced by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO ₂ -, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH =CH-, -CH=CH-, -CF=CF- or -C≡C-, one of the cycloalkyl or cycloalkenyl groups -CH ₂ -or two or more non-adjacent ones -CH _2- Can be independently Replaced with -O-, -CO-, -COO-, -OCO- or -O-CO-O-, E ¹¹ , A ¹¹ , B ¹² , F ¹² and P ¹² are respectively the same as E ^{1 in formula (1)} , A ¹ , B ¹ , F ¹ and P ¹ are defined in the same way, and can be the ^{same as or different from the above E 1} , A ¹ , B ¹ , F ¹ and P ^{1 respectively} . q represents an integer from 0 to 4, when there is In the case of a plurality of E ¹¹ and/or A ¹¹ , they may be the same or different, and U ¹ and U ² may also be bonded to form a ring]]. The polymerizable liquid crystal composition according to any one of claims 1 to 3, wherein A ¹ and A ² in formula (1) are independently 1,4-cyclohexanediyl or 1,4-phenylene diyl base. The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein P ¹ and P ² in formula (1) are acryloyl groups, respectively. The polymerizable liquid crystal composition according to any one of claims 1 to 5, which further contains a photopolymerization initiator. The polymerizable liquid crystal composition according to any one of claims 1 to 6, which further contains an organic solvent. A retardation film comprising a liquid crystal cured film as a cured product of the polymerizable liquid crystal composition according to any one of claims 1 to 7. Such as the retardation film of claim 8, in which the liquid crystal hardened film satisfies the formula (i): 0.75≦Re(450)/Re(550)＜1.00 (i) [In formula (i), Re(λ) represents the in-plane retardation value of the liquid crystal cured film at the wavelength λ nm]. An elliptical polarizing plate comprising the retardation film as claimed in claim 8 or 9. An optical display comprising the elliptical polarizer as claimed in claim 10. A flexible image display device comprising the elliptical polarizer as claimed in claim 10.