TW202112757A - Polymerizable liquid crystal mixed composition, retardation plate, elliptically polarizing plate and organic el display device - Google Patents

Abstract

The purpose of the present invention is to provide a polymerizable liquid crystal mixed composition which has excellent solubility in a solvent and excellent film forming properties, and which ideally is favorable for the production of retardation plates which exhibit reverse wavelength dispersion properties and which have excellent optical characteristics. This polymerizable liquid crystal mixed composition contains at least 3 types of polymerizable liquid crystal compounds which have different molecular structures and are represented by formula (I). Said polymerizable liquid crystal compounds include polymerizable liquid crystal compounds in which Ea and Eb in formula (I) are identical to each other; defining the polymerizable liquid crystal compound (I-1), represented by formula (I-1), as the polymerizable liquid crystal compound in which the carbon number of alkanediyl groups represented by Ea and Eb is the lowest, the polymerizable liquid crystal mixed composition contains said polymerizable liquid crystal compound (I-1), a polymerizable liquid crystal compound (I-2) which is defined on the basis of the structure of said polymerizable liquid crystal compound (I-1) and is represented by at least one formula (I-2), and the polymerizable liquid crystal compound (I-3) which is defined on the basis of the structure of said polymerizable liquid crystal compound (I-1) and is represented by at least one formula (I-3).

Description

Polymerizable liquid crystal hybrid composition, phase difference plate, elliptical polarizing plate and organic EL display device

The present invention relates to a polymerizable liquid crystal hybrid composition, a retardation plate including a liquid crystal cured film as a cured product of the polymerizable liquid crystal hybrid composition, and an elliptical polarizing plate including the retardation plate and organic EL (Electroluminescence, electroluminescence) Luminescence) display device.

As an optical film such as a phase difference plate used in a flat panel display device (FPD), for example, there is an optical film obtained by dissolving a polymerizable liquid crystal compound in a solvent, coating the obtained coating liquid on a supporting substrate, and polymerizing it. Conventionally, the polymerizable liquid crystal compound has been known, for example, a nematic liquid crystal compound having a rod-like structure formed by connecting 2 to 4 six-membered rings. On the other hand, the phase difference plate is required to be capable of polarization conversion in the full wavelength range as one of its characteristics. It is known, for example, in the wavelength range that exhibits reverse wavelength dispersion of [Re(450)/Re(550)]<1 In theory, the same polarization conversion can be performed. The polymerizable compound that can constitute such a phase difference plate is disclosed in Patent Document 1, for example. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-207765

[The problem to be solved by the invention]

Optical films such as retardation plates can be obtained by a method of dissolving a polymerizable liquid crystal compound as disclosed in Patent Document 1 in a solvent, and applying the obtained coating liquid on a supporting substrate to form a coating film, The polymerizable liquid crystal compound contained in the coating film is converted into a nematic liquid crystal phase state, the coating film is dried, and the solvent is distilled off. However, depending on the type of polymerizable liquid crystal compound, there are cases where the solubility to solvents is low due to its molecular structure. In such a polymerizable liquid crystal compound with low solubility, it is known that the obtained optical film is prone to alignment defects. Such a compound may also precipitate in the coating solution, and not only the film-forming properties may be reduced, but the obtained optical film may also have alignment defects. It is known that, in particular, polymerizable liquid crystal compounds containing aromatic rings can be used to obtain phase difference plates with reverse wavelength dispersion and excellent optical properties. On the other hand, there are molecules with higher symmetry. Compounds of the structure are the subject of further deterioration of solubility due to the molecular structure.

The object of the present invention is to provide a polymerizable liquid crystal hybrid composition with excellent solvent solubility and film forming properties, and preferably to provide a polymerizable liquid crystal mixture composition suitable for manufacturing a retardation plate that exhibits reverse wavelength dispersion and has high optical characteristics Liquid crystal hybrid composition. [Technical means to solve the problem]

[式(I)中， M¹ 表示包含至少1個芳香族烴環或芳香族雜環之二價連結基， B¹ 及B² 分別獨立地表示單鍵、碳數1～4之伸烷基、-O-、-S-、-R^a1 OR^a2 -、-R^a3 COOR^a4 -、-R^a5 OCOR^a6 -、-R^a7 OC=OOR^a8 -、-OR^b O-、-C(=O)-NR^c -、-N=N-、-CR^c =CR^d -或-C≡C-，此處，R^a1 ～R^a8 分別獨立地為單鍵或碳數1～4之伸烷基，R^b 為碳數1～4之伸烷基，R^c 及R^d 表示碳數1～4之烷基或氫原子， G¹ 及G² 分別獨立地表示二價脂環式烴基或芳香族基，該二價脂環式烴基或芳香族基中所含之氫原子可被取代為鹵素原子、碳數1～4之烷基、碳數1～4之氟烷基、碳數1～4之烷氧基、氰基或硝基，構成該二價脂環式烴基或芳香族基之碳原子可被取代為氧原子、硫原子或氮原子，於n1及/或n2為2之情形時，2個G¹ 及/或2個G² 可分別相同亦可不同， L¹ 及L² 分別獨立地表示單鍵、碳數1～4之伸烷基、-O-、-S-、-R^a1 OR^a2 -、-R^a3 COOR^a4 -、-R^a5 OCOR^a6 -、-R^a7 OC=OOR^a8 -、-OR^b O-、-C(=O)-NR^c -、-N=N-、-CR^c =CR^d -或-C≡C-，此處，R^a1 ～R^a8 分別獨立地為單鍵或碳數1～4之伸烷基，R^b 為碳數1～4之伸烷基，R^c 及R^d 表示碳數1～4之烷基或氫原子，於n1及/或n2為2之情形時，2個L¹ 及/或2個L² 可分別相同亦可不同， E^a 及E^b 分別獨立地表示碳數1～20之烷二基，此處，該烷二基中所含之氫原子可被取代為碳數1～4之烷基或鹵素原子，該烷二基中所含之-CH₂ -可被取代為-O-或-S-(其中，於存在複數個-O-及/或-S-之情形時，其等互不鄰接)， P為丙烯醯氧基或甲基丙烯醯氧基， n1及n2分別獨立地為1或2] 所表示之聚合性液晶化合物者，且 作為上述聚合性液晶化合物，包含式(I)中之E^a 與E^b 相互相同之聚合性液晶化合物， 於將該聚合性液晶化合物之中E^a 及E^b 所表示之烷二基之碳數最小之聚合性液晶化合物設為由式(I-1)：

[式(I-1)中， M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、P、n1及n2分別與上述式(I)中之M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、P、n1及n2相同地定義， E¹ 與上述式(I)中之E^a 及E^b 相同地定義，2個E¹ 相同] 所表示之聚合性液晶化合物(I-1)之情形時，包含該聚合性液晶化合物(I-1)、基於上述聚合性液晶化合物(I-1)之結構而定義之至少1種由式(I-2)：

[式(I-2)中， M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、E¹ 、P、n1及n2分別與上述式(I-1)中之M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、E¹ 、P、n1及n2相同， E² 表示與上述式(I-1)中之E¹ 不同之碳數1～20之烷二基，此處，該烷二基中所含之氫原子可被取代為碳數1～4之烷基或鹵素原子，該烷二基中所含之-CH₂ -可被取代為-O-或-S-(其中，於存在複數個-O-及/或-S-之情形時，其等互不鄰接)] 所表示之聚合性液晶化合物(I-2)、及基於上述聚合性液晶化合物(I-1)之結構而定義之至少1種由式(I-3)：

[式(I-3)中， M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、P、n1及n2分別與上述式(I-1)中之M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、P、n1及n2相同， E² 與上述式(I-2)中之E² 相同，且式(I-3)中之2個E² 相同] 所表示之聚合性液晶化合物(I-3)。 [2]如上述[1]所記載之聚合性液晶組合物，其中式(I-1)中，n1與n2相同。 [3]如上述[1]或[2]所記載之聚合性液晶化合物，其中M¹ 為包含至少1個所含之π電子數之合計數N_π 為16以上且未達36之芳香族烴環或芳香族雜環的二價連結基。 [4]如上述[1]至[3]中任一項所記載之聚合性液晶組合物，其中式(I-1)中，於n1及n2分別為1之情形時，G¹ 與G² 相互相同，於n1及n2分別為2之情形時，鍵結於B¹ 之G¹ 與鍵結於B² 之G² 相互相同，且另一G¹ 與G² 相互相同。 [5]如上述[1]至[4]中任一項所記載之聚合性液晶組合物，其中式(I-1)中，於n1及n2分別為1之情形時，L¹ 與L² 相互相同，於n1及n2分別為2之情形時，分別鍵結於E¹ 之L¹ 與L² 相互相同，且另一L¹ 與L² 相互相同。 [6]如上述[1]至[5]中任一項所記載之聚合性液晶混合組合物，其中式(I-1)及式(I-2)中之各E¹ 與式(I-2)及式(I-3)中之各E² 均為碳數4～20之烷二基，且 式(I-1)及式(I-2)中之各E¹ 所表示之烷二基之碳數與式(I-2)及式(I-3)中之各E² 所表示之烷二基之碳數的差均為2以上。 [7]如上述[1]至[6]中任一項所記載之聚合性液晶混合組合物，其中式(I)所表示之聚合性液晶化合物之中，相對於M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、P、n1及n2分別相互相同之式(I)所表示之聚合性液晶化合物之總莫耳量，分別包含式(I-1)所表示之聚合性液晶化合物、式(I-2)所表示之聚合性液晶化合物、及式(I-3)所表示之聚合性液晶化合物10莫耳%以上。 [8]如上述[1]至[7]中任一項所記載之聚合性液晶混合組合物，其包含有機溶劑。 [9]一種相位差板，其包含如下液晶硬化膜，上述液晶硬化膜係如上述[1]至[8]中任一項所記載之聚合性液晶混合組合物之硬化物，且係於該聚合性液晶混合組合物中之聚合性液晶化合物配向之狀態下硬化而成。 [10]如上述[9]所記載之相位差板，其中液晶硬化膜具有式(1)、(2)及(3)所表示之光學特性， Re(450)/Re(550)≦1.00  (1) 1.00≦Re(650)/Re(550)  (2) 100 nm≦Re(550)≦180 nm   (3) [式中，Re(λ)表示液晶硬化膜於波長λ nm下之面內相位差值，Re＝(nx(λ)－ny(λ))×d(d表示液晶硬化膜之厚度，nx表示於液晶硬化膜所形成之折射率橢球中，與液晶硬化膜之平面平行之方向的波長λ nm下之主折射率，ny表示於液晶硬化膜所形成之折射率橢球中，相對於液晶硬化膜之平面平行且相對於上述nx之方向正交之方向的波長λ nm下之折射率)]。 [11]如上述[9]所記載之相位差板，其中液晶硬化膜具有式(4)、(5)及(6)所表示之光學特性， Rth(450)/Rth(550)≦1.00  (4) 1.00≦Rth(650)/Rth(550)  (5) -100 nm≦Rth(550)≦-40 nm   (6) [式中，Rth(λ)表示液晶硬化膜於波長λ nm下之厚度方向之相位差值，Rth＝((nx(λ)＋ny(λ))/2－nz)×d(d表示液晶硬化膜之厚度，nx表示於液晶硬化膜所形成之折射率橢球中，與液晶硬化膜之平面平行之方向的波長λ nm下之折射率，ny表示於液晶硬化膜所形成之折射率橢球中，相對於液晶硬化膜之平面平行且相對於上述nx之方向正交之方向的波長λ nm下之折射率，nz表示於液晶硬化膜所形成之折射率橢球中，相對於液晶硬化膜之平面垂直之方向的波長λ nm下之折射率)]。 [12]一種橢圓偏光板，其包含如上述[9]至[11]中任一項所記載之相位差板與偏光膜。 [13]一種有機EL顯示裝置，其具備如上述[12]所記載之橢圓偏光板。 [14]一種如上述[1]至[8]中任一項所記載之聚合性液晶混合組合物之製造方法，其包括使下述式(III-1)所表示之化合物之反應性基R² 、(III-2)所表示之化合物之反應性基R² 、及(III-3)所表示之化合物之R¹ 發生反應，

[式中，R¹ 及R² 相互獨立地表示反應性基， M¹ 、L¹ 、L² 、G¹ 、G² 、P、n1及n2表示與式(I-1)中之M¹ 、L¹ 、L² 、G¹ 、G² 、P、n1及n2相同之含義， E¹ 表示與式(I-1)中之E¹ 相同之含義， E² 表示與式(I-2)中之E² 相同之含義]。 [發明之效果]The present invention provides the following preferred aspects. [1] A polymerizable liquid crystal hybrid composition, which contains at least three different molecular structures and is composed of formula (I):

[In formula (I), M ¹ represents a divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocyclic ring, and B ¹ and B ² each independently represent a single bond and an alkylene group having 1 to 4 carbon atoms , -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, -R ^a7 OC=OOR ^a8 -, -OR ^b O-, -C(=O ) -NR ^c -, -N=N-, -CR ^c =CR ^d -or -C≡C-, where R ^a1 to ^Ra8 are each independently a single bond or an alkylene group with 1 to 4 carbon atoms , R ^b is an alkylene group having 1 to 4 carbons, R ^c and R ^d represent an alkyl group having 1 to 4 carbons or a hydrogen atom, and G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group or aromatic The hydrogen atom contained in the divalent alicyclic hydrocarbon group or aromatic group may be substituted with a halogen atom, an alkyl group with 1 to 4 carbons, a fluoroalkyl group with 1 to 4 carbons, and a fluoroalkyl group with 1 to 4 carbons. The alkoxy group, cyano group or nitro group, the carbon atom constituting the divalent alicyclic hydrocarbon group or aromatic group can be substituted with oxygen atom, sulfur atom or nitrogen atom, when n1 and/or n2 are 2 , 2 G ¹ and/or 2 G ² may be the same or different, respectively, L ¹ and L ² each independently represent a single bond, a C1-C4 alkylene group, -O-, -S-,- R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, -R ^a7 OC=OOR ^a8 -, -OR ^b O-, -C(=O)-NR ^c -, -N=N -, -CR ^c =CR ^d -or -C≡C-, where R ^a1 to ^Ra8 are each independently a single bond or an alkylene group having 1 to 4 carbons, and R ^b is a carbon number of 1 to 4 Alkylene, R ^c and R ^d represent an alkyl group with 1 to 4 carbon atoms or a hydrogen atom. When n1 and/or n2 are 2, the two L ¹ and/or the two L ² may be the same or the same. Different, E ^a and E ^b each independently represent an alkanediyl group having 1 to 20 carbons. Here, the hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbon atoms or a halogen atom, _{The -CH 2} -contained in the alkanediyl group may be substituted with -O- or -S- (wherein, when there are plural -O- and/or -S-, they are not adjacent to each other), P is an acryloxy group or a methacryloxy group, n1 and n2 are each independently 1 or 2] the polymerizable liquid crystal compound represented, and the polymerizable liquid crystal compound includes E in the formula (I) ^{The polymerizable liquid crystal compound whose a} and E ^b are the same as each other, among the polymerizable liquid crystal compounds, the polymerizable liquid crystal compound having the smallest carbon number of the alkanediyl group represented by ^{E a} and E ^{b is represented by formula (I-1)} :

[In formula (I-1), M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 are respectively the same as M ¹ , B ¹ , and B 1 in the above formula (I) B ² , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 are defined the same, E ^{1 is defined the same as E a} and E ^b in the above formula (I), and two E ^{1 are the} same] So In the case of the polymerizable liquid crystal compound (I-1), including the polymerizable liquid crystal compound (I-1), at least one defined based on the structure of the above-mentioned polymerizable liquid crystal compound (I-1) is defined by the formula (I -2):

[In formula (I-2), M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , E ¹ , P, n1 and n2 are respectively the same as M in the above formula (I-1) ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , E ¹ , P, n1 and n2 are the same, E ² represents the number of carbons different from ^{E 1} in the above formula (I-1) 1 ~20 alkanediyl groups, where the hydrogen atoms contained in the alkanediyl groups may be substituted with C1-C4 alkyl groups or halogen atoms, and the -CH ₂ -contained in the alkanediyl groups may be substituted by Substituted with -O- or -S- (wherein, when there are a plurality of -O- and/or -S-, they are not adjacent to each other)] represented by the polymerizable liquid crystal compound (I-2), and At least one defined based on the structure of the polymerizable liquid crystal compound (I-1) is defined by the formula (I-3):

[In formula (I-3), M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 are respectively the same as M ¹ , B in the above formula (I-1) in the ^{1, B 2, G 1,} G 2, L 1, L 2, P, n1 and the same N2, E ² the same as (I-2) in the E above formula ^2, and formula (I-3) 2 E ^{2 is the} same] polymerizable liquid crystal compound (I-3). [2] The polymerizable liquid crystal composition as described in [1] above, wherein in formula (I-1), n1 and n2 are the same. [3] The polymerizable liquid crystal compound as described in the above [1] or [2], wherein M ¹ is an aromatic hydrocarbon containing at least one of the number of π electrons contained, N _π is 16 or more and less than 36 Divalent linking group of ring or aromatic heterocyclic ring. [4] The polymerizable liquid crystal composition as described in any one of [1] to [3] above, wherein in formula (I-1), when n1 and n2 are each 1, G ¹ and G ² the same as each other, n1 and n2 are in the time of the case 2, bonded to the ¹¹ B G and B G ² bonded to each of ^two identical, and the other G ¹ and G ^{2 are} the same to each other. [5] The polymerizable liquid crystal composition as described in any one of [1] to [4] above, wherein in formula (I-1), when n1 and n2 are each 1, L ¹ and L ² Same as each other. When n1 and n2 are 2 respectively, L ¹ and L ^{2 respectively bonded to E 1} are the same as each other, and the other L ¹ and L ² are the same as each other. [6] The polymerizable liquid crystal hybrid composition as described in any one of the above [1] to [5], wherein each E ¹ in the formula (I-1) and the formula (I-2) and the formula (I- ^{2) Each E 2} in formula (I-3) is an ^{alkanediyl group with 4 to 20 carbons, and each E 1} in formula (I-1) and formula (I-2) represents alkanedi The difference between the carbon number of the group and the carbon number of the alkanediyl group represented by ^{each E 2} in the formula (I-2) and the formula (I-3) is 2 or more. [7] The polymerizable liquid crystal hybrid composition as described in any one of [1] to [6] above, wherein the polymerizable liquid crystal compound represented by the formula (I) is relative to M ¹ , B ¹ , and B ^2. The total molar amount of the polymerizable liquid crystal compound represented by formula (I) where G ¹ , G ² , L ¹ , L ² , P, n1 and n2 are the same as each other, respectively, including those represented by formula (I-1) The polymerizable liquid crystal compound, the polymerizable liquid crystal compound represented by formula (I-2), and the polymerizable liquid crystal compound represented by formula (I-3) are 10 mol% or more. [8] The polymerizable liquid crystal hybrid composition as described in any one of [1] to [7] above, which contains an organic solvent. [9] A retardation plate comprising a liquid crystal cured film which is a cured product of the polymerizable liquid crystal hybrid composition described in any one of [1] to [8] above, and is attached to The polymerizable liquid crystal compound in the polymerizable liquid crystal hybrid composition is cured in a state where the polymerizable liquid crystal compound is aligned. [10] The phase difference plate as described in [9] above, wherein the liquid crystal cured film has optical properties represented by formulas (1), (2) and (3), Re(450)/Re(550)≦1.00 ( 1) 1.00≦Re(650)/Re(550) (2) 100 nm≦Re(550)≦180 nm (3) [where, Re(λ) represents the in-plane phase of the cured liquid crystal film at a wavelength of λ nm Difference, Re=(nx(λ)－ny(λ))×d (d represents the thickness of the liquid crystal cured film, nx represents the refractive index ellipsoid formed by the liquid crystal cured film, which is parallel to the plane of the liquid crystal cured film The principal refractive index at the wavelength λ nm of the direction, ny represents the refractive index ellipsoid formed by the liquid crystal cured film, which is parallel to the plane of the liquid crystal cured film and perpendicular to the direction of nx at the wavelength λ nm The refractive index)]. [11] The phase difference plate as described in the above [9], wherein the liquid crystal cured film has optical characteristics represented by formulas (4), (5) and (6), Rth(450)/Rth(550)≦1.00 ( 4) 1.00≦Rth(650)/Rth(550) (5) -100 nm≦Rth(550)≦-40 nm (6) [where, Rth(λ) represents the thickness of the liquid crystal cured film at the wavelength λ nm The phase difference value of the direction, Rth=((nx(λ)+ny(λ))/2-nz)×d (d represents the thickness of the liquid crystal cured film, nx represents the refractive index ellipsoid formed by the liquid crystal cured film, The refractive index at the wavelength λ nm in the direction parallel to the plane of the liquid crystal cured film, ny represents the refractive index ellipsoid formed by the liquid crystal cured film, which is parallel to the plane of the liquid crystal cured film and orthogonal to the direction of nx The refractive index at the wavelength λ nm in the direction, nz represents the refractive index at the wavelength λ nm in the direction perpendicular to the plane of the liquid crystal cured film in the refractive index ellipsoid formed by the liquid crystal cured film)]. [12] An elliptically polarizing plate comprising the phase difference plate and a polarizing film as described in any one of [9] to [11] above. [13] An organic EL display device including the elliptical polarizing plate described in [12] above. [14] A method for producing the polymerizable liquid crystal hybrid composition as described in any one of [1] to [8] above, which comprises making the reactive group R of the compound represented by the following formula (III-1) ^{2. The reactive group R 2} of the compound represented by (III-2) ^{and R 1} of the compound represented by (III-3) react,

[Wherein, R ¹ is and R ² each independently represents a reactive ^{group, M 1, L 1, L} 2, G 1, G 2, P, n1 and n2 represent the formula M ^{1 (I-1)} in the, ^{L 1, L 2, G 1} , G same as the meanings ^2, P, n1 same of n2 meaning and, E ¹ represented by the formula (I-1) in the E ^1, in E ² represented by the formula (I-2) The same meaning as ^{E 2].} [Effects of Invention]

According to the present invention, it is possible to provide a polymerizable liquid crystal hybrid composition that is excellent in solvent solubility and film-forming properties, and it is preferable to provide a polymerizable liquid crystal hybrid composition suitable for manufacturing a retardation plate that exhibits reverse wavelength dispersion and has high optical characteristics. Liquid crystal hybrid composition.

Hereinafter, embodiments of the present invention will be described in detail. In addition, the scope of the present invention is not limited to the embodiments described here, and various changes can be made without detracting from the gist of the present invention.

[式(I)中， M¹ 表示包含至少1個芳香族烴環或芳香族雜環之二價連結基， B¹ 及B² 分別獨立地表示單鍵、碳數1～4之伸烷基、-O-、-S-、-R^a1 OR^a2 -、-R^a3 COOR^a4 -、-R^a5 OCOR^a6 -、-R^a7 OC=OOR^a8 -、-OR^b O-、-C(=O)-NR^c -、-N=N-、-CR^c =CR^d -或-C≡C-，此處，R^a1 ～R^a8 分別獨立地為單鍵或碳數1～4之伸烷基，R^b 為碳數1～4之烷基，R^c 及R^d 表示碳數1～4之烷基或氫原子， G¹ 及G² 分別獨立地表示二價脂環式烴基或芳香族基，該二價脂環式烴基或芳香族基中所含之氫原子可被取代為鹵素原子、碳數1～4之烷基、碳數1～4之氟烷基、碳數1～4之烷氧基、氰基或硝基，構成該二價脂環式烴基或芳香族基之碳原子可被取代為氧原子、硫原子或氮原子，於n1及/或n2為2之情形時，2個G¹ 及/或2個G² 可分別相同亦可不同， L¹ 及L² 分別獨立地表示單鍵、碳數1～4之伸烷基、-O-、-S-、-R^a1 OR^a2 -、-R^a3 COOR^a4 -、-R^a5 OCOR^a6 -、-R^a7 OC=OOR^a8 -、-OR^b O-、-C(=O)-NR^c -、-N=N-、-CR^c =CR^d -或-C≡C-，此處，R^a1 ～R^a8 分別獨立地為單鍵或碳數1～4之伸烷基，R^b 為碳數1～4之伸烷基，R^c 及R^d 表示碳數1～4之烷基或氫原子，於n1及/或n2為2之情形時，2個L¹ 及/或2個L² 可分別相同亦可不同， E^a 及E^b 分別獨立地表示碳數1～20之烷二基，此處，該烷二基中所含之氫原子可被取代為碳數1～4之烷基或鹵素原子，該烷二基中所含之-CH₂ -可被取代為-O-或-S-(其中，於存在複數個-O-及/或-S-之情形時，其等互不鄰接)， P為丙烯醯氧基或甲基丙烯醯氧基， n1及n2分別獨立地為1或2]。<Polymerizable liquid crystal hybrid composition> The polymerizable liquid crystal hybrid composition of the present invention contains at least three types of polymerizable liquid crystal compounds whose molecular structures are different from each other and are represented by formula (I). By including at least 3 types of polymerizable liquid crystal compounds that are similar to each other as a molecular structure different from each other and represented by formula (I), higher solubility in solvents can be ensured.

[In formula (I), M ¹ represents a divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocyclic ring, and B ¹ and B ² each independently represent a single bond and an alkylene group having 1 to 4 carbon atoms , -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, -R ^a7 OC=OOR ^a8 -, -OR ^b O-, -C(=O ) -NR ^c -, -N=N-, -CR ^c =CR ^d -or -C≡C-, where R ^a1 to ^Ra8 are each independently a single bond or an alkylene group with 1 to 4 carbon atoms , R ^b is an alkyl group with 1 to 4 carbons, R ^c and R ^d represent an alkyl group with 1 to 4 carbons or a hydrogen atom, and G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group or an aromatic group , The hydrogen atoms contained in the divalent alicyclic hydrocarbon group or aromatic group can be substituted with halogen atoms, alkyl groups with 1 to 4 carbons, fluoroalkyl groups with 1 to 4 carbons, and fluoroalkyl groups with 1 to 4 carbons. Alkoxy group, cyano group or nitro group, the carbon atom constituting the divalent alicyclic hydrocarbon group or aromatic group may be substituted with oxygen atom, sulfur atom or nitrogen atom, when n1 and/or n2 are 2, Two G ¹ and/or two G ² may be the same or different, respectively, L ¹ and L ² each independently represent a single bond, a C1-C4 alkylene group, -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, -R ^a7 OC=OOR ^a8 -, -OR ^b O-, -C(=O)-NR ^c -, -N=N- , -CR ^c =CR ^d -or -C≡C-, where R ^a1 to R ^a8 are each independently a single bond or an alkylene having 1 to 4 carbons, and R ^b is an extension of 1 to 4 carbons. Alkyl group, R ^c and R ^d represent an alkyl group with 1 to 4 carbon atoms or a hydrogen atom. When n1 and/or n2 are 2, the two L ¹ and/or the two L ² may be the same or different , E ^a and E ^b each independently represent an alkanediyl group having 1 to 20 carbons. Here, the hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbons or a halogen atom. _{The -CH 2} -contained in the alkanediyl group may be substituted with -O- or -S- (wherein, when there are plural -O- and/or -S-, they are not adjacent to each other), P It is an acryloxy group or a methacryloxy group, and n1 and n2 are each independently 1 or 2].

[式(I-1)中， M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、P、n1及n2分別與上述式(I)中之M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、P、n1及n2相同地定義， E¹ 與上述式(I)中之E^a 及E^b 相同地定義，2個E¹ 相同] 所表示之聚合性液晶化合物(I-1)(以下，亦稱為「聚合性液晶化合物(I-1)」)之情形時，包含該聚合性液晶化合物(I-1)、基於上述聚合性液晶化合物(I-1)之結構而定義之至少1種由式(I-2)：

[式(I-2)中， M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、E¹ 、P、n1及n2分別與上述式(I-1)中之M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、E¹ 、P、n1及n2相同， E² 表示與上述式(I-1)中之E¹ 不同之碳數1～20之烷二基，此處，該烷二基中所含之氫原子可被取代為碳數1～4之烷基或鹵素原子，該烷二基中所含之-CH₂ -可被取代為-O-或-S-(其中，於存在複數個-O-及/或-S-之情形時，其等互不鄰接)] 所表示之聚合性液晶化合物(以下，亦稱為「聚合性液晶化合物(I-2)」)、及基於上述聚合性液晶化合物(I-1)之結構而定義之至少1種由式(I-3)：

[式(I-3)中， M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、P、n1及n2分別與上述式(I-1)中之M¹ 、B¹ 、B² 、G¹ 、G² 、L¹ 、L² 、P、n1及n2相同， E² 與上述式(I-2)中之E² 相同，且式(I-3)中之2個E² 相同] 所表示之聚合性液晶化合物(以下，亦稱為「聚合性液晶化合物(I-3)」)。於本發明中，於聚合性液晶混合組合物包含複數個相當於上述式(I-1)之化合物之情形時，將相當於式(I-1)所表示之化合物之化合物之中E^a 及E^b 所表示之烷二基之碳數最小之聚合性液晶化合物設為「聚合性液晶化合物(I-1)」。再者，於E^a 及E^b 所表示之烷二基具有取代基之情形時，「E^a 及E^b 所表示之烷二基之碳數」意指E^a 及E^b 所表示之烷二基中之構成由式(I-1)所表示之化合物之主鏈的部分之碳數。The polymerizable liquid crystal hybrid composition of the present invention comprises ^a polymerizable liquid crystal compound whose E a and E ^b in the formula (I) are the same as each other as the above-mentioned at least three polymerizable liquid crystal compounds, and among the polymerizable liquid crystal compounds, E ^a and The polymerizable liquid crystal compound with the smallest carbon number of the alkanediyl represented by E ^{b is set as the formula (I-1):}

[In formula (I-1), M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 are respectively the same as M ¹ , B ¹ , and B 1 in the above formula (I) B ² , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 are defined the same, E ^{1 is defined the same as E a} and E ^b in the above formula (I), and two E ^{1 are the} same] So In the case of the polymerizable liquid crystal compound (I-1) (hereinafter, also referred to as "polymerizable liquid crystal compound (I-1)"), the polymerizable liquid crystal compound (I-1) is included, based on the polymerizable liquid crystal The structure of compound (I-1) is defined by at least one of formula (I-2):

[In formula (I-2), M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , E ¹ , P, n1 and n2 are respectively the same as M in the above formula (I-1) ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , E ¹ , P, n1 and n2 are the same, E ² represents the number of carbons different from ^{E 1} in the above formula (I-1) 1 ~20 alkanediyl groups, where the hydrogen atoms contained in the alkanediyl groups may be substituted with C1-C4 alkyl groups or halogen atoms, and the -CH ₂ -contained in the alkanediyl groups may be substituted by Substituted with -O- or -S- (wherein, when there are a plurality of -O- and/or -S-, they are not adjacent to each other)] represented by the polymerizable liquid crystal compound (hereinafter, also referred to as " The polymerizable liquid crystal compound (I-2)"), and at least one of the types defined based on the structure of the above-mentioned polymerizable liquid crystal compound (I-1) are represented by formula (I-3):

[In formula (I-3), M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 are respectively the same as M ¹ , B in the above formula (I-1) in the ^{1, B 2, G 1,} G 2, L 1, L 2, P, n1 and the same N2, E ² the same as (I-2) in the E above formula ^2, and formula (I-3) 2 E ^{2 is the} same as the polymerizable liquid crystal compound (hereinafter, also referred to as "polymerizable liquid crystal compound (I-3)"). In the present invention, when the polymerizable liquid crystal hybrid composition contains a plurality of compounds corresponding to the above formula (I-1), among the compounds corresponding to the compound represented by the formula (I-1), E ^a and The polymerizable liquid crystal compound with the smallest carbon number of the alkanediyl group represented by E ^{b is referred to as "polymerizable liquid crystal compound (I-1)".} Further, in ^a E E ^B and the alkanediyl group represented by a substituent having a group of the case, ^"a carbon number of E and ^B E are the group represented by the alkanediyl" means ^a alkanediyl E ^B and E are represented by the The number of carbons in the main chain of the compound represented by formula (I-1) in the group.

Regarding the above three polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) constituting the polymerizable liquid crystal hybrid composition of the present invention, the molecules of the polymerizable liquid crystal compound (I-1) When the structure is the basis, only the parts of the formulas (I-1), (I-2) and (I-3) other than M ¹ (hereinafter, the M ¹ part is also referred to as the "core part"", ^{the parts other than M 1} are also referred to as "messogen") The structure of the alkanediyl group represented by ^{E 1} and/or E ^{2 is different.} By making the structures of the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) similar to each other, the polymerizable liquid crystal compounds can be easily mixed with each other, which can improve the solubility of the mixed composition in the solvent Sex. Therefore, compared with the case where the polymerizable liquid crystal compound (I-1), (I-2) or (I-3) is dissolved in the solvent alone, more polymerizable liquid crystal compounds can be easily dissolved in the same amount or A smaller amount of solvent may be able to dissolve as a mixed composition even in a solvent that cannot dissolve the polymerizable liquid crystal compound (I-1), (I-2), or (I-3) alone. Thereby, the undissolved polymerizable liquid crystal compound is unlikely to remain in the coating liquid, and high coating properties during film formation can be ensured, thereby becoming a polymerizable liquid crystal mixed composition with excellent film forming properties. Furthermore, in terms of reducing the amount of solvent required for the preparation of the coating liquid, and increasing the number of options related to the substrate or alignment film used, manufacturing conditions, etc., by increasing the types of solvents that can be selected Also beneficial. In addition, by improving the solubility of the polymerizable liquid crystal compound in the solvent, the precipitation or stacking of the polymerizable liquid crystal compound in the coating liquid can be suppressed. By this, it is possible to suppress the occurrence of alignment defects caused by undissolved polymerizable liquid crystal compounds or precipitates, or to improve storage stability, and it is possible to suppress the degradation of the optical properties that the polymerizable liquid crystal compound used originally can express and to form a film. Therefore, it is possible to obtain a polymerizable liquid crystal composition suitable for the production of a retardation plate with excellent optical properties.

所表示之聚合性液晶化合物。具有由式(I)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表現逆波長分散性之雙折射的聚合性液晶化合物，於較廣之波長區域中，可進行相同之偏光轉換。因此，藉由使用式(I)所表示之聚合性液晶化合物，可獲得於用於顯示裝置之情形時可賦予良好之顯示特性的聚合性液晶組合物。The polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) are respectively represented by formula (I):

The polymerizable liquid crystal compound represented. The compound having the structure represented by the formula (I) is usually a birefringent polymerizable liquid crystal compound that exhibits reverse wavelength dispersion when polymerized in a state aligned in one direction, and can perform the same in a wider wavelength range. Polarized light conversion. Therefore, by using the polymerizable liquid crystal compound represented by formula (I), it is possible to obtain a polymerizable liquid crystal composition that can impart good display characteristics when used in a display device.

In the formula (I), B ¹ and B ² are each independently a single bond, an alkylene having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, ^{-R a7} OC=OOR ^a8 -, -OR ^b O-, -C(=O)-NR ^c -, -N=N-, ^{-CR c} =CR ^d -or -C≡ C-. Here, R ^a1 to R ^a8 are each independently a single bond or an alkylene having 1 to 4 carbons, R ^b is an alkylene having 1 to 4 carbons, and R ^c and R ^{d are each} having 1 to 4 carbons. Alkyl group or hydrogen atom. Preferably, B ¹ and B ² are each independently a single bond, -OR ^a2-1 -, -CH ₂ -, -CH ₂ CH ₂ -, ^{-COOR a4-1} -, or -OCOR ^a6-1 -. ^{Here, R a2-1, R a4-1, R} a6-1 each independently represent a single _{bond, -CH 2 -, - CH 2} CH 2 - of any one. B ¹ and B ² are each independently and more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or -OCO-. In the formula (I), B ¹ and B ² may be the same as or different from each other. Further, B ¹ and B ² each means the same as in the case when M ¹ as central to the structure B ¹ and B ² of the same to each other. Hereinafter, the relationship between G ¹ and G ² , L ¹ and L ² , and E ^a and E ^b is also the same.

G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group or an aromatic group, and the hydrogen atoms contained in the divalent alicyclic hydrocarbon group or aromatic group may be substituted with halogen atoms, with a carbon number of 1 to 4 Alkyl group, fluoroalkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, cyano group or nitro group. The carbon atoms constituting the divalent alicyclic hydrocarbon group or aromatic group may be substituted with oxygen atoms, sulfur atoms or nitrogen atoms. When n1 and/or n2 are 2, 2 G ¹ and/or 2 G ² may be the same or different. Preferably, G ¹ and G ² are each independently a 1,4-phenylenediyl group 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, 1,4-cyclohexadiyl 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 1,4-phenylene substituted with methyl Diyl, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4-trans-cyclohexandiyl, particularly preferably unsubstituted 1,4-phenylenediyl or unsubstituted 1,4-phenylenediyl Substituted 1,4-trans cyclohexanediyl. In the formula (I), G ¹ and G ² may be the same or different from each other. When ^{there are two G 1} and G ² respectively, at least one of them is preferably a divalent alicyclic hydrocarbon group. Furthermore, it is more preferable that at least one of G ¹ and G ² bonded to B ¹ or B ² is a divalent alicyclic hydrocarbon group, and particularly in terms of exhibiting good liquid crystallinity, it is more preferable to be a bond or junction in B ² B G ¹ and G ² are of the ^{1,4-trans-1-cyclohexyl-diyl,} particularly preferably bonded to B ¹ or B ² of G ¹ and G ² are both 1,4-trans G ¹ and G ^{2 that} are not adjacent to B ¹ or B ^{2 of the} formula cyclohexanediyl are both 1,4-phenylenediyl.

L ¹ and L ² each independently represent a single bond, an alkylene having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6- , -R ^a7 OC=OOR ^a8 -, -OR ^b O-, -C(=O)-NR ^c -, -N=N-, -CR ^c =CR ^d -or -C≡C-. Here, R ^a1 to R ^a8 are each independently a single bond or an alkylene having 1 to 4 carbons, R ^b is an alkylene having 1 to 4 carbons, and R ^c and R ^d represent an alkylene having 1 to 4 carbons. Alkyl group or hydrogen atom. When n1 and/or n2 are 2, the two L ¹ and/or the two L ² may be the same or different. Preferably, L ¹ and L ² are each independently a single bond, -OR ^a2-1 -, -CH ₂ -, -CH ₂ CH ₂ -, ^{-COOR a4-1} -or OCOR ^a6-1 -. ^{Here, R a2-1, R a4-1, R} a6-1 each independently represent a single _{bond, -CH 2 -, - CH 2} CH 2 - of any one. L ¹ and L ² are each independently and more preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, -OCO- or -OCOCH ₂ CH ₂ -. In formula (I), L ¹ and L ² may be the same as or different from each other.

E ^a and E ^b each independently represent an alkanediyl group having 1 to 20 carbon atoms. Here, the hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbons or a halogen atom, and the -CH ₂ -contained in the alkanediyl group may be substituted with -O- or- S- (wherein, when there are a plurality of -O- and/or -S-, they are not adjacent to each other). E ^a and E ^b are each independently an alkanediyl group having 4 to 20 carbon atoms, and more preferably an alkanediyl group having 4 to 11 carbon atoms. The three polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) constituting the polymerizable liquid crystal hybrid composition of the present invention are equivalent to E ^a and/or E ^{b in formula (I)} The basic structure of the structure shown is different from each other.

P is acryloxy or methacryloxy. In formula (I), two Ps are the same.

n1 and n2 are 1 or 2 independently, respectively. From the viewpoint of expressing specific wavelength dispersion characteristics, it is preferable that n1 and n2 represent the same number, and it is more preferable that n1=2 and n2=2.

In formula (I), M ¹ is a divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocyclic ring. The aromatic hydrocarbon ring and aromatic heterocyclic ring referred to here refer to those in which the number of π electrons in the ring structure is [4n+2] (n represents an integer) according to Huckel's law (in the case of an aromatic heterocyclic ring) , Including non-covalent bonding electron pairs on heteroatoms such as -N= or -S-, satisfying Huckel's law), or two or more via divalent linking groups, such as the following (M ¹ -1) ~ (M ¹ -23) the base illustrated. The divalent linking group M ¹ may include one aromatic hydrocarbon ring or aromatic heterocyclic ring, or two or more. In the case of containing one aromatic hydrocarbon ring or aromatic heterocyclic ring, the divalent linking group M ¹ may be a divalent aromatic hydrocarbon group which may have a substituent, or a divalent aromatic heterocyclic ring which may have a substituent base. In the case of containing two or more aromatic hydrocarbon rings or aromatic heterocyclic rings, it may contain only a plurality of aromatic hydrocarbon rings, or only a plurality of aromatic heterocycles, or may contain more than one aromatic hydrocarbon. Rings and aromatic heterocycles. 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-.

Examples of the aromatic hydrocarbon ring that M ¹ may contain include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferred. 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, thienothiazole ring, azole ring, benzoazole ring, phenanthroline ring, etc. When M ¹ contains a nitrogen atom, it is preferable that the nitrogen atom has π electrons.

Among them, M ¹ preferably 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, and more preferably has a thiazole ring, a benzothiazole ring or a benzothiazole ring. The furan ring further preferably has a benzothiazole ring. Furthermore, when M ¹ 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 (I) B ¹ and B ^{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 B 1} and B ² , preferably M including the above-mentioned aromatic heterocyclic ring ^The entire 1-group is three-dimensionally arranged in a direction substantially orthogonal to the molecular alignment direction.

In formula (I), _{the total number N π} contained in the divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocyclic ring represented ^{by M 1} is preferably 16 or more, more preferably 18 or more, particularly preferably 20 or more. Furthermore, it is preferably less than 36, more preferably 30 or less, still more preferably 26 or less, and particularly preferably 24 or less.

Examples of the divalent linking group represented by M ^{1 include the following groups.}

In the formulas (M ¹ -1) to (M ¹ -23), the * symbol represents a connecting portion, and Z ⁰ , Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 12 carbon atoms, Cyano, nitro, alkylsulfinyl with 1-12 carbons, alkylsulfinyl with 1-12 carbons, carboxyl, fluoroalkyl with 1-12 carbons, alkane with 1-12 carbons Oxy group, alkylthio with 1-12 carbons, N-alkylamino with 1-12 carbons, N,N-dialkylamino with 2-12 carbons, N- with 1-12 carbons Alkylsulfasulfonyl or N,N-dialkylsulfasulfonyl with 2-12 carbon atoms. In addition, Z ⁰ , Z ¹ and Z ² may include a polymerizable group.

Q ¹ and Q ² each independently represent -CR ^{2 '} R ^{3 '} -, -S-, -NH-, -NR ^{2 '} -, -CO- or O-, R ^{2 '} and R ^{3 '} each independently represent A hydrogen atom or an alkyl group with 1 to 4 carbon atoms.

J ¹ and J ² each independently represent a carbon atom or a nitrogen atom.

Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group, or a halogen atom, and m represents an integer of 0-6.

Examples of the aromatic hydrocarbon groups in Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, naphthyl, anthryl, phenanthryl, and biphenyl. Preferred is phenyl, Naphthyl is more preferably phenyl. Examples of aromatic heterocyclic groups include furyl, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl and the like, including at least one nitrogen atom, oxygen atom, sulfur atom, and other heteroatoms with carbon number of 4 to The aromatic heterocyclic group of 20 is preferably furyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl.

Y ¹ , Y ² and Y ^{3 may} each independently be a substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.

Z ⁰ , Z ¹ and Z ^{2 are} preferably each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbons, a cyano group, a nitro group, an alkoxy group having 1 to 12 carbons, and Z ⁰ is more A hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group are ^{preferable, and Z 1} and Z ^{2 are more} preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group. In addition, Z ⁰ , Z ¹ and Z ² may include a polymerizable group.

Q ¹ and Q ^{2 are} preferably -NH-, -S-, -NR ^{2 '} -, -O-, and R ^{2 ' is} preferably a hydrogen atom. Among them, particularly preferred are -S-, -O-, and -NH-.

In formulas (M ¹ -16) to (M ¹ -23), Y ¹ may also form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ^0. Examples of the aromatic heterocyclic group include ^{those described above as the aromatic heterocyclic ring that M 1} may have, for example, a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyridine ring, a pyrimidine ring, Indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring, etc. The aromatic heterocyclic group may have a substituent. In addition, Y ¹ may be the above-mentioned substitutable polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ^0. For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring, etc. are mentioned.

Among the formulas (M ¹ -1) to (M ¹ -23), from the viewpoint of the stability of the molecule, the formula (M ¹ -6), the formula (M ¹ -7) and the formula (M ¹ -16).

The polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) constituting the polymerizable liquid crystal hybrid composition of the present invention are only in the structure represented by the above formula (I) E ^a and/or E The structure of the alkanediyl group represented by ^{b is different from each other.} Based on the structure of the polymerizable liquid crystal compound (I-1) constituting the polymerizable liquid crystal hybrid composition, the polymerizable liquid crystal compound (I-2) and the polymerizable liquid crystal compound (I-1) only constitute the mesogen part It is different in the structure of any one of the alkanediyl groups ^{corresponding to E a} and E ^b of formula (I) ^{[E 2 in formula (I-2)].} In addition, the polymerizable liquid crystal compound (I-3) and the polymerizable liquid crystal compound (I-1) are only included in the ^{two alkanediyl groups corresponding to E a} and E ^b of the formula (I) that constitute the mesogen part [formula (I) -3) ^{The structure of E 2} ] is different. Furthermore, the polymerizable liquid crystal compound (I-3) and the polymerizable liquid crystal compound (I-2) differ only in the structure of the alkanediyl group represented by ^{E 1 in the formula (I-2) constituting the mesogen part.} By using the above-mentioned at least three polymerizable liquid crystal compounds whose structures are similar to each other but different, the polymerizable liquid crystal compounds can be easily mixed with each other, and the solubility to solvents as a mixed composition can be improved, and excellent film forming properties can be obtained. Polymerizable liquid crystal hybrid composition.

In the polymerizable liquid crystal compound (I-1) which is the basis of the structure of the polymerizable liquid crystal compound constituting the polymerizable liquid crystal hybrid composition of the present invention, as M ¹ , B ¹ , and B ^{2 in the formula (I-1)} , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 can be enumerated as M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , P, n1, and n2 are the same as those exemplified. ^{Examples of E 1} in the formula (I-1) include the same as those exemplified as E ^a and E ^{b in the formula (I), and E 1} in the formula (I-1) is the same as each other.

In the polymerizable liquid crystal compound (I-1), it is preferable that the divalent linking group (core part) represented ^{by M 1} is used as the center, and the number of ring structures in the mesogen part other ^{than M 1 is symmetrical.} Therefore, in formula (I-1), it is preferable that n1 and n2 are the same.

Furthermore, it is more preferable that the ring structures of the mesogen parts having a symmetrical relationship with the core part as the center are the same as each other. Therefore, in formula (I-1), when n1 and n2 are each 1, it is more preferable that G ¹ and G ² are the same as each other, and when n1 and n2 are each 2, it is more preferable to bond to B ¹ of G ¹ and B ² bonded to the same G ² each other, and another (B ¹ or B ² and adjacent thereto) G ¹ and G ² each the same. Furthermore, it is more preferable that the molecular structures of the mesogens having a symmetrical relationship with the core part as the center are the same as each other. In formula (I-1), when n1 and n2 are 1, respectively, L ¹ and L are more preferable ² are the same as each other, and when n1 and n2 are 2 respectively, it is more preferable that L ¹ and L ^{2 respectively bonded to E 1} are the same as each other, and the other L ¹ and L ² are the same as each other. In a preferred aspect of the present invention, it is particularly preferred to have a ^{symmetrical molecular structure of the mesogen part other than M 1} with the core part as the center. In formula (I-1), particularly preferred are B ¹ and B ² Same, G ¹ and G ^{2 are the} same, L ¹ is the ^{same as L 2} , and n1 is the same as n2. In formula (I-1), it is particularly preferred that B ¹ is the same as ^{B 2 , G 1} and G ^{2 are the} same, and L ^{1 is the} same as L ^{2 is the} same, n1 and n2 are both 2. Liquid crystal compounds with a molecular structure with higher symmetry tend to have poor solubility. However, in the present invention, the liquid crystal compound with a molecular structure with higher symmetry is made into a liquid crystal compound with a structure similar to each other. Mixture, and improve the solubility to the solvent. Therefore, the present invention is suitable for the use of polymerizable liquid crystal compounds having a relatively high symmetrical molecular structure, which previously had insufficient solubility in solvents when alone. Furthermore, B ¹ and B ² are identical to each other means that ^{the structure of B 1} and B ^{2 is the same when M 1 is} regarded as the center. For example, when B ¹ is -O-CO-*1, it is the same as B ¹ The same B ² is *2-CO-O- (*1 and *2 each independently represent the bonding bond ^{with M 1).} Hereinafter, the relationship between G ¹ and G ² , and L ¹ and L ² is also the same.

In the present invention, as the polymerizable liquid crystal compound (I-1), for example, compounds described in Japanese Patent Laid-Open No. 2019-003177 and the like can be cited.

In the polymerizable liquid crystal compound represented by the formula (I-2), in the formula (I-2), M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , E ¹ , P, ^{n1 and n2 together with M 1} , B ¹ , B ² , G ¹ , G ² , L in the formula (I-1) in the polymerizable liquid crystal compound (I-1) contained in the polymerizable liquid crystal hybrid composition ¹ , L ² , E ¹ , P, n1 and n2 are the same. ^{E 2} in the formula (I-2) is an alkanediyl group with 1 to 20 carbons that is different from ^{E 1} in the formula (I-1) ^{, which can be exemplified as E a} and E ^{b in the formula (I)} The same exemplified ones. In formula (I-2), since E ¹ and E ² constituting the mesogen part have mutually different structures, the polymerizable liquid crystal compound (I-2) has an asymmetric structure centered on ^{M 1 of the core part} Liquid crystal original part.

The polymerizable liquid crystal compound (I-2) has a molecular structure in which the divalent linking group (core part) represented ^{by M 1 is the center, and the mesogen part other than M 1} is asymmetric, and it is more preferable to have the core part as the center. The ring structures of the mesogens in the symmetric relationship are the same as each other, and it is more preferable that only the structures ^{of E 1} and E ^{2 in formula (I-2) are asymmetric.} Therefore, in formula (I-2), it is preferable that n1 and n2 are the same, when n1 and n2 are 1 respectively, it is more preferable that G ¹ and G ² are the same as each other, and when n1 and n2 are 2 respectively , more preferably bonded to the ^{1 1} B G and B G ² bonded to the ^two mutually identical, and the other G ¹ and G ² are the same. Moreover, in the formula (I-2), when n1 and n2 are each 1, it is more preferable that L ¹ and L ² are the same as each other, and when n1 and n2 are each 2, it is more preferable that they are respectively bonded to L ¹ and L ^{2 of} E ¹ are the same as each other, and the other L ¹ and L ² are the same as each other. It is particularly preferred that B ¹ and B ^{2 are the} same, G ¹ and G ^{2 are the} same, L ¹ and L ^{2 are the} same, and n1 and n2 are the same. . In the present invention, the structure of the polymerizable liquid crystal compound (I-2) is specified in the relationship with the polymerizable liquid crystal compound (I-1) contained in the polymerizable liquid crystal hybrid composition, and the polymerizable liquid crystal compound (I-2) I-1) differs only in the structure equivalent to -E ^{1 -[-E 2} -in the formula (I-2)] in the formula (I-1) constituting the mesogen. The polymerizable liquid crystal compound (I-2) contained in the polymerizable liquid crystal hybrid composition of the present invention may be only one type or two or more types. ^{Furthermore, when the core part M 1} in the formula (I-2) is a divalent linking group with an asymmetric structure, the polymerizable liquid crystal compound (I-2) includes the compound represented by the formula (I-2a) and The compound represented by formula (I-2b).

In the present invention, in the polymerizable liquid crystal compound represented by the formula (I-3), M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , ^{P, n1 and n2 together with M 1} , B ¹ , B ² , G ¹ , G ² in the formula (I-1) in the polymerizable liquid crystal compound (I-1) contained in the polymerizable liquid crystal hybrid composition , L ¹ , L ² , P, n1 and n2 are the same. E ^{2 in the formula (I-3) is the same as E 2} in the formula (I-2) in the polymerizable liquid crystal compound (I-2) contained together in the polymerizable liquid crystal hybrid composition, and the formula (I-3 The two E ^{2 in)} are the same as each other.

It is more preferable that the polymerizable liquid crystal compound (I-3) ^{has the divalent linking group (core part) represented by M 1} as the center, and the ring structures of the mesogen parts having the core part as the center in a symmetrical relationship are the same as each other, and more preferably It has a symmetrical molecular structure of mesogen ^{except M 1.} Therefore, in formula (I-3), it is preferable that n1 and n2 are the same, when n1 and n2 are 1 respectively, it is more preferable that G ¹ and G ² are the same as each other, and when n1 and n2 are 2 respectively , more preferably bonded to the ^{1 1} B G and B G ² bonded to the ^two mutually identical, and the other G ¹ and G ² are the same. Moreover, in the formula (I-3), when n1 and n2 are each 1, it is more preferable that L ¹ and L ² are the same as each other, and when n1 and n2 are each 2, it is more preferable that they are respectively bonded to L ¹ and L ^{2 of} E ¹ are the same as each other, and the other L ¹ and L ² are the same as each other. It is particularly preferred that B ¹ and B ^{2 are the} same, G ¹ and G ^{2 are the} same, L ¹ and L ^{2 are the} same, and n1 and n2 are the same. . In the present invention, the structure of the polymerizable liquid crystal compound (I-3) is specified in the relationship with the polymerizable liquid crystal compounds (I-1) and (I-2) contained together in the polymerizable liquid crystal hybrid composition, Different from the polymerizable liquid crystal compound (I-1) only in the structure equivalent to -E ^{1 -in the formula (I-1) constituting the mesogen part [-E 2} -in the formula (I-3)], And the polymerizable liquid crystal compound (I-2) is only equivalent to the structure of -E ^1- [one of the formula (I-3) -E ² -] in the formula (I-2) constituting the mesogen part different. The polymerizable liquid crystal compound (I-3) contained in the polymerizable liquid crystal hybrid composition of the present invention may be only one type or two or more types.

The polymerizable liquid crystal compounds (I-1) and (I-3) constituting the polymerizable liquid crystal hybrid composition of the present invention preferably have the formula (I-1) or the formula (I-3) represented by M ¹ the divalent linking group (core portion) as a center, in addition part (mesogen portion) other than ¹ M symmetrical molecular structure. On the other hand, the polymerizable liquid crystal compound (I-2) has a divalent linking group (core part) represented by ^{M 1} in the formula (I-2) as the center, and a part other ^{than M 1 (mesogenic part)} Asymmetric molecular structure. The polymerizable liquid crystal hybrid composition of the present invention includes at least three polymerizable liquid crystal compounds whose structures are similar to each other: polymerizable liquid crystal compounds (I-1) and (I- 3) In the case of a polymerizable liquid crystal compound (I-2) having a mesogen part of an asymmetric structure with a core part as the center, the polymerizable liquid crystal compound becomes easy to mix with each other, which can further improve the performance of the mixed composition. Solubility to solvents. Therefore, compared with the case where the polymerizable liquid crystal compound (I-1), (I-2) or (I-3) is dissolved in a solvent alone, more polymerizable liquid crystal compounds can be easily dissolved in the same amount or A smaller amount of solvent. In addition, even in a solvent that cannot dissolve the polymerizable liquid crystal compound (I-1), (I-2), or (I-3) alone, it may be dissolved as a mixed composition. Thereby, the undissolved polymerizable liquid crystal compound is unlikely to remain in the coating liquid, and high coatability during film formation can be ensured, resulting in a polymerizable liquid crystal mixed composition with excellent film forming properties. Furthermore, it is also advantageous in that the amount of solvent required for preparing the coating liquid can be reduced, and options such as the substrate or the alignment film used, the manufacturing conditions, and the like can be increased by increasing the types of solvents that can be selected. In addition, by improving the solubility of the polymerizable liquid crystal compound in the solvent, the precipitation or stacking of the polymerizable liquid crystal compound in the coating liquid can be suppressed. Thereby, it is possible to suppress the occurrence of alignment defects caused by undissolved polymerizable liquid crystal compounds or precipitates, or to improve storage stability, and it is possible to form a film without degrading the optical properties of the polymerizable liquid crystal compound used.化. In addition, by only changing the length of the alkyl chain of the mesogen part of the polymerizable liquid crystal compound [ ^{the carbon number of E a} and E ^b in the formula (I)], the reactivity during the synthesis of the polymerizable liquid crystal compound is also different. If there is a difference, it is easy to obtain the advantage of a polymerizable liquid crystal hybrid composition containing each polymerizable liquid crystal compound in a desired composition ratio.

^{In the polymerizable liquid crystal hybrid composition of the present invention, each E 1 in} formula (I-1) and formula (I-2) and each of formula (I-2) and formula (I-3) are preferred E ² is an alkanediyl group having 4 to 20 carbon atoms, more preferably each of E ^{1 in} formula (I-1) and formula (I-2) and in formula (I-2) and formula (I-3) Each E ² is an alkanediyl group having 4-20 carbons, and the carbon number of the alkanediyl group represented by ^{each E 1} in the formula (I-1) and the formula (I-2) is the same as that of the formula (I-2) The difference in the number of carbon atoms of the alkanediyl groups represented ^{by each E 2} in the formula (I-3) is 2 or more. If the difference in carbon number of the alkanediyl group is 2 or more, it can be used as a liquid crystal mixture composition to effectively improve the solubility of each polymerizable liquid crystal compound in the solvent, so it can obtain excellent coating and film forming properties, suitable for high production Efficiently produce polymerizable liquid crystal hybrid compositions for optical films. In the carbon atoms of the formula alkanediyl group of In the formula (I-1) and formula (I-2) each E represented by the ¹ (I-2) and formula (I-3) each E represented by the ² alkyl The upper limit of the difference in the carbon number of the two groups is usually 20 or less, preferably 9 or less, and more preferably 7 or less. Furthermore, the difference in carbon number "both are 2 or more" means that when there are a plurality of types of polymerizable liquid crystal compounds (I-2) and/or (I-3), all the polymerizable liquid crystal compounds (I- ^{2) and/or the carbon number of the alkanediyl group represented by E 2} in (I-3) and the carbon number of the alkanediyl group represented by ^{each E 1} in formula (I-1) and formula (I-2) The number differs by more than two.

As a combination of the polymerizable liquid crystal compound represented by formula (I) constituting the polymerizable liquid crystal hybrid composition of the present invention, for example, the combination as exemplified in the following Tables 1 to 4 can be cited. The polymerizable liquid crystal hybrid composition described in each table contains three or more polymerizable liquid crystal compounds that are different from each other ^{only in terms of E a} and/or E ^{b in the structure described as the basic structure.}

聚合性液晶混合組合物No. 聚合性液晶化合物 E^a E^b 1 (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸己基 伸己基 伸丁基 (I-3) 伸己基 伸己基 2 (I-1) 伸己基 伸己基 (I-2) 伸己基 伸辛基 伸辛基 伸己基 (I-3) 伸辛基 伸辛基 3 (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸辛基 伸辛基 伸丁基 (I-3) 伸辛基 伸辛基 4 (3種混合) (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸己基 伸丁基 伸辛基 其他(I) 伸己基 伸辛基 (I-2) 伸己基 伸丁基 伸辛基 伸丁基 其他(I) 伸辛基 伸己基 (I-3) 伸己基 伸己基 伸辛基 伸辛基 [Table 1] Basic structure of polymerizable liquid crystal compound

Polymerizable liquid crystal hybrid composition No. Polymerizable liquid crystal compound E ^a E ^b 1 (I-1) Butyl Butyl (I-2) Butyl Shinhiki Shinhiki Butyl (I-3) Shinhiki Shinhiki 2 (I-1) Shinhiki Shinhiki (I-2) Shinhiki Octyl Octyl Shinhiki (I-3) Octyl Octyl 3 (I-1) Butyl Butyl (I-2) Butyl Octyl Octyl Butyl (I-3) Octyl Octyl 4 (3 kinds of mix) (I-1) Butyl Butyl (I-2) Butyl Shinhiki Butyl Octyl Other (I) Shinhiki Octyl (I-2) Shinhiki Butyl Octyl Butyl Other (I) Octyl Shinhiki (I-3) Shinhiki Shinhiki Octyl Octyl

聚合性液晶混合組合物No. 聚合性液晶化合物 E^a E^b 5 (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸己基 伸己基 伸丁基 (I-3) 伸己基 伸己基 6 (I-1) 伸己基 伸己基 (I-2) 伸己基 伸辛基 伸辛基 伸己基 (I-3) 伸辛基 伸辛基 7 (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸辛基 伸辛基 伸丁基 (I-3) 伸辛基 伸辛基 8 (3種混合) (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸己基 伸丁基 伸辛基 其他(I) 伸己基 伸辛基 (I-2) 伸己基 伸丁基 伸辛基 伸丁基 其他(I) 伸辛基 伸己基 (I-3) 伸己基 伸己基 伸辛基 伸辛基 [Table 2] Basic structure of polymerizable liquid crystal compound

Polymerizable liquid crystal hybrid composition No. Polymerizable liquid crystal compound E ^a E ^b 5 (I-1) Butyl Butyl (I-2) Butyl Shinhiki Shinhiki Butyl (I-3) Shinhiki Shinhiki 6 (I-1) Shinhiki Shinhiki (I-2) Shinhiki Octyl Octyl Shinhiki (I-3) Octyl Octyl 7 (I-1) Butyl Butyl (I-2) Butyl Octyl Octyl Butyl (I-3) Octyl Octyl 8 (3 kinds of mix) (I-1) Butyl Butyl (I-2) Butyl Shinhiki Butyl Octyl Other (I) Shinhiki Octyl (I-2) Shinhiki Butyl Octyl Butyl Other (I) Octyl Shinhiki (I-3) Shinhiki Shinhiki Octyl Octyl

聚合性液晶混合組合物No. 聚合性液晶化合物 E^a E^b 9 (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸己基 伸己基 伸丁基 (I-3) 伸己基 伸己基 10 (I-1) 伸己基 伸己基 (I-2) 伸己基 伸辛基 伸辛基 伸己基 (I-3) 伸辛基 伸辛基 11 (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸辛基 伸辛基 伸丁基 (1-3) 伸辛基 伸辛基 12 (3種混合) (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸己基 伸丁基 伸辛基 其他(I) 伸己基 伸辛基 (I-2) 伸己基 伸丁基 伸辛基 伸丁基 其他(I) 伸辛基 伸己基 (I-3) 伸己基 伸己基 伸辛基 伸辛基 [table 3] Basic structure of polymerizable liquid crystal compound

Polymerizable liquid crystal hybrid composition No. Polymerizable liquid crystal compound E ^a E ^b 9 (I-1) Butyl Butyl (I-2) Butyl Shinhiki Shinhiki Butyl (I-3) Shinhiki Shinhiki 10 (I-1) Shinhiki Shinhiki (I-2) Shinhiki Octyl Octyl Shinhiki (I-3) Octyl Octyl 11 (I-1) Butyl Butyl (I-2) Butyl Octyl Octyl Butyl (1-3) Octyl Octyl 12 (3 kinds of mix) (I-1) Butyl Butyl (I-2) Butyl Shinhiki Butyl Octyl Other (I) Shinhiki Octyl (I-2) Shinhiki Butyl Octyl Butyl Other (I) Octyl Shinhiki (I-3) Shinhiki Shinhiki Octyl Octyl

聚合性液晶混合組合物No. 聚合性液晶化合物 E^a E^b 13 (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸己基 伸己基 伸丁基 (I-3) 伸己基 伸己基 14 (I-1) 伸己基 伸己基 (I-2) 伸己基 伸辛基 伸辛基 伸己基 (I-3) 伸辛基 伸辛基 15 (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸辛基 伸辛基 伸丁基 (I-3) 伸辛基 伸辛基 16 (3種混合) (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸己基 伸丁基 伸辛基 其他(I) 伸己基 伸辛基 (I-2) 伸己基 伸丁基 伸辛基 伸丁基 其他(I) 伸辛基 伸己基 (I-3) 伸己基 伸己基 伸辛基 伸辛基 [Table 4] Basic structure of polymerizable liquid crystal compound

Polymerizable liquid crystal hybrid composition No. Polymerizable liquid crystal compound E ^a E ^b 13 (I-1) Butyl Butyl (I-2) Butyl Shinhiki Shinhiki Butyl (I-3) Shinhiki Shinhiki 14 (I-1) Shinhiki Shinhiki (I-2) Shinhiki Octyl Octyl Shinhiki (I-3) Octyl Octyl 15 (I-1) Butyl Butyl (I-2) Butyl Octyl Octyl Butyl (I-3) Octyl Octyl 16 (3 kinds of mix) (I-1) Butyl Butyl (I-2) Butyl Shinhiki Butyl Octyl Other (I) Shinhiki Octyl (I-2) Shinhiki Butyl Octyl Butyl Other (I) Octyl Shinhiki (I-3) Shinhiki Shinhiki Octyl Octyl

聚合性液晶混合組合物No. 聚合性液晶化合物 E^a E^b 17 (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸己基 伸己基 伸丁基 (I-3) 伸己基 伸己基 18 (I-1) 伸己基 伸己基 (I-2) 伸己基 伸辛基 伸辛基 伸己基 (I-3) 伸辛基 伸辛基 19 (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸辛基 伸辛基 伸丁基 (I-3) 伸辛基 伸辛基 20 (3種混合) (I-1) 伸丁基 伸丁基 (I-2) 伸丁基 伸己基 伸丁基 伸辛基 其他(I) 伸己基 伸辛基 (I-2) 伸己基 伸丁基 伸辛基 伸丁基 其他(I) 伸辛基 伸己基 (I-3) 伸己基 伸己基 伸辛基 伸辛基 [table 5] Basic structure of polymerizable liquid crystal compound

Polymerizable liquid crystal hybrid composition No. Polymerizable liquid crystal compound E ^a E ^b 17 (I-1) Butyl Butyl (I-2) Butyl Shinhiki Shinhiki Butyl (I-3) Shinhiki Shinhiki 18 (I-1) Shinhiki Shinhiki (I-2) Shinhiki Octyl Octyl Shinhiki (I-3) Octyl Octyl 19 (I-1) Butyl Butyl (I-2) Butyl Octyl Octyl Butyl (I-3) Octyl Octyl 20 (3 kinds of mix) (I-1) Butyl Butyl (I-2) Butyl Shinhiki Butyl Octyl Other (I) Shinhiki Octyl (I-2) Shinhiki Butyl Octyl Butyl Other (I) Octyl Shinhiki (I-3) Shinhiki Shinhiki Octyl Octyl

With regard to the polymerizable liquid crystal hybrid composition of the present invention, among the polymerizable liquid crystal compounds represented by the formula (I), it is preferable to compare M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , and L ^{2 among the polymerizable liquid crystal compounds represented by formula (I).} , P, n1, and n2 are the same as each other [that is, the molecular structures are the same as each other except for the structure represented by ^{E a} and/or E ^{b in formula (I)] The polymerization represented by formula (I)} The total molar amount of the liquid crystal compound includes the polymerizable liquid crystal compound represented by formula (I-1), the polymerizable liquid crystal compound represented by formula (I-2), and the polymerizable liquid crystal compound represented by formula (I-3), respectively. The liquid crystal compound is more than 10 mol%. By including 3 kinds of polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) whose molecular structures are similar to each other, 10 mol% or more, it is easy to make the content of the 3 kinds of polymerizable liquid crystal compounds insignificant Mixed with each other unevenly, so that the solubility of each polymerizable liquid crystal compound to the solvent can be effectively improved.

In one aspect of the present invention, regarding the polymerizable liquid crystal hybrid composition of the present invention, it is preferable that the content of the polymerizable liquid crystal compound (I-2) is greater than the content of the polymerizable liquid crystal compound (I-1). The content ratio of the polymerizable liquid crystal compound (I-1) and (I-2) in the liquid crystal hybrid composition [molar ratio, (I-1): (I-2)] is preferably 1:1 to 1: 5. More preferably, it is 1:1 to 1:2. Furthermore, it is preferable that the content of the polymerizable liquid crystal compound (I-2) is greater than the content of the polymerizable liquid crystal compound (I-3), and the polymerizable liquid crystal compounds (I-2) and (I-2) in the polymerizable liquid crystal hybrid composition -3) The content ratio [mole ratio, (I-2):(I-3)] is preferably 1:8-8:1, more preferably 1:4-4:1. In addition, when the polymerizable liquid crystal hybrid composition contains a plurality of polymerizable liquid crystal compounds (I-1), (I-2) and/or (I-3), the above-mentioned content ratios are regarded as equivalent to the respective polymerizable liquid crystal compounds (I-1), (I-2) and/or (I-3). The total amount of the compounds of the liquid crystal compound is calculated.

The polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) constituting the polymerizable liquid crystal hybrid composition of the present invention are not subject to the method for producing polymerizable liquid crystal compounds represented by formula (I) Particularly limited, according to its structure, it is possible to combine the well-known organic synthesis reactions described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Lectures, etc. (for example, condensation reaction, esterification reaction, William Musson reaction, Ulmann reaction, Witti reaction, Schiff base formation reaction, benzylation reaction, saccato reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartway The Greek reaction, the Friedel-Crafts reaction, the Heck reaction, the aldol reaction, etc.) are appropriately combined and manufactured. Specifically, according to, for example, the method for producing a polymerizable liquid crystal compound described in Japanese Patent Laid-Open No. 2019-003177, etc., an alcohol compound and a carboxylic acid compound having a structure corresponding to the structure of the desired polymerizable liquid crystal compound can be used. The esterification reaction is prepared.

[式中，R¹ 及R² 相互獨立地表示反應性基， M¹ 、L¹ 、L² 、G¹ 、G² 、P、n1及n2表示與式(I-1)中之M¹ 、L¹ 、L² 、G¹ 、G² 、P、n1及n2相同之含義， E¹ 表示與式(I-1)中之E¹ 相同之含義， E² 表示與式(I-2)中之E² 相同之含義] 就合成簡便，可更高效率地製造聚合性液晶混合組合物之觀點而言，較佳為藉由後一種方法進行製造。The polymerizable liquid crystal compounds (I-1), (I-2), and (I-3) constituting the polymerizable liquid crystal hybrid composition of the present invention can be prepared by separately preparing each, and then mixing the three to form a liquid crystal mixture . In addition, a liquid crystal mixture containing polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) can also be prepared by the following method, which includes making the following formula (III-1) R reactive group of the reactive compound of the compound represented by the group R ^{2, (III-2)} represented by the ^2, and (III-3) R ¹ of the compound represented by the reaction.

[Wherein, R ¹ is and R ² each independently represents a reactive ^{group, M 1, L 1, L} 2, G 1, G 2, P, n1 and n2 represent the formula M ^{1 (I-1)} in the, ^{L 1, L 2, G 1} , G same as the meanings ^2, P, n1 same of n2 meaning and, E ¹ represented by the formula (I-1) in the E ^1, in E ² represented by the formula (I-2) The same meaning of E ² ] From the viewpoint of simple synthesis and a more efficient production of the polymerizable liquid crystal hybrid composition, it is preferable to produce it by the latter method.

^{M 1} , L ¹ , L ² , G ¹ , G ² , E ¹ , E ² , P, n1 and n2 in formulas (III-1), (III-2) and (III-3) The molecular structure corresponding to the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) is determined.

In the (III-3) R of formula ¹ and the formula (III-1) and R (III-2) in the ^two long they can react with each other to form a represents a polymerizable liquid crystal compound (I-1) ~ (I -3) of The structures represented by ^{B 1} and B ² in formulas (I-1) to (I-3) are sufficient. For example, ^{the reactive group represented by R 1} and/or R ² includes a hydroxyl group, a carboxyl group, an amino group, etc., as long as the reaction represented by ^{R 1} and R ^{2 is selected according to the reaction used in the production of the polymerizable liquid crystal compound} Sexual base can be.

From the viewpoints of ease of reaction, operability of materials, ease of acquisition, etc., typically, for example, R in formula (III-3) as a compound represented by formula (III-3) can be used ¹ is the alcohol compound of the hydroxyl group and the compound represented by the formula (III-1) and the compound represented by the formula (III-2) in the formulas (III-1) and (III-2), R ² is the carboxyl group, respectively The carboxylic acid compound undergoes an esterification reaction to produce the polymerizable liquid crystal mixture of the present invention. 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 in Japanese Patent Laid-Open No. 2019-003177 mentioned above can be used. Or condition.

By adjusting the amount of the compound represented by the formula (III-1) and the compound represented by the formula (III-2) used in the preparation, the polymerizable liquid crystal compound (I-1) in the obtained liquid crystal mixture can be controlled ), (I-2) and (I-3) content. 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. When the total of carboxylic acid compounds is set to 1, and the molar fractions of the carboxylic acid compounds are set to An, Bn, and Cn, respectively, the polymerizable liquid crystal compounds (I-1) and (I-2) When the total of) is set to 1, the theoretical molar fraction Sn of the polymerizable compound (I-1) is as follows. Sn=Σ(An ² +Bn ² +Cn ² ) In addition, the theoretical molar fraction of the polymerizable compound (I-2) is similarly represented by 1-Sn.

As long as the effect of the present invention is not affected, the polymerizable liquid crystal hybrid composition of the present invention may also contain polymerizable liquid crystal compounds other than polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) . As other polymerizable liquid crystal compounds other than the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3), for example, although having a molecular structure represented by formula (I), it is (I-1) The polymerizable liquid crystal compound does not belong to any one of the polymerizable liquid crystal compounds (I-2) and (I-3) in the relationship of the polymerizable liquid crystal compound represented by (I-1). In addition, it can be exemplified that it usually exhibits a positive wavelength Dispersible polymerizable liquid crystal compounds, such as "3.8.6 Network (Completely Cross-linked)", "6.5.1 Liquid Crystals" (Edited by the Editorial Committee of Liquid Crystals Handbook, published by Maruzen Co., Ltd. on October 30, 2000) Material b. Polymerizable nematic liquid crystal material" among the compounds described in "Compounds having a polymerizable group, etc.".

When the polymerizable liquid crystal hybrid composition of the present invention contains polymerizable liquid crystal compounds other than the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3), its content is relative to the polymerizable liquid crystal compound The total 100 parts by mass of the compounds (I-1), (I-2) and (I-3) is preferably 150 parts by mass or less, more preferably 100 parts by mass or less, and still more preferably 50 parts by mass or less. In particular, if the content of liquid crystal compounds with very different molecular structures is too large, phase separation may occur and the appearance may be significantly impaired. Therefore, the polymerizable liquid crystal compound constituting the polymerizable liquid crystal hybrid composition of the present invention is preferably substantially composed of The polymerizable liquid crystal compound represented by formula (I) is more preferably composed substantially of M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 is composed of the same polymerizable liquid crystal compound as ^{M 1} , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 in formula (I-1). Furthermore, the above-mentioned "substantially constituted" means that the content of the polymerizable liquid crystal compound and the like represented by the above formula (I) is 90 relative to the total mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal hybrid composition of the present invention. Above mass%.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal hybrid 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 hybrid composition is, for example, 70-99.5 parts by mass, preferably It is 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and still more preferably 90 to 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 content of the polymerizable liquid crystal mixed composition means all the components obtained by removing volatile components such as an organic solvent from the polymerizable liquid crystal mixed composition.

In addition to the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3), the polymerizable liquid crystal hybrid composition of the present invention may further include an organic solvent, a photopolymerization initiator, and a polymerization inhibitor , Photosensitizer, leveling agent and other additives. These components may be used individually by only 1 type, and may be used in combination of 2 or more types.

In the present invention, since the polymerizable liquid crystal mixed composition is usually applied to a substrate or the like in a state of being dissolved in a solvent, it preferably contains a solvent. As the solvent, a solvent that can dissolve the polymerizable liquid crystal compound constituting the polymerizable liquid crystal mixed composition such as polymerizable liquid crystal compounds (I-1) to (I-3) is preferred, and it is preferably a solvent for the polymerizable liquid crystal compound. The polymerization reaction is an inert solvent. Examples of solvents include: water; methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxy Alcohol solvents such as ethyl alcohol 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, Ketone solvents such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; lipids such as ethyl cyclohexane Cyclic 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; dimethylacetamide, dimethylacetamide Amine-based solvents such as methamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidone. These solvents can be used alone or in combination of two or more. Among these, organic solvents are preferred, and alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amine-based solvents, and aromatic hydrocarbon solvents are more preferred.

The content of the solvent in the polymerizable liquid crystal mixed 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 mixed composition. Therefore, the solid content in 100 parts by mass of the polymerizable liquid crystal mixed composition 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 mixed composition becomes low, so the thickness of the film becomes substantially uniform, and unevenness tends to be less likely to occur. The above-mentioned solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.

The polymerizable liquid crystal hybrid composition of the present invention preferably contains a polymerization initiator. The polymerization initiator is a compound that generates reactive species with the help of heat or light, thereby starting the polymerization reaction of polymerizable liquid crystals and the like. Examples of reactive species include reactive species such as radicals, cations, and 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, benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxy ketal compounds, α-amino ketone compounds, tris-compounds, iodonium salts, phosphonium salts, etc. . Specifically, it can include: Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure Japan EG (above BA 379 shares) Company manufacture), Seikuol BZ, Seikuol Z, Seikuol BEE (the above are manufactured by Seiko Chemical Co., Ltd.), 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 Arkls NCI-831, Adeka Arkls NCI-930 (the above are manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (the above are Nihon SiberHegner Corporation) and TAZ-104 (Sanwa Chemical Corporation). In the present invention, the polymerizable liquid crystal hybrid composition preferably contains at least one photopolymerization initiator, and may also contain two or more photopolymerization initiators.

The photopolymerization initiator can make full use of the energy emitted from the light source. In terms of excellent productivity, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and among them, α-benzene is preferred. Ethyl ketone-based polymerization initiator, oxime-based photopolymerization initiator.

Examples of α-acetophenone compounds include: 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1- (4-morpholinylphenyl)-2-benzylbutane-1-one and 2-dimethylamino-1-(4-morpholinylphenyl)-2-(4-methylphenyl) Methyl)butan-1-one, etc., more preferably 2-methyl-2-morpholin-1-(4-methylthiophenyl)propan-1-one and 2-dimethylamine -1-(4-morpholinylphenyl)-2-benzylbutan-1-one. As commercial products of the α-acetophenone compound, Irgacure 369, 379EG, 907 (manufactured by BASF Japan Co., Ltd. above), Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.), and the like can be cited.

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

The addition amount of the photopolymerization initiator is usually 0.1 parts by mass to 30 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound, preferably 1 part by mass to 20 parts by mass, and more preferably 1 part by mass to 15 parts by mass. If it is in the above range, the reaction of the polymerizable group proceeds sufficiently, and the alignment of the polymerizable liquid crystal compound is not easily disturbed.

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 butyl catechol; o-benzene Triphenols; 2,2,6,6-tetramethyl-1-piperidinoxy radicals and other free radical scavengers; 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 relative to 100 parts by mass of the polymerizable liquid crystal compound is usually 0.01-10 parts by mass, preferably 0.1-5 parts by mass, and more preferably 0.1 ~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。作為光敏劑，例如可列舉：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。光敏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. Examples of photosensitizers include: ketone, 9-oxysulfur

And other ketones; anthracene and anthracene with alkyl ether and other substituents; phenanthrene; red fluorene. Examples of photosensitizers include: ketone, 9-oxysulfur

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 hybrid 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 mixed composition to make the film obtained by coating it flatter. Examples include: silicone-based, polyacrylate-based, and perfluorinated Alkyl-based leveling agent. Specifically, include: DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of the above are manufactured by Toray Dow Corning Co., Ltd.), KP321, KP323, KP324, KP326, KP340 , KP341, X22-161A, KF6001 (all of the above are manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all of the above are Momentive Advanced Materials Japan Limited Manufactured by the company), fluorinert (registered trademark) FC-72, fluorinert FC-40, fluorinert FC-43, fluorinert FC-3283 (all of the above are manufactured by Sumitomo 3M Co., Ltd.), 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 Co., Ltd.), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (all of the above are manufactured by Mitsubishi Materials Electronic Chemicals 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 of the above are manufactured by AGC Seimi Chemical Co., Ltd.), trade name E1830, Trade names E5844 (manufactured by Daikin Fine Chemical Research Institute 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 hybrid 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, the polymerizable liquid crystal compound tends to be easily aligned, and the obtained liquid crystal cured film tends to become smoother, which is preferable. The polymerizable liquid crystal mixed composition may contain two or more types of leveling agents.

The polymerizable liquid crystal hybrid composition of the present invention can be prepared by adding a solvent, a polymerization initiator, a polymerization inhibitor, a photosensitizer, or a photosensitizer to the polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) as necessary. Additives such as leveling agents are prepared by stirring and mixing at a specific temperature.

＜Phase difference plate＞ Regarding the polymerizable liquid crystal hybrid composition of the present invention, since the polymerizable liquid crystal compound has high solubility in solvents and is excellent in coating properties and film forming properties, it can suppress undissolved polymerizable liquid crystal compounds or deposits during storage. Occurrence of alignment defects caused by etc. Therefore, by using the polymerizable liquid crystal hybrid composition of the present invention, it is possible to form a film without degrading the optical properties that the polymerizable liquid crystal compound can originally express, and a liquid crystal cured film having excellent optical properties can be obtained. Therefore, the present invention also relates to a retardation plate comprising a liquid crystal cured film, the liquid crystal cured film being a cured product of the polymerizable liquid crystal hybrid composition of the present invention, and a cured product of the polymerizable liquid crystal hybrid composition, and It is formed by curing in a state where the polymerizable liquid crystal compound in the polymerizable liquid crystal hybrid composition is aligned. The retardation plate including the above-mentioned liquid crystal cured film can be a retardation plate that can fully express the optical characteristics that the polymerizable liquid crystal compound used originally can exert and has high optical performance.

The liquid crystal cured film constituting the phase difference plate of the present invention may also include the homopolymer of the polymerizable liquid crystal compound (I-1) in the aligned state, the homopolymer of the polymerizable liquid crystal compound (I-2), and the polymerizable liquid crystal compound The homopolymer of (I-3) may also include a copolymer in an aligned state of a mixture of polymerizable liquid crystal compounds (I-1), (I-2) and (I-3). 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 plate of the present invention preferably contains polymerizable liquid crystal compounds (I-1), (I-2) and (I-3) ) The copolymer in the alignment state of the mixture.

In one aspect of the present invention, the retardation plate of the present invention is a cured product of the polymerizable liquid crystal hybrid composition of the present invention, and includes optical properties represented by the following formulas (1), (2) and (3) The liquid crystal hardened film. The liquid crystal cured film is usually a cured product cured in a state where the polymerizable liquid crystal compound is aligned in a horizontal direction relative to the plane of the liquid crystal cured film (hereinafter, also referred to as "horizontal aligned liquid crystal cured film"). Re(450)/Re(550)≦1.00 (1) 1.00≦Re(650)/Re(550) (2) 100 nm≦Re(550)≦180 nm (3) [In the formula, Re(λ) represents the in-plane retardation value of the liquid crystal cured film at the wavelength λ nm, Re=(nx(λ)－ny(λ))×d(d represents the thickness of the liquid crystal cured film, nx represents In the refractive index ellipsoid formed by the liquid crystal cured film, the principal refractive index at the wavelength λ nm in the direction parallel to the plane of the liquid crystal cured film, ny represents the refractive index ellipsoid formed by the liquid crystal cured film, relative to the liquid crystal The plane of the cured film is parallel and the refractive index at the wavelength λ nm in the direction orthogonal to the direction of nx)]

When the horizontally aligned liquid crystal cured film satisfies the formulas (1) and (2), the horizontally aligned liquid crystal cured film exhibits the so-called reverse wavelength dispersion in which the in-plane retardation value at the short wavelength is smaller than the in-plane retardation value at the long wavelength Sex. In terms of improving the reverse wavelength dispersion and further improving the optical properties of the retardation plate, Re(450)/Re(550) is preferably 0.70 or more, more preferably 0.78 or more, and preferably 0.92 or less, more preferably 0.90 Hereinafter, it is more preferably 0.87 or less, particularly preferably 0.86 or less, and even more preferably 0.85 or less. In addition, Re(650)/Re(550) is preferably 1.00 or more, more preferably 1.01 or more, and still more preferably 1.02 or more.

The above-mentioned in-plane retardation value can be adjusted by the thickness d of the horizontally aligned liquid crystal cured film. Since the in-plane retardation value is determined by the above formula Re(λ)=(nx(λ)-ny(λ))×d, in order to obtain the required in-plane retardation value (Re(λ): wavelength λ( nm), the in-plane retardation value of the horizontally aligned liquid crystal cured film), as long as the three-dimensional refractive index and the film thickness d are adjusted.

In addition, when the horizontally aligned liquid crystal cured film satisfies the formula (3), when an elliptical polarizing plate equipped with a retardation plate including the horizontally aligned liquid crystal cured film is applied to an organic EL display device, the front reflection hue is improved The effect (the effect of suppressing coloration) 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.

In one aspect of the present invention, the retardation plate of the present invention is a cured product of the polymerizable liquid crystal hybrid composition of the present invention, and includes optical properties represented by the following formulas (4), (5) and (6) The liquid crystal hardened film. The liquid crystal cured film is usually a cured product obtained by curing in a state where the polymerizable liquid crystal compound is aligned in a direction perpendicular to the plane of the liquid crystal cured film (hereinafter, also referred to as "vertical alignment liquid crystal cured film"). Rth(450)/Rth(550)≦1.00 (4) 1.00≦Rth(650)/Rth(550) (5) -100 nm≦Rth(550)≦-40 nm (6) [In the formula, Rth(λ) represents the retardation value of the thickness direction of the liquid crystal cured film at the wavelength λ nm, Rth=((nx(λ)+ny(λ))/2-nz)×d(d represents the liquid crystal hardening The thickness of the film, 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, and ny represents the refractive index ellipsoid formed by the liquid crystal cured film In the sphere, 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, nz represents the refractive index ellipsoid formed by the liquid crystal cured film, which is hardened with respect to the liquid crystal The refractive index under the wavelength λ nm in the direction perpendicular to the plane of the film)]

When the vertical alignment liquid crystal cured film satisfies the formulas (4) and (5), in the elliptical polarizing plate provided with the retardation plate including the vertical alignment liquid crystal cured film, the decrease in ellipticity can be suppressed on the short wavelength side, and the ellipticity can be suppressed. Improve the oblique reflection hue. The value of Rth(450)/Rth(550) in the vertical alignment liquid crystal cured film is preferably 0.70 or more, more preferably 0.78 or more, and preferably 0.92 or less, more preferably 0.90 or less, and still more preferably 0.87 or less, It is particularly preferably 0.86 or less, and more particularly preferably 0.85 or less. In addition, Rth(650)/Rth(550) is preferably 1.0 or more, more preferably 1.01 or more, and still more preferably 1.02 or more.

In addition, when the vertical alignment liquid crystal cured film satisfies the formula (6), when an elliptical polarizing plate equipped with a retardation plate including the vertical alignment liquid crystal cured film is applied to an organic EL display device, the oblique reflection can be improved Hue. The retardation value Rth(550) of the film thickness direction of the vertical alignment liquid crystal cured film is more preferably -90 nm or more, still more preferably -80 nm or more, and still more preferably -50 nm or less.

The phase difference plate 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 hybrid composition of the present invention, drying the coating film, and aligning the polymerizable liquid crystal compound in the polymerizable liquid crystal hybrid composition; and The step of forming a liquid crystal cured film by polymerizing the polymerizable liquid crystal compound by light irradiation while maintaining the alignment state.

The coating film of the polymerizable liquid crystal hybrid composition can be formed by coating the polymerizable liquid crystal composition on a substrate or an alignment film described below. As a base material, a glass base material, a film base material, etc. are mentioned, for example, From the viewpoint of processability, a resin film base material is preferable. Examples of the resin constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norene-based polymers; cycloolefin-based resins; polyvinyl alcohol; polyethylene terephthalate; Methacrylate; polyacrylate; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; Ether stubble; polyether ketone; polyphenylene sulfide and polyphenylene ether and other plastics. The resin can be made into a substrate by forming a film of this resin by a known method such as a solvent casting method and a melt extrusion method. The surface of the substrate can also have a protective layer formed of acrylic resin, methacrylic resin, epoxy resin, oxetane resin, urethane resin, melamine resin, etc., and can also be treated with silicone Such as release treatment, corona treatment, plasma treatment and other surface treatments.

Commercial products can also be used as substrates. Examples of commercially available cellulose ester substrates include: cellulose ester substrates manufactured by Fujifilm Co., Ltd. such as FUJITAC films; KONICA MINOLTA OPTO such as "KC8UX2M", "KC8UY", and "KC4UY" Cellulose ester substrate manufactured by Co., Ltd., etc. As commercially available cycloolefin resins, for example, cycloolefin resins made by Ticona in Germany, such as "Topas (registered trademark)"; and rings made by JSR Co., Ltd., such as "ARTON (registered trademark)". Olefin resins; "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)" cycloolefin resins manufactured by Zeon Corporation; "APEL" (registered trademark), Mitsui Chemicals Co., Ltd. Cycloolefin resin manufactured by the company. 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.; ZeonorFilm (registered trademark)" is a cycloolefin resin substrate manufactured by Optes Co., Ltd.; "Arton Film (registered trademark)" is a cycloolefin resin substrate manufactured by JSR Co., Ltd.

From the viewpoints of thinning of the phase difference plate, easy peelability of the substrate, and 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 hybrid composition to a substrate, etc., spin coating, extrusion, gravure coating, die nozzle coating, bar coating, applicator method, etc. can be cited. Well-known methods such as printing methods such as cloth method and soft plate method.

Next, the solvent is removed by drying or the like, thereby forming a dry coating film. As the drying method, a natural drying method, a ventilation drying method, a heat drying method, a reduced pressure drying method, and the like can be cited. 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 moved in a desired direction relative to the plane of the coating film (for example, horizontal Or vertical direction) alignment. 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. In order to make the polymerizable liquid crystal compound phase transition into the liquid crystal phase state, it usually needs to be higher than the liquid crystal phase transition temperature. temperature. In order to remove the solvent contained in the polymerizable liquid crystal composition while setting the polymerizable liquid crystal compound into a desired alignment state, for example, it can be heated to the liquid crystal phase of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal hybrid composition. The temperature above the transition temperature (smectic phase transition temperature or nematic phase transition temperature). Furthermore, the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature adjustment platform, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analysis device (TG-DTA), or the like. The above-mentioned phase transition temperature in the polymerizable liquid crystal hybrid composition of the present invention containing at least 3 types of polymerizable liquid crystal compounds means to use the same ratio as the composition in the polymerizable liquid crystal composition to polymerize all of the polymerizable liquid crystal composition. The measured temperature of a mixture of polymerizable liquid crystal compounds formed by mixing liquid crystal compounds.

The polymerizable liquid crystal hybrid composition of the present invention contains at least three polymerizable liquid crystal compounds (I-1), (I-2), and (I-3), which are generally comparable to the polymerizable liquid crystal compound (I-1). , (I-2) or (I-3) Transition into liquid crystal phase at a low temperature for liquid crystal phase transition. Therefore, when the polymerizable liquid crystal hybrid composition of the present invention is used to manufacture a phase difference plate, the excessive consumption of heat energy can be suppressed, and the production efficiency can be improved. In addition, by heating at a relatively low temperature to perform liquid crystal phase transition, there is also an advantage that there are more options for supporting substrates for coating the polymerizable liquid crystal hybrid 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 or its boiling point and its amount, etc., and it is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.

The removal of the solvent from the coating film may be performed simultaneously with heating to the liquid crystal phase transition temperature of the polymerizable liquid crystal compound or higher, or it may be performed separately. From the viewpoint of productivity improvement, it is preferably performed simultaneously. Before heating to above the liquid crystal phase transition temperature of the polymerizable liquid crystal compound, a pre-drying step can also be provided for the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal hybrid composition is not polymerized Appropriately remove the solvent in the coating film. Examples of the drying method in the pre-drying step include natural drying, air-drying, heat drying, and reduced-pressure drying. The drying temperature (heating temperature) in the drying step can be based on the polymerizable liquid crystal compound used. The type of solvent, the type of solvent, its boiling point and its amount, etc. are appropriately determined.

Secondly, in the obtained dry coating film, while maintaining the alignment state of the polymerizable liquid crystal compound, the polymerizable liquid crystal compound is polymerized by light irradiation, thereby forming the polymerizable liquid crystal compound existing in the desired alignment state The polymer is the liquid crystal hardened film. The polymerizable liquid crystal composition of the present invention generally uses a photopolymerization method as a polymerization method. The reason is that damage to the polymerizable liquid crystal compound can be suppressed, and the polymerizable liquid crystal composition is highly polymerized by irradiation with light such as high-intensity ultraviolet rays. 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 or active electron beams selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays can be cited. Among them, in terms of the ease of controlling the progress of the polymerization reaction, or in terms of the use of photopolymerization equipment for a wide range of users in the field, ultraviolet light is preferred, and ultraviolet light is more preferred to enable photopolymerization. The method is to select the type of polymerizable liquid crystal compound or polymerization initiator contained in the polymerizable liquid crystal hybrid composition. In addition, during polymerization, it is also possible to control the polymerization temperature by cooling the dry coating film with an appropriate cooling method and irradiating light with it. If the polymerization of the polymerizable liquid crystal compound is performed at a lower temperature by adopting such a cooling method, even if a substrate having relatively low heat resistance is used, a liquid crystal cured film can be appropriately formed. In addition, it is also possible to promote the polymerization reaction by increasing the polymerization temperature within a range in which abnormalities (deformation of the substrate due to heat, etc.) caused by heat during light irradiation do not occur. During photopolymerization, a patterned cured film can also be obtained by masking or developing.

Examples of the light source of the above-mentioned active energy rays include: 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 wavelength LED (Light Emitting Diode) light source, chemical lamp, black light lamp, microwave excited mercury lamp, metal halide lamp, etc. in the 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 the ultraviolet radiation intensity is irradiated 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 display device, and is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm.

The coating film of the polymerizable liquid crystal hybrid 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. Among them, sometimes the alignment film having the alignment restricting force to align the polymerizable liquid crystal compound in the horizontal direction is called the horizontal alignment film, and the alignment film having the alignment restricting force to align the polymerizable liquid crystal compound in the vertical direction is sometimes called the vertical alignment film. membrane. The alignment restriction force can be arbitrarily adjusted according to the type of alignment film, surface condition, rubbing conditions, and the like. When the alignment film is formed of a photo-alignment polymer, it can be arbitrarily adjusted by polarized light irradiation conditions and the like.

As the alignment film, it is preferable to have solvent resistance that does not dissolve due to coating of the polymerizable liquid crystal hybrid composition, etc., and also have heat resistance to heat treatment for solvent removal or alignment of the polymerizable liquid crystal compound described below Sex. Examples of the alignment film include: alignment films containing alignment polymers, photo-alignment films, groove alignment films with concave and convex patterns or grooves on the surface, stretched films extending in the alignment direction, etc., as regards the accuracy of the alignment angle and From the viewpoint of quality, a photo-alignment film is preferred.

As the alignment polymer, for example, polyamides or gelatins having an amide bond in the molecule, polyimines having an amide bond in the molecule, and polyamides and polyvinyl alcohols as hydrolysates thereof are mentioned. , 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.

An alignment film containing an alignment polymer is usually obtained by applying a composition obtained by dissolving an alignment polymer in a solvent (hereinafter, sometimes referred to as "alignment polymer composition") on a substrate. Remove the solvent; or apply the aligning polymer composition to the substrate, remove the solvent, and perform rubbing (rubbing method). As the solvent, the same as the solvents exemplified above as the solvent that can be used in the polymerizable liquid crystal mixed composition can be mentioned.

The concentration of the aligning polymer in the aligning polymer composition only needs to be within the range where the aligning polymer material can be completely dissolved in the solvent, and it is preferably 0.1-20% in terms of the solid content of the solution. , And more preferably about 0.1 to 10%.

As the alignment polymer composition, commercially available alignment film materials can also be used directly. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industry Co., Ltd.), Optomer (registered trademark, manufactured by JSR Co., Ltd.), 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 hybrid composition to the substrate can be cited.

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, and the like can be cited.

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 friction method, the following method can be cited, that is, a film of an alignment polymer formed on the surface of the substrate by applying an alignment polymer composition to the substrate and annealing The friction cloth is wound and the rotating friction roller touches. During the rubbing treatment, if masking is performed, a plurality of regions (patterns) with different alignment directions can also be formed on the alignment film.

The photo-alignment film is usually obtained by coating 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 The substrate is irradiated with polarized light (preferably polarized UV) after removing the solvent. The photo-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 generates liquid crystal alignment ability by light irradiation. Specifically, examples include: groups involved in photoreactions that are the origin of the alignment ability of liquid crystals, such as the alignment induction or isomerization reaction, dimerization reaction, photocrosslinking reaction, or photolysis reaction of molecules generated by light irradiation. Among them, in terms of excellent alignment, a group that participates in a dimerization reaction or a photocrosslinking reaction is preferred. The photoreactive group is preferably a group having an unsaturated bond, especially a double bond, and particularly preferably one having a carbon-carbon double bond (C=C bond) and a carbon-nitrogen double bond (C=N bond) , At least one group in the group consisting 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 groups, polyalkenyl groups, stilbene groups, stilbazole groups, stilbazolium groups, chalcone groups, and cinnamyl groups. Examples of the photoreactive group having a C=N bond include groups having structures such as aromatic Schiff bases and aromatic hydrazones. Examples of photoreactive groups having N=N bonds include: azophenyl, azonaphthyl, aromatic heterocyclic azo, bisazo, formazan, and those having an oxyazobenzene structure Base and so on. Examples of the photoreactive group having a C=O bond include 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 or stability over time, it is more Preferred are cinnamon base and chalcone base. As a polymer having a photoreactive group, it is particularly preferable that the end portion of the side chain of the polymer has a cinnamyl group that becomes a cinnamic acid structure.

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

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 or the thickness of the target photo-alignment film, compared to the composition for forming a photo-alignment film The mass of it is preferably set to at least 0.2% by mass, more preferably in the range of 0.3-10% by mass. Within a range that does not significantly impair the characteristics of the photo-alignment film, the composition for forming the photo-alignment film may also include a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer.

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 cited. As a method of removing the solvent from the applied 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 can be cited.

The polarized light irradiation may be in the form of directly irradiating the polarized UV light obtained by removing the solvent from the composition for forming a photo-alignment film coated on the substrate, or may be in the form of irradiating the polarized light from the substrate side to transmit the polarized light. In addition, the polarized light is particularly preferably parallel light in nature. The wavelength of the polarized light irradiated may be within the wavelength range in which the photoreactive group of the polymer or monomer having the photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferred. Examples of the light source used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, KrF, ArF and other ultraviolet lasers, and more preferably high-pressure mercury lamps, ultra-high pressure mercury lamps, and metal halide lamps. Among them, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferable 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 or a polarizing element such as Glan-Thompson or Glan-Taylor or a wire grid type polarizing element can be used.

Furthermore, when rubbing or polarized light irradiation is performed, if shielding is performed, it is also possible to form a plurality of regions (patterns) in which the directions of the liquid crystal alignment are different.

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

As a method of obtaining a groove alignment film, a method of forming a concave-convex pattern after exposure through an exposure mask with patterned slits on the surface of the photosensitive polyimide film, followed by development and rinsing treatment; A method of forming a UV-curing resin layer on a plate-shaped master with grooves before hardening, and then moving the formed resin layer to the base material to harden it; and pressing a roll-shaped master with a plurality of grooves against the formed layer The method of UV hardening resin film before hardening of the base material to form unevenness, and then hardening it, etc.

Furthermore, as a material that exhibits the alignment restraining force for aligning the polymerizable liquid crystal compound in a direction perpendicular to the plane of the cured liquid crystal film, in addition to the above-mentioned aligning polymers, fluorine polymers such as perfluoroalkyl groups, and silanes can also be used. Compounds and polysiloxane compounds obtained by their condensation reaction, etc.

In the case of using a silane compound as the material for forming the alignment film, it is easy to reduce the surface tension and improve the adhesion to the layer adjacent to the alignment film, and it is preferable that the constituent elements include Si element and C element. , Silane compounds can be used well. As the silane compound, an ionic compound containing silane can be used. By using such a silane compound, the vertical alignment restraining force can be improved. As the silane compound, one type may be used alone, two or more types may be used in combination, or it may be used in combination with other materials. When the silane compound is a nonionic silane compound, from the viewpoint of easily increasing the vertical alignment restraining force, a silane compound having an alkyl group at the molecular end is preferred, and a silane compound having an alkyl group with 3 to 30 carbon atoms is more preferred. Silane compounds.

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.

The present invention includes an elliptical polarizing plate including the retardation plate 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 on which a pigment with absorption anisotropy is adsorbed or a film coated with a pigment with absorption anisotropy as a polarizing element. Examples of dyes having absorption anisotropy include dichroic dyes.

A film containing a polarizing element with a stretched film adsorbed with a pigment with absorption anisotropy is usually produced by sandwiching at least one surface of the polarizing element manufactured by the following steps with a transparent protective film through an adhesive: The step of uniaxially extending the resin film; the step of dyeing the polyvinyl alcohol resin film with a dichroic pigment to thereby adsorb the dichroic pigment; the step of adsorbing the dichroic pigment to the polyvinyl alcohol by the boric acid aqueous solution A step of processing the resin film; and a step of washing with water after the 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 resin, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and other monomers copolymerizable therewith is 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 can be modified. For example, polyvinyl formal or polyvinyl acetal modified with aldehydes can 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 formed of this polyvinyl alcohol-based resin was used as the blank film of the polarizing film. The method of forming a polyvinyl alcohol-based resin into a film is not particularly limited, and a known method can be used for forming a film. 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 dyeing with a dichroic dye, simultaneously with dyeing, or after dyeing. In the case of uniaxial stretching after dyeing, the uniaxial stretching may be performed before the boric acid treatment, or may be performed 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 hot roll 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 swelled using 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 can be 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 dichroic direct dyes containing bisazo compounds such as C.I. Direct Red 39, and dichroic direct dyes containing compounds such as trisazo and tetrasazo. The polyvinyl alcohol-based resin film is preferably subjected to water immersion treatment 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 per 100 parts by mass of water. In addition, the content of potassium iodide is usually about 0.5 to 20 parts by mass per 100 parts by mass of water. The temperature of the aqueous solution used for dyeing is usually about 20-40°C. In addition, the immersion time (dyeing time) of 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 per 100 parts by mass of water is usually about 1×10 ^-4 to 10 parts by mass, 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) of 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-based 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 per 100 parts by mass of water, and preferably 5 to 12 parts by mass. In the case of using iodine as a dichroic pigment, it is preferable that the boric acid aqueous solution contains potassium iodide. In this case, the content of potassium iodide per 100 parts by mass of water is usually about 0.1-15 parts by mass, preferably 5-12 Mass parts. The immersion time for 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 the boric acid treatment is usually washed with water. The water washing treatment can be performed by, for example, immersing a polyvinyl alcohol-based resin film treated with boric acid in water. The temperature of the water in the water washing treatment is usually about 5 to 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 moisture content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. If the moisture content is less than 5% by mass, the flexibility of the polarizing element will disappear, and the polarizing element may be damaged or broken after drying. In addition, if the moisture content exceeds 20% by mass, the thermal stability of the polarizing element may deteriorate.

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

Examples of the film coated with a dye having absorption anisotropy include a film obtained by coating a composition containing a dichroic dye having liquid crystallinity, or a composition containing a dichroic dye and a polymerizable liquid crystal. The film preferably has a protective film on one or both sides. As this protective film, the same thing as the resin film exemplified above as a base material which can be used for the manufacture of a liquid crystal cured film is mentioned.

The film coated with the pigment having absorption anisotropy is preferably thinner, but if it is too thin, the strength will decrease and the workability tends to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

As the film coated with a dye having absorption anisotropy, specifically, a film described in Japanese Patent Laid-Open No. 2012-33249 and the like can be cited.

The polarizing film is obtained by laminating a transparent protective film on at least one surface of the polarizing element obtained in this way through an adhesive. As the transparent protective film, the same transparent film as the resin film exemplified above as the base material that can be used for the production of the liquid crystal cured film can be used favorably.

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

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

The elliptical polarizing plate of the present invention may also have the structure of the conventional elliptical polarizing plate, or the polarizing film and the retardation plate. As such a structure, for example, the adhesive layer (sheet) used for bonding an ellipsoidal polarizing plate to a display element such as an organic EL or the like is used for the purpose of protecting the surface of the polarizing film or retardation plate from damage or contamination. The protective film and so on.

The elliptical polarizing plate of the present invention can be used in various display devices. A display device is a device with a display element, which includes a light-emitting element or a light-emitting device as a light-emitting source. Examples of display devices include: liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, touch panel display devices, electron emission display devices (for example, field emission display devices (FED)) , Surface field emission display device (SED)), electronic paper (display device using electronic ink or electrophoresis element), plasma display device, projection display device (such as grating light valve (GLV) display device, digital micromirror Device (DMD) display device) and 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 elliptical polarizing plate of the present invention can be used well for organic electroluminescence (EL) display devices and inorganic electroluminescence (EL) display devices, and the laminate of the present invention can be used well for liquid crystal display devices and touch panels Display device. These display devices can exhibit good image display characteristics by having the elliptically polarizing plate of the present invention with excellent optical characteristics. [Example]

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

[Example 1: Production of liquid crystal mixture (A-1)] The liquid crystal mixture represented by the following formula (A-1) (hereinafter referred to as "liquid crystal mixture (A-1)") was synthesized according to the following procedure.

The inside of a 100 mL-four-necked flask equipped with a Dai’s condenser and a thermometer was set in a nitrogen atmosphere, and compound 2.70 represented by formula (E-1) synthesized with patent document (Japanese Patent Laid-Open No. 2010-31223) as a reference was added. Parts, 2.88 parts of the compound represented by the formula (E-2) [the compound represented by the formula (E-1): the molar ratio of the compound represented by the formula (E-2)=50:50], according to the patent document ( Japanese Patent Laid-Open No. 2019-003177) synthesized as a reference: 2 parts of the compound represented by formula (G-1), dimethylaminopyridine (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) 0.02 parts, dibutylhydroxytoluene 0.2 part (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) and 30 parts of chloroform (manufactured by Kanto Chemical Co., Ltd.). After mixing them, use a dropping funnel to further add IPC (Wako Pure Chemical Industries, Ltd.) Manufacturing) 1.92 g to make it equal to 0°C and react overnight. After the reaction, the insoluble components were removed by filtration. The obtained chloroform solution was added dropwise to heptane (manufactured by Wako Pure Chemical Industries, Ltd.) 3 times the weight of the chloroform contained in the solution, and a solid was deposited. Then, the precipitated solid was taken out by filtration, washed with 20 g of heptane 3 times, and dried under reduced pressure at 40° C., thereby obtaining 5.96 g of a liquid crystal mixture (A-1). The yield of the liquid crystal mixture (A-1) was 98% based on the compound (G-1).

[Example 2: Production of Liquid Crystal Mixture (A-2)] Use the compound represented by the formula (E-3) shown below instead of the compound represented by the formula (E-2), and use the compound represented by the formula (E-1): the compound represented by the formula (E-3) Except for the molar ratio of 50:50, the liquid crystal mixture (A-2) was produced in the same manner as in Example 1.

[Example 3: Production of Liquid Crystal Mixture (A-3)] Use the compound represented by the formula (E-3) shown below instead of the compound represented by the formula (E-1), and use the compound represented by the formula (E-2): the compound represented by the formula (E-3) Except for the molar ratio of 50:50, the liquid crystal mixture (A-3) was produced in the same manner as in Example 1.

[Example 4: Production of Liquid Crystal Mixture (A-4)] In addition to using the compound represented by the formula (E-1) and the compound represented by the formula (E-2), the compound represented by the formula (E-3) shown below is used. The molar ratios of the compound represented by the formula (E-1), the compound represented by the formula (E-2) and the compound represented by the formula (E-3) are divided into equal parts. Otherwise, the molar ratios of the compound represented by the formula (E-1), the compound represented by the formula (E-2) and the compound represented by the formula (E-3) are divided into equal parts. 1 The liquid crystal mixture (A-4) is produced in the same manner.

[Example 5: Production of Liquid Crystal Mixture (A-5)] The compound represented by the formula (G-2) shown below was used instead of the compound represented by the formula (G-1), and the liquid crystal mixture (A-5) was produced in the same manner as in Example 1 except for the addition.

[Example 6: Production of Liquid Crystal Mixture (A-6)] The compound represented by the formula (G-2) shown below was used instead of the compound represented by the formula (G-1), and the other was divided, and the liquid crystal mixture (A-6) was produced in the same manner as in Example 2.

[Example 7: Production of Liquid Crystal Mixture (A-7)] The compound represented by the formula (G-2) shown below was used instead of the compound represented by the formula (G-1), and except for the addition, the liquid crystal mixture (A-7) was produced in the same manner as in Example 3.

[Example 8: Production of Liquid Crystal Mixture (A-8)] The compound represented by the formula (G-2) shown below was used in place of the compound represented by the formula (G-1), and the rest was divided, and the liquid crystal mixture (A-8) was produced in the same manner as in Example 4.

[Comparative Example 1] Except that the compound represented by formula (E-2) was not used, only 5.40 parts of the compound represented by formula (E-1) was used, and the polymerizable liquid crystal compound was synthesized in the same manner as in Example 1.

[Comparative Example 2] Except for not using the compound represented by the formula (E-1), only 5.96 parts of the compound represented by the formula (E-2) was used, and the polymerizable liquid crystal compound was synthesized in the same manner as in Example 1.

Table 6 shows the obtained liquid crystal mixture and polymerizable liquid crystal compound. In addition, the polymerizable liquid crystal compound contained in the liquid crystal mixture and the polymerizable liquid crystal compound synthesized in Comparative Examples 1 and 2 represent a compound represented by the following formula (I'). In addition, (G1-1) and (G2-1) in Table 6 respectively represent the following partial structures (* in the formula represents a bond with an oxygen atom).

[表6] 聚合性液晶混合組合物 聚合性液晶化合物 理論混合比率(%)    羧酸化合物混合比(莫耳比) 烷二基碳數    M¹ E-1 E-2 E-3 E^a E^b 比較例1 G1-1 100 0 0 6 6 (I-1) 100 比較例2 G2-1 100 0 0 6 6 (I-1) 100 實施例1 G1-1 50 50 0 4 4 (I-1) 25 4 6 (I-2) 25 6 4 (I-2) 25 6 6 (I-3) 25 實施例2 G1-1 50 0 50 6 6 (I-1) 25 6 8 (I-2) 25 8 6 (I-2) 25 8 8 (I-3) 25 實施例3 G1-1 0 50 50 4 4 (I-1) 25 4 8 (I-2) 25 8 4 (I-2) 25 8 8 (I-3) 25 實施例4 G1-1 33 33 33 4 4 (I-1) 11 4 6 (I-2) 11 6 4 (I-2) 11 4 8 (I-2) 11 8 4 (I-2) 11 6 6 (I-3) 11 6 8 其他(I) 11 8 6 其他(I) 11 8 8 (I-3) 11 實施例5 G2-1 50 50 0 4 4 (I-1) 25 4/6 (G-2對稱結構) (I-2) 50 6 6 (I-3) 25 實施例6 G2-1 50 0 50 6 6 (I-1) 25 6/8 (G-2對稱結構) (I-2) 50 8 8 (I-3) 25 實施例7 G2-1 0 50 50 4 4 (I-1) 25 4/8 (G-2對稱結構) (I-2) 50 8 8 (I-3) 25 實施例8 G2-1 33 33 33 4 4 (I-1) 11 4/6 (G-2對稱結構) (I-2) 22 6/8 (G-2對稱結構) (I-2) 22 6 6 (I-3) 11 4/8 (G-2對稱結構) (I-2) 22 8 8 (I-3) 11

[Table 6] Polymerizable liquid crystal hybrid composition Polymerizable liquid crystal compound Theoretical mixing ratio (%) Mixing ratio of carboxylic acid compound (molar ratio) Alkanediyl carbon number M ¹ E-1 E-2 E-3 E ^a E ^b Comparative example 1 G1-1 100 0 0 6 6 (I-1) 100 Comparative example 2 G2-1 100 0 0 6 6 (I-1) 100 Example 1 G1-1 50 50 0 4 4 (I-1) 25 4 6 (I-2) 25 6 4 (I-2) 25 6 6 (I-3) 25 Example 2 G1-1 50 0 50 6 6 (I-1) 25 6 8 (I-2) 25 8 6 (I-2) 25 8 8 (I-3) 25 Example 3 G1-1 0 50 50 4 4 (I-1) 25 4 8 (I-2) 25 8 4 (I-2) 25 8 8 (I-3) 25 Example 4 G1-1 33 33 33 4 4 (I-1) 11 4 6 (I-2) 11 6 4 (I-2) 11 4 8 (I-2) 11 8 4 (I-2) 11 6 6 (I-3) 11 6 8 Other (I) 11 8 6 Other (I) 11 8 8 (I-3) 11 Example 5 G2-1 50 50 0 4 4 (I-1) 25 4/6 (G-2 symmetric structure) (I-2) 50 6 6 (I-3) 25 Example 6 G2-1 50 0 50 6 6 (I-1) 25 6/8 (G-2 symmetric structure) (I-2) 50 8 8 (I-3) 25 Example 7 G2-1 0 50 50 4 4 (I-1) 25 4/8 (G-2 symmetric structure) (I-2) 50 8 8 (I-3) 25 Example 8 G2-1 33 33 33 4 4 (I-1) 11 4/6 (G-2 symmetric structure) (I-2) twenty two 6/8 (G-2 symmetric structure) (I-2) twenty two 6 6 (I-3) 11 4/8 (G-2 symmetric structure) (I-2) twenty two 8 8 (I-3) 11

[Determination of solubility] Prepare 4 kinds of organic solvents (o-xylene, toluene, cyclopentane, N-methyl-2-pyrrolidone), and add 1 g of each organic solvent to the screw-top bottle. The liquid crystal mixture of the above Example 1 was added to each screw-top bottle, and the complete dissolution was confirmed visually, and the solubility was measured. For the liquid crystal mixtures or polymerizable liquid crystal compounds of Examples 2 to 8, Comparative Examples 1 and 2, the solubility to each organic solvent was also measured in the same manner. The results obtained are shown in Table 7.

[Table 7] Liquid crystal compound O-xylene Toluene Cyclopentanone N-methyl-2-pyrrolidone Comparative example 1 0% 0% 4% 7% Comparative example 2 0% 0% 2% 2% Example 1 5% 7% 20% 26% Example 2 3% 4% 16% twenty four% Example 3 3% 3% 15% twenty two% Example 4 6% 8% 20% 27% Example 5 2% 3% 8% 10% Example 6 2% 2% 7% 9% Example 7 2% 2% 7% 9% Example 8 3% 4% 10% 12%

Claims (14)

A polymerizable liquid crystal hybrid composition, which contains at least 3 different molecular structures and is composed of formula (I): [化1]

[In formula (I), M ¹ represents a divalent linking group containing at least one aromatic hydrocarbon ring or aromatic heterocyclic ring, and B ¹ and B ² each independently represent a single bond and an alkylene group having 1 to 4 carbon atoms , -O-, -S-, -R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, -R ^a7 OC=OOR ^a8 -, -OR ^b O-, -C(=O ) -NR ^c -, -N=N-, -CR ^c =CR ^d -or -C≡C-, where R ^a1 to ^Ra8 are each independently a single bond or an alkylene group with 1 to 4 carbon atoms , R ^b is an alkylene group having 1 to 4 carbons, R ^c and R ^d represent an alkyl group having 1 to 4 carbons or a hydrogen atom, and G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group or aromatic The hydrogen atom contained in the divalent alicyclic hydrocarbon group or aromatic group may be substituted with a halogen atom, an alkyl group with 1 to 4 carbons, a fluoroalkyl group with 1 to 4 carbons, and a fluoroalkyl group with 1 to 4 carbons. The alkoxy group, cyano group or nitro group, the carbon atom constituting the divalent alicyclic hydrocarbon group or aromatic group can be substituted with oxygen atom, sulfur atom or nitrogen atom, when n1 and/or n2 are 2 , 2 G ¹ and/or 2 G ² may be the same or different, respectively, L ¹ and L ² each independently represent a single bond, a C1-C4 alkylene group, -O-, -S-,- R ^a1 OR ^a2 -, -R ^a3 COOR ^a4 -, -R ^a5 OCOR ^a6 -, -R ^a7 OC=OOR ^a8 -, -OR ^b O-, -C(=O)-NR ^c -, -N=N -, -CR ^c =CR ^d -or -C≡C-, where R ^a1 to ^Ra8 are each independently a single bond or an alkylene group having 1 to 4 carbons, and R ^b is a carbon number of 1 to 4 Alkylene, R ^c and R ^d represent an alkyl group with 1 to 4 carbon atoms or a hydrogen atom. When n1 and/or n2 are 2, the two L ¹ and/or the two L ² may be the same or the same. Different, E ^a and E ^b each independently represent an alkanediyl group having 1 to 20 carbons. Here, the hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbon atoms or a halogen atom, _{The -CH 2} -contained in the alkanediyl group may be substituted with -O- or -S- (wherein, when there are plural -O- and/or -S-, they are not adjacent to each other), P is an acryloxy group or a methacryloxy group, n1 and n2 are each independently 1 or 2] the polymerizable liquid crystal compound represented, and the polymerizable liquid crystal compound includes E in the formula (I) ^{The polymerizable liquid crystal compound whose a} and E ^b are the same as each other, among the polymerizable liquid crystal compounds, the polymerizable liquid crystal compound having the smallest carbon number of the alkanediyl group represented by ^{E a} and E ^{b is represented by formula (I-1)} : [化2]

[In formula (I-1), M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 are respectively the same as M ¹ , B ¹ , and B 1 in the above formula (I) B ² , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 are defined the same, E ^{1 is defined the same as E a} and E ^b in the above formula (I), and two E ^{1 are the} same] So In the case of the polymerizable liquid crystal compound (I-1), including the polymerizable liquid crystal compound (I-1), at least one defined based on the structure of the above-mentioned polymerizable liquid crystal compound (I-1) is defined by the formula (I -2): [化3]

[In formula (I-2), M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , E ¹ , P, n1 and n2 are respectively the same as M in the above formula (I-1) ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , E ¹ , P, n1 and n2 are the same, E ² represents the number of carbons different from ^{E 1} in the above formula (I-1) 1 ~20 alkanediyl groups, where the hydrogen atoms contained in the alkanediyl groups may be substituted with C1-C4 alkyl groups or halogen atoms, and the -CH ₂ -contained in the alkanediyl groups may be substituted by Substituted with -O- or -S- (wherein, when there are a plurality of -O- and/or -S-, they are not adjacent to each other)] represented by the polymerizable liquid crystal compound (I-2), and At least one defined based on the structure of the above-mentioned polymerizable liquid crystal compound (I-1) is defined by the formula (I-3): [化4]

[In formula (I-3), M ¹ , B ¹ , B ² , G ¹ , G ² , L ¹ , L ² , P, n1 and n2 are respectively the same as M ¹ , B in the above formula (I-1) in the ^{1, B 2, G 1,} G 2, L 1, L 2, P, n1 and the same N2, E ² the same as (I-2) in the E above formula ^2, and formula (I-3) 2 E ^{2 is the} same] polymerizable liquid crystal compound (I-3). The polymerizable liquid crystal composition of claim 1, wherein in formula (I-1), n1 and n2 are the same. The polymerizable liquid crystal compound of claim 1 or 2, wherein M ¹ is an aromatic hydrocarbon ring or an aromatic heterocyclic ring containing at least one of the total number of π electrons N _{π is 16 or more and less than 36} Valence link base. Such as the polymerizable liquid crystal composition of any one of claims 1 to 3, wherein in formula (I-1), when n1 and n2 are 1, respectively, G ¹ and G ² are the same as each other, and n1 and n2 are respectively the case 2 is, bonded to the ¹¹ B G and B G ² bonded to each of ^two identical, and the other G ¹ and G ² each the same. Such as the polymerizable liquid crystal composition of any one of claims 1 to 4, wherein in formula (I-1), when n1 and n2 are 1, respectively, L ¹ and L ² are the same as each other, and n1 and n2 are respectively In the case of 2, L ¹ and L ^{2 respectively bonded to E 1} are the same as each other, and the other L ¹ and L ² are the same as each other. The polymerizable liquid crystal hybrid composition according to any one of claims 1 to 5, wherein each E ^{1 in} formula (I-1) and formula (I-2) and formula (I-2) and formula (I-3) Each E ² in) is an alkanediyl group with 4-20 carbons, and the carbon number of the alkanediyl group represented by ^{each E 1} in formula (I-1) and formula (I-2) is the same as that of formula (I The difference in carbon number of the alkanediyl group represented by ^{each E 2} in -2) and formula (I-3) is 2 or more. The polymerizable liquid crystal hybrid composition according to any one of claims 1 to 6, wherein among the polymerizable liquid crystal compounds represented by formula (I), relative to M ¹ , B ¹ , B ² , G ¹ , G ² , The total molar amount of the polymerizable liquid crystal compound represented by formula (I) in which L ¹ , L ² , P, n1 and n2 are mutually the same respectively includes the polymerizable liquid crystal compound represented by formula (I-1) and the formula ( 10 mol% or more of the polymerizable liquid crystal compound represented by I-2) and the polymerizable liquid crystal compound represented by formula (I-3). The polymerizable liquid crystal hybrid composition according to any one of claims 1 to 7, which contains an organic solvent. A phase difference plate comprising a liquid crystal cured film, the liquid crystal cured film being a cured product of the polymerizable liquid crystal hybrid composition according to any one of claims 1 to 8, and which is in the polymerizable liquid crystal hybrid composition The polymerizable liquid crystal compound is hardened in the aligned state. Such as the phase difference plate of claim 9, wherein the liquid crystal cured film has the optical characteristics represented by formulas (1), (2) and (3), Re(450)/Re(550)≦1.00 (1) 1.00≦Re(650)/Re(550) (2) 100 nm≦Re(550)≦180 nm (3) [In the formula, Re(λ) represents the in-plane retardation value of the liquid crystal cured film at the wavelength λ nm, Re=(nx(λ)－ny(λ))×d(d represents the thickness of the liquid crystal cured film, nx represents In the refractive index ellipsoid formed by the liquid crystal cured film, the principal refractive index at the wavelength λ nm in the direction parallel to the plane of the liquid crystal cured film, ny represents the refractive index ellipsoid formed by the liquid crystal cured film, relative to the liquid crystal The plane of the cured film is parallel and the refractive index at the wavelength λ nm in the direction orthogonal to the direction of nx)]. Such as the phase difference plate of claim 9, wherein the liquid crystal cured film has optical properties represented by formulas (4), (5) and (6), Rth(450)/Rth(550)≦1.00 (4) 1.00≦Rth(650)/Rth(550) (5) -100 nm≦Rth(550)≦-40 nm (6) [In the formula, Rth(λ) represents the retardation value of the thickness direction of the liquid crystal cured film at the wavelength λ nm, Rth=((nx(λ)+ny(λ))/2-nz)×d(d represents the liquid crystal hardening The thickness of the film, nx represents the 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, and ny represents the refractive index ellipsoid formed by the liquid crystal cured film Wherein, the refractive index at the wavelength λ nm parallel to the plane of the liquid crystal cured film and orthogonal to the direction of nx, nz represents the refractive index ellipsoid formed by the liquid crystal cured film, relative to the liquid crystal cured film The refractive index at the wavelength λ nm in the direction perpendicular to the plane)]. An elliptical polarizing plate comprising the phase difference plate and polarizing film according to any one of claims 9 to 11. An organic EL display device provided with an elliptical polarizing plate as in claim 12. A method for producing a polymerizable liquid crystal hybrid composition according to any one of claims 1 to 8, which comprises making the reactive groups R ² and (III-2) of the compound represented by the following formula (III-1) The reactive group R ^{2 of the compound represented and R 1} of the compound represented by (III-3) react, [Chemical 5]

[Wherein, R ¹ is and R ² each independently represents a reactive ^{group, M 1, L 1, L} 2, G 1, G 2, P, n1 and n2 represent the formula M ^{1 (I-1)} in the, ^{L 1, L 2, G 1} , G same as the meanings ^2, P, n1 same of n2 meaning and, E ¹ represented by the formula (I-1) in the E ^1, in E ² represented by the formula (I-2) The same meaning as ^{E 2].}