Polymerizable liquid crystal composition and liquid crystal display element

Abstract

The present invention provides a liquid crystal composition containing a polymerizable compound, which does not hinder the alignment restraint force that makes the liquid crystal molecules align vertically, does not cause or rarely causes display defects due to changes in the pretilt angle, and has a high voltage holding rate, and also provides a liquid crystal display element using the liquid crystal composition. The liquid crystal composition of the present invention solves the above-mentioned problems by providing a liquid crystal composition containing a specific polymerizable compound and providing a liquid crystal display element using the liquid crystal composition.

Description

Technical Field

[0001] The present invention relates to a liquid crystal composition containing a polymerizable compound and a liquid crystal display element using the same. Background Art

[0002] Generally speaking, liquid crystal display elements such as liquid crystal panels and liquid crystal displays change the arrangement of liquid crystal molecules through external stimuli such as electric fields, and use the accompanying changes in optical properties for display. Usually, such liquid crystal display elements are composed of liquid crystal molecules filled in the gap between two transparent substrates, and an alignment film is formed on the surface of the substrate that contacts the liquid crystal molecules to pre-align the liquid crystal molecules in a specific direction.

[0003] However, there are the following problems: during the manufacturing process of liquid crystal display elements, alignment defects occur due to damage and dust on the alignment film surface, and as the substrate size increases, it is difficult to design and manage the alignment film for obtaining a long-term uniform orientation across the entire surface of the substrate.

[0004] In contrast, in recent years, a liquid crystal display element that does not require an alignment film by using a liquid crystal composition containing a spontaneous alignment material that controls the alignment of liquid crystal molecules in a liquid crystal layer has been developed (Patent Documents 1 and 2).

[0005] The manufacture of a liquid crystal display element that does not require an alignment film is performed in the following manner: a liquid crystal composition containing a liquid crystal compound, a spontaneous alignment material, and a polymerizable compound is injected between substrates, and the spontaneous alignment material and the polymerizable compound are polymerized under a voltage applied to align the liquid crystal molecules, thereby fixing the alignment of the liquid crystal molecules. As causes of poor display (i.e., screen burn-in) of the liquid crystal display element, it is known that the cause is caused by impurities and changes in the alignment of the liquid crystal molecules (changes in the pretilt angle).

[0006] Burn-in caused by the change in the pretilt angle of liquid crystal molecules is that when the same pattern is displayed for a long time in a liquid crystal display element, the structure of the polymer changes, resulting in a change in the pretilt angle. Therefore, it is necessary to form a polymerizable compound having a rigid structure that does not change the polymer structure.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: U.S. Patent Publication No. 2017-0123275

[0010] Patent Document 2: Japanese Patent Application No. 2015-168826 Summary of the invention

[0011] Problems to be solved by the invention

[0012] The present invention provides a liquid crystal composition containing a polymerizable compound, which does not hinder the orientation restraining force that makes the liquid crystal molecules vertically oriented, suppresses the residual polymerizable compound when the liquid crystal display element is made, and the display defects caused by the decrease of voltage holding ratio and the change of pretilt angle do not occur or occur very rarely; and provides a liquid crystal display element using the liquid crystal composition.

[0013] Means for solving problems

[0014] The present inventors have conducted intensive studies and have found that the above-mentioned problems can be solved by a liquid crystal composition containing one or two or more polymerizable compounds represented by the general formula (i), thereby completing the present invention.

[0015] [Chemistry 1]

[0016]

[0017] (Where X i1 , X i2 , X i3 , X i4 , X i5 , X i6 , X i7 , X i8 , X i9 , X i10 , X i11 and X i12 each independently represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom,

[0018] Selected from X i1 ~X i12 At least two of the above are independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a halogen atom,

[0019] P i1 and P i2 Each independently represents any one of the following formula (RI) to formula (R-IX),

[0020] [Chemistry 2]

[0021]

[0022] (Where R 21 , R 31 , R 41 , R 51 and R 61each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, W represents a single bond, -O- or a methylene group, T represents a single bond or -COO-, p, t and q each independently represent 0, 1 or 2,

[0023] Sp i1 and Sp i2 each independently represents a single bond or an alkylene group having 1 to 15 carbon atoms, wherein one or more -CH2- in the alkylene group may be substituted by -O-, -OCO- or -COO- in a manner that the oxygen atom is not directly adjacent thereto,

[0024] n i1 represents 0, 1 or 2,

[0025] L i1 and L i2 Each independently represents a single bond, -OCH2-, -CH2O-, -C2H4-, -OC2H4O-, -COO-, -OCO-, -CH=CR a -COO-, -CH=CR a -OCO-, -COO-CR a =CH-, -OCO-CR a =CH-, -(CH2) z -COO-, -(CH2) z -OCO-, -OCO-(CH2) z -、-COO-(CH2) z -, -CH=CH-, -CF2O-, -OCF2- or -C≡C- (where R a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and z represents an integer of 1 to 4),

[0026] When there are multiple X i5 , X i6 , X i7 , X i8 and / or L i2 In the case of , they may be the same or different.)

[0027] In addition, the object of the present invention is to provide a liquid crystal display element using the liquid crystal composition, an active matrix driven liquid crystal display element using the liquid crystal composition, a liquid crystal display element for PSA mode, PSVA mode, PS-IPS mode or PS-FSS mode using the liquid crystal composition, and a liquid crystal display element using the liquid crystal composition and having no orientation film on the surface of at least one substrate in a pair of substrates.

[0028] Effects of the Invention

[0029] By using the polymerizable liquid crystal composition of the present invention, a liquid crystal display element with little change in pretilt angle can be obtained. In addition, the liquid crystal display element made using the polymerizable liquid crystal composition of the present invention has the following characteristics, namely: having a high voltage holding ratio (VHR), and further, there is very little unpolymerized polymerizable compound in the element. DETAILED DESCRIPTION

[0030] In the above general formula (i), X i1 , X i2 , X i3 , X i4 , X i5 , X i6 , X i7 , X i8 , X i9 , X i10 , X i11 and X i12 Each independently represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, and the alkyl group and the alkoxy group are preferably linear, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a propoxy group, a fluorine atom or a chlorine atom, preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group or a fluorine atom, preferably a hydrogen atom, a methyl group, a methoxy group or a fluorine atom. Preferably, two or more groups are other than hydrogen atoms, preferably two or three groups are other than hydrogen atoms, and preferably two groups are other than hydrogen atoms.

[0031] When the orientation of the liquid crystal is important, the preferred carbon number of the alkyl group and the alkoxy group is preferably 10 to 18, and when the solubility in the liquid crystal compound is important, it is preferably 1 to 4. In addition, when the tilt angle stability is important, the alkyl group is preferred. In addition, the alkyl group and the alkoxy group may be linear or branched, and linear is particularly preferred.

[0032] Preferably X i1 , X i2 , X i3 , X i4 , X i5 , X i6 , X i7 , X i8 , X i9 , X i10 , X i11 and X i12Two or more of them represent an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a halogen atom. When the orientation of the liquid crystal is important, the preferred carbon number of the alkyl group and the alkoxy group is preferably 10 to 18, and when the solubility in the liquid crystal compound is important, it is preferably 1 to 4. In addition, when the tilt angle stability is important, the alkyl group is preferred. In addition, the alkyl group and the alkoxy group may be linear or branched, and linear is particularly preferred.

[0033] In addition, when the voltage holding ratio is important, it is preferable to i5 , X i6 , X i7、 X i8 , X i9 , X i10 , X i11 and X i12 At least one of the above is an alkyl group having 1 to 18 carbon atoms. When the orientation of the liquid crystal is important, the number of carbon atoms of the above alkyl group is preferably 10 to 18, and when the solubility in the liquid crystal compound is important, the number of carbon atoms is preferably 1 to 4. In addition, when the tilt stability is important, the number of carbon atoms is preferably 1 to 3. The above alkyl group may be linear or branched, and linear is particularly preferred.

[0034] In the above general formula (i), in order to reduce the amount of residual monomers after UV irradiation, it is preferred that X i11 or X i12 One or two of them are hydrogen atoms.

[0035] In the above general formula (i), when solubility in a liquid crystal composition is important, X is preferably i5 , X i6 , X i7、 X i8 , X i9 , X i10 , X i11 and X i12 At least one of them is a halogen atom, particularly preferably fluorine.

[0036] In the above general formula (i), n i1 When it is 1, if the tilt angle stability is important, select X i5 , X i6 , X i7 , and X i8 Two of them are preferably an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a halogen atom, and particularly preferably an alkyl group having 1 to 3 carbon atoms or fluorine.

[0037] In the above general formula (i), L i1Preferred is a single bond, -OCH2-, -CH2O-, -C2H4-, -COO-, -OCO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -C2H4-COO-, -C2H4-OCO-, -OCO-C2H4-, -COO-C2H4-, -CH=CH-, -CF2O-, -OCF2- or -C≡C-; more preferred is a single bond, -OCH2-, -CH2O-, -C2H4-, -COO-, -OCO-, -C2H4-COO-, -C2H4-OCO-, -OCO-C2H4-, -COO-C2H4-, -CF2O-, -OCF2- or -C≡C-; particularly preferred is a single bond.

[0038] In the above general formula (i), L i2 Preferred is a single bond, -OCH2-, -CH2O-, -C2H4-, -COO-, -OCO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -C2H4-COO-, -C2H4-OCO-, -OCO-C2H4-, -COO-C2H4-, -CH=CH-, -CF2O-, -OCF2- or -C≡C-; more preferred is a single bond, -OCH2-, -CH2O-, -C2H4-, -COO-, -OCO-, -C2H4-COO-, -C2H4-OCO-, -OCO-C2H4-, -COO-C2H4-, -CH=CH-, -CF2O-, -OCF2- or -C≡C-; particularly preferred is a single bond.

[0039] In the above general formula (i), L i1 With L i2 They may be the same or different from each other, and more preferably L i1 With L i2 same.

[0040] In the general formula (i), P i1 and P i2 Each independently represents any one of the following formula (RI) to formula (R-IX).

[0041] [Chemistry 3]

[0042]

[0043] (Where R 21 , R 31 , R 41 , R 51 and R 61are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, W is a single bond, -O-, or a methylene group, T is a single bond or -COO-, and p, t, and q are independently 0, 1, or 2.

[0044] Among them, in the above general formula (i), P i1 and P i2 Preferably, they are independently selected from the group consisting of formula (RI), formula (R-II), formula (R-III), formula (R-IV), formula (RV) or formula (R-VII), more preferably formula (RI), formula (R-II), formula (R-III) or formula (R-IV), more preferably formula (RI), and further preferably acryloyloxy (R in (RI) 21 is a substituent of a hydrogen atom) or a methacryloyloxy group (R in (RI) 21 is a methyl substituent), and more preferably a methacryloyloxy group.

[0045] In the general formula (i), Sp i1 and Sp i2 Preferably, each independently represents a single bond or an alkylene group having 1 to 3 carbon atoms, and more preferably a single bond.

[0046] The polymerizable compound represented by the general formula (i) may be used alone or in combination of two or more.

[0047] The liquid crystal composition of the present invention preferably contains 1 to 5 polymerizable compounds represented by general formula (i), preferably 1 to 4 polymerizable compounds represented by general formula (i), and preferably 1 to 3 polymerizable compounds represented by general formula (i).

[0048] Regarding the lower limit of the content of the polymerizable compound represented by the general formula (i) in the liquid crystal composition of the present invention, it is preferably 0.05 mass %, preferably 0.08 mass %, preferably 0.1 mass %, preferably 0.15 mass %, preferably 0.17 mass %, preferably 0.2 mass %, preferably 0.22 mass %, preferably 0.25 mass %, preferably 0.27 mass %, preferably 0.3 mass %, preferably 0.32 mass %, preferably 0.35 mass %, preferably 0.37 mass %, preferably 0.4 mass %, preferably 0.42 mass %, preferably 0.45 mass %, preferably 0.48 mass %, preferably 0.5 mass %, preferably 0.53 mass %, preferably 0.55 mass %, preferably 0.58 mass %, preferably 0.60 mass %, preferably 0.63 mass %, preferably 0.65 mass %, preferably 0.68 mass %, preferably 0.70 mass %, preferably 0.73 mass %, preferably 0.75 mass %, preferably 0.78 mass %, preferably 0.8 mass %. Regarding the upper limit of the content of the polymerizable compound represented by the general formula (i) in the liquid crystal composition of the present invention, it is preferably 2.5 mass %, preferably 2.3 mass %, preferably 2.1 mass %, preferably 2 mass %, preferably 1.8 mass %, preferably 1.6 mass %, preferably 1.5 mass %, preferably 1 mass %, preferably 0.95 mass %, preferably 0.9 mass %, preferably 0.85 mass %, preferably 0.8 mass %, preferably 0.75 mass %, preferably 0.7 mass %, preferably 0.65 mass %, preferably 0.6 mass %, preferably 0.55 mass %, preferably 0.5 mass %, preferably 0.45 mass %, preferably 0.4 mass %.

[0049] When the polymerizable compound represented by the general formula (i) is used alone, a smaller amount is preferred from the viewpoint of storage stability at low temperatures, and when a plurality of polymerizable compounds represented by the general formula (i) are used in combination, a larger amount is preferred in order to better exhibit the effects of the present application.

[0050] In order to achieve both storage stability at low temperatures and change in pretilt angle, the content of the polymerizable compound represented by general formula (i) in the liquid crystal composition of the present invention is preferably 0.1 to 1%, preferably 0.2 to 0.8%, preferably 0.3 to 0.75%, preferably 0.35 to 0.7%, preferably 0.4 to 0.7%. Suitable polymerizable compounds represented by general formula (i) of the present invention include the following formulas RM-1 to RM-33.

[0051] [Chemistry 4]

[0052]

[0053] [Chemistry 5]

[0054]

[0055] Preferred are the above-mentioned formulas RM-1 to RM-33, more preferred are RM-3 to RM-11, RM-22 to RM-30, and further preferred are RM-3, RM-11, RM-25, RM-28 to RM-30.

[0056] Although the liquid crystal composition of the present invention contains a polymerizable compound represented by general formula (i), other polymerizable compounds may also be used in combination. As the other polymerizable compound, a compound represented by the following general formula (P) is preferred. In addition, it is preferred to contain one or more of the polymerizable monomers.

[0057] [Chemistry 6]

[0058]

[0059] (In the above general formula (P), R p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms, or -Sp p2 -P p2 , one or more non-adjacent -CH2- in the alkyl group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and one or more hydrogen atoms in the alkyl group may be independently substituted by cyano, fluorine or chlorine atoms,

[0060] P p1 and P p2 Each independently represents the general formula (P p1 -1)~Formula(P p1 -9) any one of the following,

[0061] [Chemistry 7]

[0062]

[0063] (Where R p11 and R p12 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, and W p11 represents a single bond, -O-, -COO- or methylene, t p11 Represents 0, 1 or 2, and there are multiple R in the molecule p11 , R p12 , W p11 and / or p11 , they can be the same or different. )

[0064] Sp p1 and Spp2 Each independently represents a single bond or a spacer,

[0065] Z p1 and Z p2 Each independently represents a single bond, -O-, -S-, -CH2-, -OCH2-, -CH2O-, -CO-, -C2H4-, -COO-, -OCO-, -OCOOCH2-, -CH2OCOO-, -OCH2CH2O-, -CO-NR ZP1 -、-NR ZP1 -CO-, -SCH2-, -CH2S-, -CH=CR ZP1 -COO-, -CH=CR ZP1 -OCO-, -COO-CR ZP1 =CH-, -OCO-CR ZP1 =CH-, -COO-CR ZP1 =CH-COO-, -COO-CR ZP1 =CH-OCO-, -OCO-CR ZP1 =CH-COO-, -OCO-CR ZP1 =CH-OCO-, -(CH2)2-COO-, -(CH2)2-OCO-, -OCO-(CH2)2-, -(C=O)-O-(CH2)2-, -CH=CH-, -CF= CF-, -CF=CH-, -CH=CF-, -CF2-, -CF2O-, -OCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2- or -C≡C- (where R ZP1 Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and there are multiple R ZP1 , they may be the same or different),

[0066] A p1 , A p2 and A p3 Each independently represents a group selected from the following groups (a p )~group (c p ),

[0067] (a p ) 1,4-cyclohexylene (one -CH2- or two or more non-adjacent -CH2- in the group may be substituted by -O-),

[0068] (b p ) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= in the group may be substituted with -N=), and

[0069] (cp ) naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl (one -CH= or two or more non-adjacent -CH= in these groups may be substituted with -N=),

[0070] Present in the above group (a p ), group (b p ) and group (c p ) may be replaced by a halogen atom, a cyano group, an alkyl group having 1 to 8 carbon atoms, or -Sp p2 -P p2 Substitution, one or two or more non-adjacent -CH2- in the alkyl group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-,

[0071] m p1 Represents 0, 1, 2 or 3, there are multiple Z in the molecule p1 , A p2 、Sp p2 and / or P p2 When they are the same or different, p1 is 0 and A p1 When A is phenanthrene-2,7-diyl or anthracene-2,6-diyl p3 Represents a single bond.

[0072] However, the compounds represented by general formula (i) are excluded.)

[0073] In the general formula (P) of the present invention, R p1 Preferably -Sp p2 -P p2 .

[0074] P p1 and P p2 Preferably, they are independently p1 -1)~Formula(P p1 -3), preferably (P p1 -1).

[0075] R p11 and R p12 Each independently preferably is a hydrogen atom or a methyl group.

[0076] t p11 Preferably 0 or 1.

[0077] W p11 Preferred is a single bond, a methylene group or an ethylene group.

[0078] mp1 Preferably it is 0, 1 or 2, preferably 0 or 1.

[0079] Z p1 and Z p2 Each independently represents preferably a single bond, -OCH2-, -CH2O-, -CO-, -C2H4-, -COO-, -OCO-, -COOC2H4-, -OCOC2H4-, -C2H4OCO-, -C2H4COO-, -CH=CH-, -CF2-, -CF2O-, -(CH2)2-COO-, -(CH2)2-OCO-, -OCO-(CH2)2-, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH2)2-, -OCF2- or -C≡C-, preferably a single bond, -OCH2-, -CH2O-, -C2H4-, -COO-, -OCO-, -COOC2H4-, -OCOC2H4-, -C2H4OCO-, -C2H4COO-, -CH=CH-, -(CH2)2-COO-, -(CH2)2-OCO-, -OCO-(CH2)2-, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH2)2- or -C≡C-, preferably only one of -OCH2-, -CH2O-, -C2H4-, -COO-, -OCO-, -COOC2H4-, -OCOC2H4-, -C2H4OCO-, -C2H4COO-, -CH=CH-, - (CH2)2-COO-, -(CH2)2-OCO-, -OCO-(CH2)2-, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH2)2- or -C≡C- and all the others are single bonds. It is preferred that only one of -OCH2-, -CH2O-, -C2H4-, -COO- or -OCO- exists in the molecule and all the others are single bonds. It is preferred that all are single bonds.

[0080] In addition, Z present in the molecule is preferably p1 and Z p2 Only one of them is a linking group selected from the group consisting of -CH=CH-COO-, -COO-CH=CH-, -(CH2)2-COO-, -(CH2)2-OCO-, -O-CO-(CH2)2-, and -COO-(CH2)2-, and the others are single bonds.

[0081] Sp p1 and Sp p2Each independently represents a single bond or a spacer, the spacer is preferably an alkylene group having 1 to 30 carbon atoms, the -CH2- in the alkylene group may be replaced by -O-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C- when the oxygen atoms are not directly connected to each other, the hydrogen atom in the alkylene group may be replaced by a halogen atom, and is preferably a straight-chain alkylene group having 1 to 10 carbon atoms or a single bond.

[0082] Preferably A p1 , A p2 and A p3 Each independently represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and is preferably a 1,4-phenylene group. In order to improve compatibility with liquid crystal compounds, the 1,4-phenylene group is preferably substituted with one fluorine atom, one methyl group or one methoxy group.

[0083] The total content of the compounds represented by the general formula (P) relative to the composition of the present application containing the compounds represented by the general formula (P) is preferably 0.05 to 10%, preferably 0.1 to 8%, preferably 0.1 to 5%, preferably 0.1 to 3%, preferably 0.2 to 2%, preferably 0.2 to 1.3%, preferably 0.2 to 1%, preferably 0.2 to 0.56%.

[0084] The preferred lower limit of the total content of the compounds represented by the general formula (P) is 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, or 0.3% relative to the composition containing the compounds represented by the general formula (P) of the present application.

[0085] The preferred upper limit of the total content of the compounds represented by the general formula (P) is 10%, 8%, 5%, 3%, 1.5%, 1.2%, 1%, 0.8%, or 0.5% relative to the composition containing the compounds represented by the general formula (P) of the present application.

[0086] If the content is too low, the effect of adding the compound represented by the general formula (P) will be difficult to show, and the alignment restraint of the liquid crystal composition will be weak or weakened over time. If it is too high, the amount of residue after curing will increase, curing will take time, and the reliability of the liquid crystal will decrease. Therefore, the balance between them is considered to set the content.

[0087] Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-1-1) to (P-1-46).

[0088] [Chemistry 8]

[0089]

[0090] [Chemistry 9]

[0091]

[0092] [Chemistry 11]

[0093]

[0094] [Chemistry 12]

[0095]

[0096] (Where P p11 , P p12 、Sp p11 and Sp p12 Indicates that P in the general formula (P-1) p11 , P p12 、Sp p11 and Sp p12 Same meaning.)

[0097] Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-2-1) to (P-2-12).

[0098] [Chemistry 13]

[0099]

[0100] (Where P p21 , P p22 、Sp p21 and Sp p22 Indicates that P in the general formula (P-2) p21 , P p22 、Sp p21 and Sp p22 Same meaning.)

[0101] Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-3-1) to (P-3-15).

[0102] [Chemistry 14]

[0103]

[0104] [Chemistry 15]

[0105]

[0106] (Where P p31 , P p32 、Sp p31 and Sp p32Indicates that P in the general formula (P-3) p31 , P p32 、Sp p31 and Sp p32 Same meaning.)

[0107] Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-4-1) to (P-4-21).

[0108] [Chemistry 16]

[0109]

[0110] [Chemistry 17]

[0111]

[0112] [Chemistry 18]

[0113]

[0114] [Chemistry 19]

[0115]

[0116] (Where P p41 , P p42 、Sp p41 and Sp p42 Indicates that P in the general formula (P-4) p41 , P p42 、Sp p41 and Sp p42 Same meaning.)

[0117] The liquid crystal composition according to the present invention may contain one to three polymerizable compounds represented by the general formula (i) and one to three polymerizable compounds represented by the general formula (P) having a structure different from that of the general formula (i).

[0118] Regarding the lower limit of the total content of the compound represented by the general formula (i) and the polymerizable compound represented by the general formula (P), the general formula (i) is preferably 0.01 mass %, preferably 0.03 mass %, preferably 0.05 mass %, preferably 0.08 mass %, preferably 0.10 mass %, preferably 0.12 mass %, preferably 0.15 mass %, preferably 0.17 mass %, preferably 0.2 mass %, preferably 0.22 mass %, preferably 0.25 mass %, preferably 0.27 mass %, preferably 0.3 mass %, preferably 0.32 mass %, preferably 0.35 mass %, preferably 0.37 mass %, preferably 0.4 mass %.

[0119] Regarding the upper limit of the total content of the polymerizable compound represented by the general formula (i) and the polymerizable compound represented by the general formula (P) in the liquid crystal composition of the present invention, it is preferably 2.0 mass %, preferably 1.8 mass %, preferably 1.5 mass %, preferably 1.0 mass %, preferably 0.8 mass %, preferably 0.5 mass %, preferably 0.47 mass %, preferably 0.5 mass %, preferably 0.45 mass %, preferably 0.43 mass %, preferably 0.40 mass %, preferably 0.37 mass %, preferably 0.35 mass %, preferably 0.32 mass %, preferably 0.30 mass %, preferably 0.27 mass %, preferably 0.25 mass %, preferably 0.23 mass %, preferably 0.20 mass %.

[0120] The liquid crystal composition may further contain liquid crystal molecules and an alignment aid having a function of spontaneously aligning the liquid crystal molecules and having an adsorption group (polar group).

[0121] (Orientation aid)

[0122] Orientation aids (spontaneous orientation compounds) have the following functions: interacting with components that are directly in contact with the liquid crystal layer containing the liquid crystal composition (electrodes (such as ITO), substrates (such as glass substrates, acrylic substrates, transparent substrates, flexible substrates, etc.), resin layers (such as color filters, orientation films, overcoats, etc.), insulating films (such as inorganic material films, SiNx, etc.)), and inducing vertical arrangement or planar orientation of liquid crystal molecules contained in the liquid crystal layer.

[0123] The alignment aid preferably contains a polymerizable group for polymerization, a mesogen group similar to liquid crystal molecules, an adsorption group (polar group) capable of interacting with a member directly in contact with the liquid crystal layer, and an alignment inducing group that induces the alignment of liquid crystal molecules.

[0124] The adsorbing group and the alignment inducing group are linked to the mesogen group, and the polymerizable group is preferably substituted on the mesogen group, the adsorbing group and the alignment inducing group directly or via a spacer as required. It is particularly preferred that the polymerizable group is substituted on the mesogen group in a state of being incorporated into the adsorbing group.

[0125] In the following chemical formulas, * on the left and * on the right represent connecting bonds.

[0126] “Orientation-inducing group”

[0127] The alignment inducing group has a function of inducing the alignment of liquid crystal molecules, and is preferably a group represented by the following general formula (AK).

[0128] [Chemistry 20]

[0129] R AK1 -* (AK)

[0130] In the formula, R AK1 It represents a linear or branched alkyl group having 1 to 20 carbon atoms. One or more -CH2- in the alkyl group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- when the oxygen atom is not directly connected, and one or more hydrogen atoms in the alkyl group may be independently substituted by a halogen group.

[0131] R AK1 It preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably represents a linear alkyl group having 1 to 20 carbon atoms, and further preferably represents a linear alkyl group having 1 to 8 carbon atoms.

[0132] Furthermore, one or two or more non-adjacent -CH2- groups in the alkyl group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-.

[0133] Furthermore, the hydrogen atom in the alkyl group may be substituted by a fluorine atom or a chlorine atom, and may be substituted by a fluorine atom.

[0134] From the viewpoint of imparting so-called amphiphilicity to the liquid crystal layer to the alignment auxiliary agent, the alignment inducing group is preferably linked to a mesogen group.

[0135] "Polymerization Group"

[0136] The polymerizable group is preferably P AP1 -Sp AP1 -express.

[0137] P AP1 Preferred are groups selected from the group represented by the following general formulae (AP-1) to (AP-9).

[0138] [Chemistry 21]

[0139]

[0140] In the formula, R AP1 and R AP2 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. Among them, one or more -CH2- in the alkyl group may be substituted by -O- or -CO-, and one or more hydrogen atoms in the alkyl group may be independently substituted by a halogen atom or a hydroxyl group.

[0141] W AP1 It represents a single bond, -O-, -COO- or -CH2-.

[0142] t AP1 Represents 0, 1, or 2.

[0143] P AP1 Preferred are groups represented by the following general formulae (AP-1) to (AP-7), more preferred are groups represented by the following general formulae (AP-1) or (AP-2), and still more preferred are groups represented by general formula (AP-1).

[0144] Sp AP1 It preferably represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably represents a single bond or a linear alkylene group having 1 to 20 carbon atoms, and further preferably represents a single bond or a linear alkylene group having 2 to 10 carbon atoms.

[0145] In addition, Sp AP1 In the alkylene group, one or two or more non-adjacent -CH2- groups may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-.

[0146] In the orientation aid, the polymerizable group (P AP1 -Sp AP1 The number of -) is preferably 1 to 5, more preferably 1 to 4, further preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.

[0147] P AP1 -Sp AP1 The hydrogen atoms in - may be substituted by polymerizable groups, adsorbable groups and / or orientation inducing groups.

[0148] Polymerization group (P AP1 -Sp AP1 -) can be connected to a polymerizable group, a mesogen group, an adsorption group and / or an alignment inducing group.

[0149] In addition, the polymerizable group (P AP1 -Sp AP1 -) is preferably connected to a mesogen group, an adsorption group or an alignment inducing group, and more preferably connected to a mesogen group or an adsorption group.

[0150] Among them, there are multiple P in the molecule AP1 and / or Sp AP1 -, they may be the same as or different from each other.

[0151] "Liquid Crystal Primordial"

[0152] The mesogen group means a group having a rigid part, for example, a group having one or more cyclic groups, preferably a group having 2 to 4 cyclic groups, and more preferably a group having 3 to 4 cyclic groups. The cyclic groups may be connected by a linking group as required. The mesogen group preferably has a skeleton similar to that of the liquid crystal molecule (liquid crystal compound) used in the liquid crystal layer.

[0153] In this specification, "cyclic group" means an atomic group whose constituent atoms are connected to form a ring, including a carbocyclic ring, a heterocyclic ring, a saturated or unsaturated cyclic structure, a monocyclic ring, a bicyclic structure, a polycyclic structure, an aromatic group, a non-aromatic group, etc.

[0154] The cyclic group may contain at least one heteroatom, and may be substituted with at least one substituent (a halogen group, a polymerizable group, an organic group (alkyl group, alkoxy group, aryl group, etc.)). When the cyclic group is a monocyclic ring, the mesogen group preferably contains two or more monocyclic rings.

[0155] The mesogen group is preferably represented by, for example, the general formula (AL).

[0156] [Chemistry 22]

[0157]

[0158] In the formula, Z AL1 It represents a single bond, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CF2O-, -OCF2-, -CH=CHCOO-, -OCOCH=CH-, -CH2-CH2COO-, -OCOCH2-CH2-, -CH=C(CH3)COO-, -OCOC(CH3)=CH-, -CH2-CH(CH3)COO-, -OCOCH(CH3)-CH2-, -OCH2CH2O-, or an alkylene group having 1 to 20 carbon atoms. In the alkylene group, one or two or more non-adjacent -CH2- groups may be substituted with -O-, -COO-, or -OCO-.

[0159] A AL1 and A AL2 Each independently represents a divalent cyclic group.

[0160] Z AL1 , A AL1 and A AL2 One or more hydrogen atoms in the molecule may be independently replaced by halogen groups, adsorbent groups, P AP1 -Sp AP1 - or substituted by a monovalent organic group.

[0161] Among them, there are multiple Z in the molecule AL1 and A AL1, they may be the same as or different from each other.

[0162] m AL1 Indicates an integer from 1 to 5.

[0163] In the general formula (AL), Z AL1 It is preferably a single bond or an alkylene group having 2 to 20 carbon atoms, more preferably a single bond or an alkylene group having 2 to 10 carbon atoms, and still more preferably a single bond, -(CH2)2- or -(CH2)4-. One or two or more non-adjacent -CH2- groups in the alkylene group may be substituted with -O-, -COO- or -OCO-.

[0164] Furthermore, when the linearity of the rod-shaped molecule is to be improved, Z AL1 The preferred embodiment is a single bond directly connecting the rings, where the number of atoms directly connecting the rings is an even number. For example, in the case of -CH2-CH2COO-, the number of atoms directly connecting the rings is 4.

[0165] In the general formula (AL), A AL1 and A AL2 Each independently represents a divalent cyclic group. The divalent cyclic group is preferably selected from 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrothiopyran-2,5-diyl, thiophene-2,5-diyl, 1,4-bicyclo(2,2,2)octylene, decahydronaphthalene-2,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl, thiophene-2,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 2,6-naphthylene, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7 The present invention is one selected from the group consisting of 1,4-phenylene, 1,4-naphthylene, benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl, benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl, [1]benzothieno[3,2-b]thiophene-2,7-diyl, [1]benzothieno[3,2-b]thiophene-2,7-diyl and fluorene-2,7-diyl, more preferably 1,4-phenylene, 1,4-cyclohexylene, 2,6-naphthylene or phenanthrene-2,7-diyl, and still more preferably 1,4-phenylene or 1,4-cyclohexylene.

[0166] These groups may be unsubstituted or substituted. The substituent is preferably a fluorine atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group may be substituted with a fluorine atom or a hydroxyl group.

[0167] In addition, one or more hydrogen atoms in the cyclic group may be halogenated, adsorbed, or P- AP1 -Sp AP1 - or substituted with a monovalent organic group.

[0168] In the general formula (AL), the monovalent organic group is a group constituting a chemical structure in which an organic compound becomes a monovalent group, and means an atomic group formed by removing one hydrogen atom from an organic compound.

[0169] Examples of the monovalent organic group include an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, and an alkenyloxy group having 2 to 15 carbon atoms. An alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms is more preferred, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is further preferred, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms is particularly preferred, and an alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 carbon atom is most preferred.

[0170] In addition, one or two or more non-adjacent -CH2- in the above-mentioned alkyl, alkenyl, alkoxy and alkenyloxy groups may be substituted with -O-, -COO- or -OCO-. Furthermore, the above-mentioned monovalent organic group may have a role as an alignment inducing group as described below.

[0171] In the above general formula (AL), m AL1 It is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 2 or 3.

[0172] Preferred embodiments of the mesogen group include the following formulae (me-1) to (me-44).

[0173] [Chemistry 23]

[0174]

[0175] [Chemistry 24]

[0176]

[0177] [Chemistry 25]

[0178]

[0179] [Chemistry 26]

[0180]

[0181] General formula (AL) is a structure in which two hydrogen atoms are separated from these compounds.

[0182] In these formulae (me-1) to (me-44), one or more hydrogen atoms in the cyclohexane ring, benzene ring or naphthalene ring may be independently replaced by a halogen group, a P AP1 -Sp AP1 -, a monovalent organic group (for example, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorbing group or an orientation inducing group.

[0183] Among the above-mentioned liquid crystal bases, the preferred form is formula (me-8) to (me-44), the more preferred form is formula (me-8) to (me-10), formula (me-12) to (me-18), formula (me-22) to (me-24), formula (me-26) to (me-27) and formula (me-29) to (me-44), and the further preferred form is formula (me-12), (me-15) to (me-16), (me-22) to (me-24), (me-29), (me-34), (me-36) to (me-37), (me-42) to (me-44).

[0184] Among the above-mentioned mesogens, a particularly preferred embodiment is the following general formula (AL-1) or (AL-2), and a most preferred embodiment is the following general formula (AL-1).

[0185] [Chemistry 27]

[0186]

[0187] Where, X AL101 ~X AL118 , X AL201 ~X AL214 Each independently represents a hydrogen atom, a halogen group, P APl -Sp APl -, adsorption group or orientation inducing group.

[0188] Ring A AL11 , Ring A AL12 and Ring A AL21 Each independently represents a cyclohexane ring or a benzene ring.

[0189] X AL101 ~X AL118 , X AL201 ~X AL214 Any one or two or more of them may be substituted by an adsorbent group.

[0190] X AL101 ~X AL118 , X AL201 ~X AL214 Any one or two or more of them may be substituted by an orientation inducing group.

[0191] Adsorption groups and orientation-inducing groups can be AP1 -Sp AP1 -replace.

[0192] Regarding the general formula (AL-1) or the general formula (AL-2), the molecule has one or more P AP1 -Sp APl -.

[0193] In the general formula (AL-1), X AL101 An orientation inducing group is preferred.

[0194] In the general formula (AL-1), X is preferably AL109 , X AL110 and X AL111 At least one of them is an adsorption group, and more preferably X AL109 and X AL110 All are adsorbents or X AL110 is an adsorption group, and X is further preferably AL110 For adsorption base.

[0195] In the general formula (AL-1), X is preferably AL109 , X AL110 and X AL111 At least one of them is P AP1 -Sp AP1 - or an adsorbent having a polymerizable site in the structure, more preferably X AL109 and X AL111 Both or one of them is P AP1 -Sp AP1 -.

[0196] In the general formula (AL-1), X AL104 ~X AL108 , X AL112 ~X AL116 One or more of them are independently preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group, and more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. AL105 , X AL106 or X AL107 Particularly preferably, each independently is an alkyl group having 1 to 3 carbon atoms or a fluorine atom.

[0197] In the general formula (AL-2), X AL201 An orientation inducing group is preferred.

[0198] In the general formula (AL-2), X is preferably AL207 , X AL208 and X AL209 At least one of them is an adsorption group, and more preferably X AL207 and X AL208 All are adsorbents or XAL208 is an adsorption group, and X is further preferably AL208 For adsorption base.

[0199] In the general formula (AL-2), X is preferably AL207 , X AL208 and X AL209 At least one of them is P AP1 -Sp AP1 - or an adsorbent having a polymerizable site in the structure, more preferably X AL207 and X AL209 Both or one of them is P AP1 -Sp AP1 -.

[0200] In the general formula (AL-2), X AL202 ~X AL206 , X AL210 ~X AL214 One or more of them are independently preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen group, and more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. AL204 , X AL205 or X AL206 Particularly preferably, each independently is an alkyl group having 1 to 3 carbon atoms or a fluorine atom.

[0201] "Adsorption base"

[0202] The adsorption group is a group having the function of adsorbing an adsorption medium, and the adsorption medium is a layer such as a substrate, a film, an electrode, etc., which is in contact with the liquid crystal composition.

[0203] Adsorption is generally divided into chemical adsorption, which forms a chemical bond (covalent bond, ionic bond or metallic bond) between the adsorption medium and the adsorbent, and physical adsorption other than chemical adsorption. In this specification, adsorption may be either chemical adsorption or physical adsorption, preferably physical adsorption. Therefore, the adsorption group is preferably a group that can be physically adsorbed with the adsorption medium, and more preferably a group that can be connected to the adsorption medium through intermolecular forces.

[0204] Examples of the method of connecting with the adsorption medium by intermolecular force include a method utilizing interactions such as permanent dipole, permanent quadrupole, dispersion force, charge transfer force, or hydrogen bond.

[0205] A preferred embodiment of the adsorbent group is one that can be connected to the adsorption medium by hydrogen bonding. In this case, the adsorbent group may play the role of either a proton donor or an acceptor with hydrogen bonding intermittently present, or may play both roles.

[0206] The adsorbent group is preferably a group containing a polar element (hereinafter, "adsorbent group" is also referred to as "polar group") having an atomic group formed by connecting a carbon atom and a heteroatom. In the present specification, the polar element means an atomic group formed by directly connecting a carbon atom and a heteroatom.

[0207] The hetero atom is preferably at least one selected from the group consisting of N, O, S, P, B and Si, more preferably at least one selected from the group consisting of N, O and S, further preferably at least one selected from the group consisting of N and O, and particularly preferably O.

[0208] In the alignment aid, the valence of the polar element is not particularly limited, and may be monovalent, divalent, trivalent, or the like. Also, the number of polar elements in the adsorption group is not particularly limited.

[0209] The alignment aid preferably has 1 to 8 adsorption groups in one molecule, more preferably 1 to 4 adsorption groups, and further preferably 1 to 3 adsorption groups.

[0210] Among them, polymerizable groups and orientation-inducing groups are excluded from the adsorption groups, but the hydrogen atoms in the adsorption groups are P AP1 -Sp AP1 -substituted structure and P AP1 -Sp AP1 The structure in which the hydrogen atom in - is replaced by -OH is included in the adsorption group.

[0211] The adsorption group contains one or more polar elements and is roughly divided into a ring type and a chain type.

[0212] The cyclic radical type is an embodiment in which a cyclic group is included in its structure, and the cyclic group has a cyclic structure containing a polar element, and the chain radical type is an embodiment in which a cyclic group is not included in its structure, and the cyclic group has a cyclic structure containing a polar element.

[0213] The chain group type is an embodiment in which a polar element is present in a linear or branched chain group, and a part of the linear or branched chain group may have a cyclic structure without a polar element.

[0214] The cyclic group-type adsorbent group means a form having a structure including at least one polar element in a cyclic atomic array.

[0215] In this specification, the cyclic group is as described above. Therefore, the cyclic group type adsorbent may contain a cyclic group including a polar element, and the adsorbent as a whole may be branched or linear.

[0216] On the other hand, the chain-type adsorbent group means a structure having a structure that does not contain a cyclic atomic arrangement containing a polar element in the molecule and contains at least one polar element in a linear atomic arrangement (which may be branched).

[0217] In this specification, a chain group means an atomic group that does not contain a cyclic atomic arrangement in the structural formula and whose constituent atoms are connected in a linear (branchable) manner, and is called a non-cyclic group. In other words, a chain group means a straight-chain or branched aliphatic group, which may contain either a saturated bond or an unsaturated bond.

[0218] Therefore, the chain group includes, for example, alkyl, alkenyl, alkoxy, ester, ether or ketone. Among them, the hydrogen atom in these groups may be substituted by at least one substituent (reactive functional group (vinyl, acryloyl, methacryloyl, etc.), chain organic group (alkyl, cyano, etc.)). In addition, the chain group may be either linear or branched.

[0219] As the cyclic group type adsorbent, preferably a heteroaromatic group (including condensed ring) having 3 to 20 carbon atoms or a heteroalicyclic group (including condensed ring) having 3 to 20 carbon atoms, more preferably a heteroaromatic group (including condensed ring) having 3 to 12 carbon atoms or a heteroalicyclic group (including condensed ring) having 3 to 12 carbon atoms, further preferably a 5-membered heteroaromatic group, a 5-membered heteroalicyclic group, a 6-membered heteroaromatic group or a 6-membered heteroalicyclic group. The hydrogen atoms in these ring structures may be substituted with a halogen group, a linear or branched alkyl group or an alkoxy group having 1 to 5 carbon atoms.

[0220] As the chain-type adsorbent, a linear or branched alkyl group having 1 to 20 carbon atoms in which the hydrogen atom or -CH2- in the structure is substituted by a polar element is preferred. Among them, one or more non-adjacent -CH2- in the alkyl group may be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO-, -OCO-, or -OCO-COO-. In addition, the chain-type adsorbent preferably contains one or more polar elements at its end.

[0221] The hydrogen atoms in the adsorbent groups may be replaced by polymerizable groups.

[0222] Specific examples of polar elements include polar elements containing oxygen atoms (hereinafter referred to as oxygen-containing polar elements), polar elements containing nitrogen atoms (hereinafter referred to as nitrogen-containing polar elements), polar elements containing phosphorus atoms (hereinafter referred to as phosphorus-containing polar elements), polar elements containing boron atoms (hereinafter referred to as boron-containing polar elements), polar elements containing silicon atoms (hereinafter referred to as silicon-containing polar elements), or polar elements containing sulfur atoms (hereinafter referred to as sulfur-containing polar elements). From the viewpoint of adsorption capacity, the polar element is preferably a nitrogen-containing polar element, a nitrogen-containing polar element, or an oxygen-containing polar element, and more preferably an oxygen-containing polar element.

[0223] The oxygen-containing polar element is preferably at least one group selected from the group consisting of a hydroxyl group, an alkanol group, an alkoxy group, a formyl group, a carboxyl group, an ether group, a carbonyl group, a carbonate group, and an ester group, or a group in which the group is bonded to a carbon atom.

[0224] The nitrogen-containing polar element is preferably at least one group selected from the group consisting of a cyano group, a primary amino group, a secondary amino group, a tertiary amino group, a pyridyl group, a carbamoyl group, and a urea group, or a group in which the group is bonded to a carbon atom.

[0225] The phosphorus-containing polar element is preferably at least one group selected from the group consisting of a phosphinyl group and a phosphoric acid group, or a group in which the group is bonded to a carbon atom.

[0226] Therefore, as the adsorbent group, it is preferred that the group itself contains one or more kinds of groups selected from the group consisting of a cyclic group having an oxygen-containing polar element (hereinafter referred to as an oxygen-containing cyclic group), a cyclic group having a nitrogen-containing polar element (hereinafter referred to as a nitrogen-containing cyclic group), a cyclic group having a sulfur-containing polar element (hereinafter referred to as a sulfur-containing cyclic group), a chain group having an oxygen-containing polar element (hereinafter referred to as an oxygen-containing chain group) and a chain group having a nitrogen-containing polar element (hereinafter referred to as a nitrogen-containing chain group). From the viewpoint of adsorption ability, it is more preferred that the group contains one or more kinds of groups selected from the group consisting of an oxygen-containing cyclic group, a sulfur-containing cyclic group, an oxygen-containing chain group and a nitrogen-containing chain group.

[0227] As the oxygen-containing cyclic group, any of the following groups having an oxygen atom as an ether group in the ring structure is preferably included.

[0228] [Chemistry 28]

[0229]

[0230] In addition, as the oxygen-containing cyclic group, it is preferable to contain any of the following groups having an oxygen atom in the form of a carbonyl group, a carbonate group, and an ester group in the ring structure.

[0231] [Chemistry 29]

[0232]

[0233] As the nitrogen-containing cyclic group, it is preferred that any of the following groups be contained.

[0234] [Chemistry 30]

[0235]

[0236] As the oxygen-containing chain group, any of the following groups is preferably contained.

[0237] [Chemistry 31]

[0238]

[0239] In the formula, R at1 It represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0240] Z at1 It represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms. In particular, -CH2- in the alkylene group or alkenylene group may be substituted by -O-, -COO-, -C(=O)-, or -OCO- in a manner that the oxygen atom is not directly adjacent.

[0241] X at1 It represents an alkyl group having 1 to 15 carbon atoms. In this case, -CH2- in the alkyl group may be substituted by -O-, -COO-, -C(=O)-, or -OCO- so that the oxygen atom is not directly adjacent thereto.

[0242] As the nitrogen-containing chain group, any of the following groups is preferably contained.

[0243] [Chemistry 32]

[0244]

[0245] In the formula, R at , R bt , R ct and R dt Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

[0246] As the adsorption group, a group represented by the following general formula (AT) is preferred.

[0247] [Chemistry 33]

[0248] *-Sp AT1 -W AT1 -Z AT1 (AT)

[0249] Where Sp AT1 represents a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms. The hydrogen atoms in the alkylene group may be -OH, -CN, -W AT1 -Z AT1 or P AP1 -Sp AP1 -substituted, the -CH2- in the alkylene group can be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO-, -CH=CH- or -OCO-COO- in a manner that the oxygen atom is not directly connected.

[0250] W AT1represents a single bond or the following general formula (WAT1) or (WAT2).

[0251] Z AT1 represents a monovalent group containing a polar element. AT1 The hydrogen atoms in the AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -replace.

[0252] [Chemistry 34]

[0253]

[0254] (Where Sp WAT1 and Sp WAT2 Each independently represents a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms, and the hydrogen atom in the alkylene group may be -OH, -CN, -Sp AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -substituted, the -CH2- in the alkylene group can be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- in a manner that the oxygen atom is not directly connected.)

[0255] Sp AT1 、Sp WAT1 and Sp WAT2 Each independently preferably represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably represents a single bond or a linear alkylene group having 1 to 20 carbon atoms, and further preferably represents a single bond or a linear alkylene group having 2 to 10 carbon atoms.

[0256] In addition, Sp AT1 、Sp WAT1 and Sp WAT2 In the alkylene group, one or two or more non-adjacent -CH2- groups may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- in a manner that the oxygen atom is not directly connected.

[0257] In addition, Sp AT1 and Sp WAT1 The hydrogen atoms in the AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -replace.

[0258] Z AT1 It represents a monovalent group containing a polar element, and is preferably a group represented by the following general formula (ZAT1-1) or (ZAT1-2).

[0259] [Chemistry 35]

[0260] *-Sp ZAT11 -Z ZAT11 -R ZAT11 (ZAT1-1

[0261]

[0262] Where Sp ZAT11 and Sp ZAT12 Each independently represents a linear or branched alkylene group having 1 to 25 carbon atoms. The hydrogen atoms in the alkylene group may be -OH, -CN, -Sp AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -substituted, the -CH2- in the alkylene group may be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- in a manner that the oxygen atom is not directly adjacent.

[0263] Z ZAT11 It represents a group containing a polar element.

[0264] The general formula (ZAT1-2) contains Z ZAT12 The structure represented by the ring represents a 5- to 7-membered ring.

[0265] Z ZAT11 and Z ZAT12 The hydrogen atoms in the AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -replace.

[0266] R ZAT11 and R ZAT12 Each independently represents a linear or branched alkyl group having 1 to 8 carbon atoms. The hydrogen atom in the alkyl group may be -OH, -CN, -Sp AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -substituted, the -CH2- in the alkyl group can be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- in a manner that the oxygen atom is not directly connected.

[0267] As the group represented by the general formula (ZAT1-1), groups represented by the following general formulae (ZAT1-1-1) to (ZAT1-1-30) are preferred.

[0268] [Chemistry 36]

[0269]

[0270] [Chemistry 37]

[0271]

[0272] In the formula, the hydrogen atom connected to the carbon atom can be -OH, -CN, -Sp AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -replace.

[0273] Sp ZAT11 represents a linear or branched alkylene group having 1 to 25 carbon atoms. The hydrogen atoms in the alkylene group may be -OH, -CN, -Sp AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -substituted, the -CH2- in the alkylene group may be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- in a manner that the oxygen atom is not directly adjacent.

[0274] R ZAT11 represents a linear or branched alkyl group having 1 to 8 carbon atoms. The hydrogen atom in the alkyl group may be -OH, -CN, -Sp AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -substituted, the -CH2- in the alkyl group can be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- in a manner that the oxygen atom is not directly connected.

[0275] As the group represented by the general formula (ZAT1-2), groups represented by the following general formulae (ZAT1-2-1) to (ZAT1-2-9) are preferred.

[0276] [Chemistry 38]

[0277]

[0278] In the formula, the hydrogen atom connected to the carbon atom can be halogen atoms, -OH, -CN, -SpAT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -replace.

[0279] Sp ZAT11 represents a linear or branched alkylene group having 1 to 25 carbon atoms. The hydrogen atoms in the alkylene group may be -OH, -CN, -Sp AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -substituted, the -CH2- in the alkylene group may be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- in a manner that the oxygen atom is not directly adjacent.

[0280] Examples of the group represented by the general formula (ZAT1-1) include the following groups.

[0281] [Chemistry 39]

[0282]

[0283] [Chemistry 40]

[0284]

[0285] [Chemistry 41]

[0286]

[0287] [Chemistry 42]

[0288]

[0289] [Chemistry 43]

[0290]

[0291] In the formula, R tc represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or P AP1 -Sp AP1 -. The hydrogen atom in the alkyl group can be -OH, -CN, -Sp AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -substituted, the -CH2- in the alkyl group can be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- in a manner that the oxygen atom is not directly adjacent.

[0292] The hydrogen atoms in the molecule can beAP1 -Sp AP1 -replace.

[0293] * indicates a connection key.

[0294] The alignment aid is preferably a polar element contained in the adsorption group and a polar element contained in the polymerizable group that are locally present. The adsorption group is an important structure for vertically aligning liquid crystal molecules. By making the adsorption group adjacent to the polymerizable group, better alignment can be obtained, and good solubility in the liquid crystal composition is exhibited.

[0295] Specifically, the alignment aid is preferably in a form in which a polymerizable group and an adsorbent group are on the same ring of the mesogen group. This form includes: a form in which one or more polymerizable groups and one or more adsorbent groups are respectively connected to the same ring; a form in which at least one of the one or more polymerizable groups or at least one of the one or more adsorbent groups is connected to the other, and the polymerizable group and the adsorbent group are on the same ring.

[0296] In this case, the hydrogen atom in the spacer included in the polymerizable group may be substituted with the adsorbing group, and further, the hydrogen atom in the adsorbing group may be substituted with the polymerizable group via the spacer.

[0297] As the alignment aid, a compound represented by the following general formula (SAL) is preferred.

[0298] [Chemistry 44]

[0299]

[0300] In the formula, the hydrogen atom connected to the carbon atom may be a straight-chain or branched alkyl group having 1 to 25 carbon atoms, -OH, -CN, -Sp AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -substituted. The hydrogen atom in the alkyl group can be replaced by -OH, -CN, -Sp AT1 -W AT1 -Z AT1 or P AP1 -Sp AP1 -substituted, the -CH2- in the alkyl group can be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- in a manner that the oxygen atom is not directly connected.

[0301] R AK1 Represents the same as R in the general formula (AK) AK1 Same meaning.

[0302] A AL1 and A AL2Each independently represents the same as A in the general formula (AL) AL1 and A AL2 Same meaning.

[0303] Z AL1 It represents the same as Z in the general formula (AL) AL1 Same meaning.

[0304] m AL1 Indicates the same as m in the general formula (AL) AL1 Same meaning.

[0305] Sp AT1 Indicates the same as Sp in the general formula (AT) AT1 Same meaning.

[0306] W AT1 Indicates the same as W in the general formula (AT) AT1 Same meaning.

[0307] Z AT1 It represents the same as Z in the general formula (AT) AT1 Same meaning.

[0308] As the compound represented by the general formula (SAL), compounds represented by the following formulas (SAL-1.1) to (SAL-2.9) are preferred.

[0309] [Chemistry 45]

[0310]

[0311] [Chemistry 46]

[0312]

[0313] [Chemistry 47]

[0314]

[0315] [Chemistry 48]

[0316]

[0317] [Chemistry 49]

[0318]

[0319] [Chemistry 50]

[0320]

[0321] [Chemistry 51]

[0322]

[0323] [Chemistry 52]

[0324]

[0325] [Chemistry 53]

[0326]

[0327] [Chemistry 54]

[0328]

[0329] [Chemistry 55]

[0330]

[0331] [Chemistry 56]

[0332]

[0333] [Chemistry 57]

[0334]

[0335] The amount of the orientation aid contained in the liquid crystal composition is preferably about 0.01 to 50 mass%. From the viewpoint of more appropriately aligning the liquid crystal molecules, the more preferred lower limit is 0.05 mass%, 0.1 mass%. On the other hand, from the viewpoint of improving the response characteristics, the more preferred upper limit is 30 mass%, 10 mass%, 7 mass%, 5 mass%, 4 mass%, 3 mass%.

[0336] The compound represented by the general formula (i), the compound represented by the general formula (SAL) (i.e., as a compound containing an adsorbent group Z AT1 The total content of the compound represented by the general formula (P) is preferably 0.05 to 10 mass %, preferably 0.1 to 8 mass %, preferably 0.1 to 5 mass %, preferably 0.1 to 3 mass %, preferably 0.2 to 2 mass %, preferably 0.2 to 1.3 mass %, preferably 0.2 to 1 mass %, preferably 0.2 to 0.56 mass % relative to the liquid crystal composition.

[0337] The polymerizable liquid crystal composition of the present invention contains a compound represented by the general formula (i) as a polymerizable compound, and preferably further contains a compound represented by the general formula (SAL) (i.e., as a polymerizable compound containing an adsorbent group Z). AT1 An alignment aid of a compound of the formula (P) and a compound represented by the general formula (P).

[0338] Here, the compound represented by the general formula (SAL) as an alignment aid has the function of aligning the liquid crystal compound in the liquid crystal composition approximately vertically with respect to the substrate, and the compound represented by the general formula (i) and the compound represented by the general formula (P) are used to stabilize the orientation of the liquid crystal compound tilted in a certain direction with respect to the substrate in a state where no voltage is applied. Although the tilt of the liquid crystal compound with respect to the substrate can be stabilized to a certain extent even if only the compound represented by the general formula (P) is used, the problem to be solved in this application can be achieved by using the compound represented by the general formula (i).

[0339] The compound represented by the general formula (i), the compound represented by the general formula (SAL) (i.e., as a compound containing an adsorbent group Z AT1 The preferred lower limit of the total content of the compound represented by the general formula (P) is 0.01 mass %, 0.03 mass %, 0.05 mass %, 0.08 mass %, 0.1 mass %, 0.15 mass %, 0.2 mass %, 0.25 mass %, and 0.3 mass % relative to the liquid crystal composition.

[0340] The preferred upper limit value of the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is 10 mass%, 8 mass%, 5 mass%, 3 mass%, 1.5 mass%, 1.2 mass%, 1 mass%, 0.8 mass%, and 0.5 mass% relative to the liquid crystal composition.

[0341] If the compound represented by the general formula (i) or the compound represented by the general formula (SAL) (i.e., as a compound containing an adsorbent group Z AT1 If the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is small, it is difficult to show the effect of adding these compounds to the liquid crystal composition. Depending on the type of liquid crystal molecules, for example, the orientation constraint of the liquid crystal molecules is weak or weakens over time. On the other hand, if the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is too much, for example, depending on the illumination of the active energy ray, the following problems may sometimes occur: the amount of the compound remaining after curing becomes more, the curing takes time, and the reliability of the liquid crystal composition is reduced. Therefore, it is preferred to consider their balance to set its content.

[0342] The liquid crystal composition of the present invention preferably contains one or more compounds selected from the group of compounds represented by general formulae (N-01), (N-02), (N-03), (N-04) and (N-05). These compounds are equivalent to compounds having negative dielectric anisotropy. "Compounds having negative dielectric anisotropy" means compounds showing a negative sign of Δε and an absolute value greater than 2. Among them, Δε of the compound is the following value: a value extrapolated from the measured value of the dielectric anisotropy of a composition prepared by adding the compound to a composition having approximately neutral dielectric properties at 25°C.

[0343] The liquid crystal composition of the present invention preferably contains one or two or more compounds selected from the group consisting of compounds represented by general formulae (N-01), (N-02), (N-03) and (N-04).

[0344] [Chemistry 58]

[0345]

[0346] In the formula, R 21 and R 22 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, and one or more non-adjacent -CH2- in the group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and Z 1 Each independently represents a single bond, -CH2CH2-, -OCH2-, -CH2O-, -COO-, -OCO-, -OCF2-, -CF2O-, -CH=CH-, -CF=CF- or -C≡C-, and m each independently represents 1 or 2.

[0347] R 21 It is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and further preferably an alkyl group having 1 to 4 carbon atoms. 1 When R represents anything other than a single bond, 21 An alkyl group having 1 to 3 carbon atoms is preferred.

[0348] R 22 An alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms is preferred, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is more preferred, and an alkoxy group having 1 to 4 carbon atoms is further preferred.

[0349] R 21 and R 22When it is an alkenyl group, it is preferably a group represented by any one selected from the group consisting of formula (R1) to formula (R5) (the black dots in each formula represent carbon atoms in the ring structure),

[0350] [Chemistry 59]

[0351]

[0352] More preferably, it is the formula (R1) or the formula (R2). 21 and R 22 The content of the alkenyl compound is preferably as small as possible, and is preferably not contained.

[0353] Z 1 Each independently represents a single bond, -CH2CH2-, -OCH2-, -CH2O-, -COO-, -OCO-, -OCF2-, -CF2O-, -CH=CH-, -CF=CF- or -C≡C-, preferably a single bond, -CH2CH2-, -OCH2-, -CH2O-, more preferably a single bond or -CH2O-.

[0354] When m is 1, Z 1 Preferred is a single bond.

[0355] When m is 2, Z 1 Preferred is -CH2CH2- or -CH2O-.

[0356] The fluorine atoms of the compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) may be substituted by chlorine atoms belonging to the same halogen group. The content of the compounds substituted by chlorine atoms is preferably as small as possible, and preferably no chlorine atoms are contained.

[0357] The hydrogen atoms present on the rings of the compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) may be substituted by fluorine atoms or chlorine atoms, but chlorine atoms are not preferred.

[0358] The compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) are preferably compounds having a negative Δε and an absolute value greater than 3. Specifically, R 22 It preferably represents an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and particularly preferably represents an alkoxy group having 1 to 4 carbon atoms.

[0359] In the liquid crystal composition of the present invention, the compound represented by the general formula (N-01) preferably contains one or more compounds selected from the group of compounds represented by the general formula (N-01-1), the general formula (N-01-2), the general formula (N-01-3) and the general formula (N-01-4).

[0360] [Chemistry 60]

[0361]

[0362] (Where R 21 Means the same as above, R 23 Each independently represents an alkoxy group having 1 to 4 carbon atoms. )

[0363] The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, and one or two or more compounds selected from the group consisting of compounds represented by General Formulae (N-01-1) to (N-01-4).

[0364] The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by General Formula (N-01-1), and a compound represented by General Formula (N-01-4).

[0365] The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by General Formula (N-01-3), and a compound represented by General Formula (N-01-4).

[0366] In the liquid crystal composition of the present invention, the compound represented by general formula (N-02) preferably contains one or more compounds selected from the group consisting of compounds represented by general formula (N-02-1), general formula (N-02-2), and general formula (N-02-3).

[0367] [Chemistry 61]

[0368]

[0369] (Where R 21 Means the same as above, R 23 Each independently represents an alkoxy group having 1 to 4 carbon atoms. )

[0370] The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, and a compound represented by General Formula (N-02-1).

[0371] The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by General Formula (N-02-1), and a compound represented by General Formula (N-02-3).

[0372] The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by General Formula (N-02-1), and a compound represented by General Formula (N-01-4).

[0373] The liquid crystal composition of the present invention preferably contains one or two or more compounds represented by the general formula (N-03-1) as the compound represented by the general formula (N-03).

[0374] [Chemistry 62]

[0375]

[0376] (Where R 21 Means the same as above, R 23 represents an alkoxy group having 1 to 4 carbon atoms. )

[0377] The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, and a compound represented by General Formula (N-03-1).

[0378] The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by General Formula (N-03-1), and a compound represented by General Formula (N-01-4).

[0379] The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by General Formula (N-03-1), and a compound represented by General Formula (N-02-1).

[0380] The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-03-1), a compound represented by the general formula (N-01-4), and a compound represented by the general formula (N-02-1).

[0381] The liquid crystal composition of the present invention preferably contains one or two or more compounds represented by the general formula (N-04-1) as the compound represented by the general formula (N-04).

[0382] [Chemistry 63]

[0383]

[0384] (Where R 21 Means the same as above, R 23 represents an alkoxy group having 1 to 4 carbon atoms. )

[0385] The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, and a compound represented by General Formula (N-04-1).

[0386] The liquid crystal composition of the present invention particularly preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-04-1), and a compound represented by the general formula (N-01-4) simultaneously.

[0387] The liquid crystal composition of the present invention particularly preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4), and a compound represented by the general formula (N-02-1).

[0388] The liquid crystal composition of the present invention particularly preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4), and a compound represented by the general formula (N-03-1).

[0389] The liquid crystal composition of the present invention particularly preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-02-1), and a compound represented by the general formula (N-03-1).

[0390] The liquid crystal composition of the present invention particularly preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4), a compound represented by the general formula (N-02-1), and a compound represented by the general formula (N-03-1).

[0391] The liquid crystal composition of the present invention may contain, as the compound represented by the general formula (N-05), a compound selected from the group consisting of compounds represented by formulae (N-05-1) to (N-05-3).

[0392] [Chemistry 64]

[0393]

[0394] Relative to the total amount of the liquid crystal composition of the present invention, the preferred lower limit of the content of the compound represented by the general formula (N-01) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of the content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.

[0395] Relative to the total amount of the liquid crystal composition of the present invention, the preferred lower limit of the content of the compound represented by the general formula (N-02) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of the content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.

[0396] Relative to the total amount of the liquid crystal composition of the present invention, the preferred lower limit of the content of the compound represented by the general formula (N-03) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of the content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.

[0397] Relative to the total amount of the liquid crystal composition of the present invention, the preferred lower limit of the content of the compound represented by the general formula (N-04) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of the content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.

[0398] Relative to the total amount of the liquid crystal composition of the present invention, the preferred lower limit of the content of the compound represented by formula (N-05) is 0%, 2%, 5%, 8%, 10%, 13%, 15%, 17%, and 20%. The preferred upper limit of the content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, and 13%.

[0399] The liquid crystal composition of the present invention may further contain one or two or more compounds represented by the general formula (N-06).

[0400] [Chemistry 65]

[0401]

[0402] (Where R 21 and R 22 Meanings the same as above.)

[0403] The compound represented by the general formula (N-06) is useful when it is desired to adjust various physical properties, and can be used to obtain a large refractive index anisotropy (Δn), a high T NI , and use it with large Δε.

[0404] Relative to the total amount of the liquid crystal composition of the present invention, the preferred lower limit of the content of the compound represented by formula (N-06) is 0%, 2%, 5%, 8%, 10%, 13%, 15%, 17%, and 20%. The preferred upper limit of the content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, and 5%.

[0405] The liquid crystal composition of the present invention contains one or two or more compounds selected from the group consisting of compounds represented by General Formula (NU-01) to General Formula (NU-08).

[0406] [Chemistry 66]

[0407]

[0408] (Where R NU11 , R NU12 , R NU21 , R NU22 , R NU31 , R NU32 , R NU41 , R NU42 , R NU51 , R NU52 , R NU61 , R NU62 , R NU71 , R NU72 , R NU81 and R NU82 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, and one or more non-adjacent -CH2- in the group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO-, or -OCO-.)

[0409] If described in more detail, R NU11 , R NU12 , RNU21 , R NU22 , R NU31 , R NU32 , R NU41 , R NU42 , R NU51 , R NU52 , R NU61 , R NU62 , R NU71 , R NU72 , R NU81 and R NU82 It is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. When the response speed is important, it is preferred that at least one R NU11 , R NU21 , R NU41 and R NU51 It is an alkenyl group having 2 to 3 carbon atoms, preferably an alkenyl group represented by the formula (R2).

[0410] The amount of the compound having an alkenyl group is preferably 30% or less, preferably 25% or less, preferably 20% or less, preferably 15% or less, preferably 10% or less, and preferably 5% or less relative to the total amount of the liquid crystal composition of the present invention. When high VHR is important, the amount of the compound having an alkenyl group is preferably 10% or less, preferably 5% or less, preferably 1% or less, and preferably not contained.

[0411] If described in more detail, R NU11 , R NU21 , R NU31 , R NU41 , R NU51 , R NU61 , R NU71 , R NU81 Particularly preferred is an alkyl group having 1 to 5 carbon atoms, NU12 , R NU22 , R NU32 , R NU42 , R NU52 , R NU62 , R NU72 and R NU82 An alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is particularly preferred.

[0412] The liquid crystal composition of the present invention preferably contains a compound represented by General Formula (NU-01) and a compound represented by General Formula (NU-02).

[0413] The liquid crystal composition of the present invention preferably contains a compound represented by General Formula (NU-01) and a compound represented by General Formula (NU-03).

[0414] The liquid crystal composition of the present invention preferably contains a compound represented by General Formula (NU-03) and a compound represented by General Formula (NU-04).

[0415] The liquid crystal composition of the present invention preferably contains a compound represented by General Formula (NU-03) and a compound represented by General Formula (NU-05).

[0416] The liquid crystal composition of the present invention preferably contains a compound represented by General Formula (NU-01) and a compound represented by General Formula (NU-06).

[0417] The liquid crystal composition of the present invention preferably contains a compound represented by General Formula (NU-01) and a compound represented by General Formula (NU-07).

[0418] The liquid crystal composition of the present invention preferably contains a compound represented by General Formula (NU-01) and a compound represented by General Formula (NU-08).

[0419] The liquid crystal composition of the present invention further preferably contains a compound represented by General Formula (NU-01), a compound represented by General Formula (NU-02), and a compound represented by General Formula (NU-04).

[0420] The liquid crystal composition of the present invention further preferably contains a compound represented by General Formula (NU-01), a compound represented by General Formula (NU-03), and a compound represented by General Formula (NU-05).

[0421] The liquid crystal composition of the present invention further preferably contains a compound represented by General Formula (NU-01), a compound represented by General Formula (NU-02), a compound represented by General Formula (NU-03), and a compound represented by General Formula (NU-05).

[0422] The content of the compound represented by the general formula (NU-01) is preferably 1 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass.

[0423] The content of the compound represented by the general formula (NU-02) is preferably 1 to 40% by mass, more preferably 5 to 25% by mass, and even more preferably 5 to 20% by mass.

[0424] The content of the compound represented by the general formula (NU-03) is preferably 1 to 20% by mass, more preferably 0 to 15% by mass, and even more preferably 0 to 10% by mass.

[0425] The content of the compound represented by the general formula (NU-04) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 3 to 10% by mass.

[0426] The content of the compound represented by the general formula (NU-05) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 3 to 20% by mass.

[0427] The content of the compound represented by the general formula (NU-06) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 3 to 10% by mass.

[0428] The content of the compound represented by the general formula (NU-07) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 3 to 10% by mass.

[0429] The content of the compound represented by the general formula (NU-08) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 3 to 10% by mass.

[0430] The liquid crystal composition of the present invention may contain one or more compounds having positive dielectric anisotropy described in paragraphs 0236 to 0509 of Patent Document 4 (Japanese Patent No. 6233550).

[0431] The composition of the present invention preferably does not contain a compound having a structure in which oxygen atoms are linked to each other, such as a peracid (—CO—OO—) structure, in the molecule.

[0432] When reliability and long-term stability of the composition are important, the content of the compound having a carbonyl group is preferably 5% or less, more preferably 3% or less, further preferably 1% or less, and particularly preferably substantially free of the compound.

[0433] When stability due to UV irradiation is important, the content of the compound substituted by chlorine atoms is preferably set to 15% relative to the total mass of the above-mentioned composition, preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially free of it.

[0434] It is preferred that the content of compounds whose ring structures in the molecules are all 6-membered rings is higher. It is preferred that the content of compounds whose ring structures in the molecules are all 6-membered rings is 80% or more relative to the total mass of the above-mentioned composition, more preferably 90% or more, further preferably 95% or more, and it is particularly preferred that the composition is substantially composed only of compounds whose ring structures in the molecules are all 6-membered rings.

[0435] In order to suppress the deterioration of the composition due to oxidation, it is preferred to reduce the content of the compound having a cyclohexenylene group as a ring structure. The content of the compound having a cyclohexenylene group is preferably set to 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially free of the compound.

[0436] When emphasis is placed on improvement in viscosity and improvement in TNI, it is preferred that the content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule whose hydrogen atom may be substituted by a halogen be reduced. The content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and even more preferably substantially free of the compound.

[0437] In the present application, “substantially not containing” means not containing anything except for substances contained unintentionally.

[0438] The liquid crystal composition of the present invention may contain, in addition to the above-mentioned compounds, common nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, antioxidants, ultraviolet absorbers, light stabilizers, infrared absorbers, and the like.

[0439] The liquid crystal composition of the present invention preferably contains an antioxidant so that polymerization does not proceed during the heat treatment, which is one of the steps for manufacturing a liquid crystal display element. If no antioxidant is contained, polymerization proceeds during the heat treatment before the UV irradiation step, and the desired alignment cannot be obtained.

[0440] Examples of the antioxidant include hindered phenols represented by general formula (H-1) to general formula (H-4).

[0441] [Chemistry 67]

[0442]

[0443] In the general formula (H-1) to the general formula (H-3), R H1 Each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms. More specifically, R H1 More preferably, it is an alkyl group having 3 carbon atoms.

[0444] In the general formula (H-4), M H1It represents an alkylene group having 4 to 10 carbon atoms (one or more -CH2- in the alkylene group may be replaced by -O-, -CO-, -COO-, or -OCO- in a manner where the oxygen atom is not directly adjacent to the group), -OCH2-, -CH2O-, -COO-, -OCO-, -CF2O-, -OCF2-, -CF2CF2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -C≡C-, a single bond, 1,4-phenylene (any hydrogen atom in the 1,4-phenylene group may be replaced by a fluorine atom), or trans-1,4-cyclohexylene.

[0445] When the liquid crystal composition of the present invention contains an antioxidant, the lower limit is preferably 10 mass ppm, preferably 20 mass ppm, preferably 50 mass ppm, and the upper limit is preferably 10000 mass ppm, preferably 1000 mass ppm, preferably 500 mass ppm, preferably 100 mass ppm.

[0446] The nematic phase-isotropic liquid phase transition temperature (T NI ) is 60°C to 120°C, more preferably 70°C to 100°C, and particularly preferably 70°C to 85°C. In the present invention, 60°C or above is referred to as T NI high.

[0447] In the case of LCD TV applications, T NI Preferably, it is 70 to 80°C. In the case of portable use, T NI It is preferably 80 to 90°C. In the case of outdoor display applications such as PID (Public Information Display), T NI Preferably it is 90 to 110°C.

[0448] The liquid crystal composition of the present invention has a refractive index anisotropy (Δn) of 0.08 to 0.14 at 20°C, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. If further described, in the case of a thin cell gap, it is preferably 0.10 to 0.13, and in the case of a thick cell gap, it is preferably 0.08 to 0.10. Among them, the liquid crystal composition of the present invention is particularly preferably 0.098 to 0.118 at 20°C.

[0449] The rotational viscosity (γ1) of the liquid crystal composition of the present invention at 20°C is 50 to 160 mPa·s, preferably 55 to 160 mPa·s, preferably 60 to 160 mPa·s, preferably 80 to 150 mPa·s, preferably 90 to 140 mPa·s, preferably 90 to 130 mPa·s, and preferably 90 to 115 mPa·s.

[0450] The dielectric anisotropy (Δε) of the liquid crystal composition of the present invention at 20° C. is from −1.7 to −4.0, preferably from −1.7 to −3.5, more preferably from −1.8 to −3.5, and further preferably from −1.9 to −3.3.

[0451] The liquid crystal composition of the present invention preferably contains a polymerizable compound of the first component and a polymerizable compound of the second component, and further contains one or two or more compounds selected from the group consisting of compounds represented by general formula (N-01), general formula (N-02), general formula (N-03), general formula (N-04), general formula (N-05) and general formula (N-06), and further contains one or two or more compounds selected from the group consisting of compounds represented by general formulas (NU-01) to (NU-08), and the upper limit of the total content of these compounds is preferably 100% by mass, 99% by mass, 98% by mass, 97% by mass, 96% by mass, 98% by mass, 99% by mass, 98 ... %, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass%, and the lower limit of the total of these contents is preferably 78 mass%, 80 mass%, 81 mass%, 83 mass%, 85 mass%, 86 mass%, 87 mass%, 88 mass%, 89 mass%, 90 mass%, 91 mass%, 92 mass%, 93 mass%, 94 mass%, 95 mass%, 96 mass%, 97 mass%, 98 mass%, 99 mass%, 100 mass%.

[0452] The liquid crystal composition of the present invention particularly preferably contains a polymerizable compound of the first component and a polymerizable compound of the second component, and further contains one or more compounds selected from the group consisting of compounds represented by general formula (N-01), general formula (N-02), general formula (N-03) and general formula (N-04), and further contains one or more compounds selected from the group consisting of compounds represented by general formulae (NU-01) to (NU-08), and the upper limit of the total content of these compounds is preferably 100% by mass, 99% by mass, 98% by mass, 97% by mass, 96% by mass, 95% by mass, %, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass%, and the lower limit of the total content of these is preferably 78 mass%, 80 mass%, 81 mass%, 83 mass%, 85 mass%, 86 mass%, 87 mass%, 88 mass%, 89 mass%, 90 mass%, 91 mass%, 92 mass%, 93 mass%, 94 mass%, 95 mass%, 96 mass%, 97 mass%, 98 mass%, 99 mass%, 100 mass%.

[0453] The liquid crystal composition of the present invention can provide a sufficiently fast polymerization speed and a sufficiently large pretilt angle. In addition, the liquid crystal display element using the liquid crystal composition of the present invention has a small amount of residual polymerizable compounds in the liquid crystal display element after polymerization, and display defects such as IS of high-definition PSA or PSVA liquid crystal display elements such as 4K and 8K will not occur or can be significantly suppressed. Therefore, the production efficiency of high-definition PSA or PSVA liquid crystal display elements such as 4K and 8K can be significantly improved, and the industrial utilization value is very high.

[0454] The liquid crystal composition of the present invention is suitable for producing PSA type or PSVA type liquid crystal display elements, and is also suitable for producing NPS type liquid crystal display elements. In addition, it is also suitable for producing PI-less type liquid crystal display elements characterized by having no alignment film.

[0455] The liquid crystal composition of the present invention is also suitable for a liquid crystal display element without an alignment film, which is commonly known as a PI-less mode. For example, it is preferred to use a compound having spontaneous orientation as described in Japanese Patent Application No. 2013-552125, Japanese Patent Application No. 2014-517515, Japanese Patent Application No. 06081361, Japanese Patent Application No. 2015-546888, Japanese Patent Application No. 2017-12710, WO2017041893A, Japanese Patent Application No. 06070973, WO17 / 047177, etc. in combination with the liquid crystal composition of the present invention.

[0456] The liquid crystal composition of the present invention is useful for liquid crystal display elements for active matrix driving, and can be used for liquid crystal display elements such as PSA, PSVA, PS-IPS, PS-FFS, and NPS.

[0457] The liquid crystal display element of the present invention preferably has: a first substrate and a second substrate arranged opposite to each other, a common electrode arranged on the first substrate or the second substrate, a pixel electrode arranged on the first substrate or the second substrate and having a thin film transistor, and a liquid crystal layer arranged between the first substrate and the second substrate and containing a liquid crystal composition. It is also possible to arrange an orientation film for controlling the orientation direction of liquid crystal molecules on the opposite side of at least one substrate of the first substrate and / or the second substrate in contact with the liquid crystal layer as required. As the orientation film, a vertical orientation film, a horizontal orientation film, etc. can be appropriately selected in accordance with the driving mode of the liquid crystal display element, and a known orientation film such as a friction orientation film (for example, polyimide) or a light orientation film (decomposable polyimide, etc.) can be used. Further, a color filter can also be appropriately arranged on the first substrate or the second substrate, and a color filter can be arranged on the pixel electrode and the common electrode.

[0458] The two substrates of the liquid crystal unit used in the liquid crystal display element of the present invention can be made of glass or a flexible transparent material such as plastic, and one of them can also be an opaque material such as silicon. The transparent substrate with a transparent electrode layer can be obtained by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.

[0459] The color filter can be made, for example, by a pigment dispersion method, a printing method, an electrodeposition method or a dyeing method. If the method of making a color filter by a pigment dispersion method is used as an example, the curable coloring composition for the color filter is applied to the transparent substrate, patterned, and then cured by heating or light. By performing this process on the three colors of red, green, and blue, a pixel portion for a color filter can be made. In addition, a pixel electrode provided with active components such as a TFT, a thin film diode, a metal insulator metal resistivity element, etc. can also be provided on the substrate.

[0460] It is preferable that the first substrate and the second substrate face each other such that the common electrode and the pixel electrode layer are located inside.

[0461] The interval between the first substrate and the second substrate can also be adjusted through a spacer. At this time, it is preferably adjusted to a thickness of the obtained dimming layer of 1 to 100 μm. More preferably, it is 1.5 to 10 μm. When a polarizing plate is used, it is preferred to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the unit thickness d in a way that the contrast is maximized. In addition, when there are two polarizing plates, the polarization axis of each polarizing plate can also be adjusted to adjust the viewing angle and contrast to be good. Furthermore, a phase difference film for expanding the viewing angle can also be used. As spacers, for example, glass particles, plastic particles, aluminum oxide particles, photoresist materials, etc. Then, as needed, a sealant such as an epoxy-based thermosetting composition is screen-printed on the substrate with a mold provided with a liquid crystal injection port, the substrates are bonded to each other, and heated to thermally cure the sealant.

[0462] As a method for sandwiching the liquid crystal composition between two substrates, a common vacuum injection method, ODF method, or the like can be used.

[0463] As a method for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention, in order to obtain good orientation properties of the liquid crystal, it is ideal to polymerize at a moderate polymerization speed. Therefore, it is preferably polymerized by single or combined use or sequential irradiation of active energy rays such as ultraviolet rays or electron beams. When ultraviolet rays are used, a polarized light source can be used, and a non-polarized light source can also be used. In addition, when the polymerization is performed in a state where the liquid crystal composition is clamped between two substrates, at least the substrate on the irradiated side must be given appropriate transparency relative to the active energy rays. In addition, the following means can also be used: after using a mask to polymerize only a specific part during irradiation, the conditions such as the electric field, magnetic field or temperature are changed, thereby changing the orientation state of the unpolymerized part, and further irradiating the active energy rays to polymerize it. In particular, when ultraviolet exposure is performed, it is preferred to apply a DC electric field or an AC electric field to the liquid crystal composition and simultaneously perform ultraviolet exposure. Among them, the applied AC electric field is preferably an AC with a frequency of 1Hz to 10kHz, more preferably a frequency of 60Hz to 10kHz, and the voltage is selected depending on the desired pre-tilt angle of the liquid crystal display element. In other words, the pre-tilt angle of the liquid crystal display element can be controlled by the applied voltage. In the case of a PSA type or PSVA type liquid crystal display element, the pretilt angle is preferably controlled to be 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.

[0464] In a PSA or PSVA type liquid crystal display element, if a polymerizable compound remains without being polymerized after element production, IS will occur. The amount of the remaining polymerizable compound is preferably 100 ppm or less, more preferably 50 ppm or less, particularly preferably 20 ppm or less, and particularly preferably below the detection limit or 0.

[0465] There is no particular restriction on the temperature of irradiation with active energy rays such as ultraviolet rays or electron beams used to polymerize the polymerizable compound contained in the liquid crystal composition of the present invention. For example, when the liquid crystal composition of the present invention is applied to a liquid crystal display element having a substrate with an alignment film, it is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained. In other words, it is preferably polymerized at 15 to 50°C.

[0466] As the lamp generating ultraviolet rays, metal halide lamps, high pressure mercury lamps, ultra-high pressure mercury lamps, etc. can be used, preferably ultra-high pressure UV lamps of USHIO Company and fluorescent ultraviolet lamps of TOSHIBA Company. In addition, as the wavelength of the ultraviolet rays irradiated, it is preferred to irradiate ultraviolet rays whose wavelength region is not in the absorption wavelength region of the liquid crystal composition, and it is preferred to filter out the ultraviolet rays and use them as needed. The intensity of the irradiated ultraviolet rays is preferably 0.1 mW / cm 2 ~100W / cm 2 , more preferably 2mW / cm 2 ~50W / cm 2 The energy of the irradiated ultraviolet light can be adjusted appropriately, preferably 10 mJ / cm 2 Up to 500J / cm 2 , more preferably 100 mJ / cm 2 Up to 200J / cm 2 .

[0467] Example

[0468] The present invention is further described in detail with reference to the following examples, but the present invention is not limited to these examples. In addition, "%" in the compositions of the following examples and comparative examples means "mass %". The following abbreviations are used for describing the compounds in the examples.

[0469] (Sidechain)

[0470] -nC n H 2n+1 A linear alkyl group with n carbon atoms

[0471] nC n H 2n+1 - a linear alkyl group having n carbon atoms

[0472] -On-OC n H 2n+1 A linear alkoxy group with n carbon atoms

[0473] nO-C n H 2n+1 O-straight-chain alkoxy with n carbon atoms

[0474] -V-CH=CH2

[0475] V-CH2=CH-

[0476] -V--CH=CH-

[0477] -O1V-O-CH2-V

[0478] -V1-CH=CH-CH3

[0479] 1V-CH3-CH=CH-

[0480] -2V-CH2-CH2-CH=CH2

[0481] V2-CH2=CH-CH2-CH2-

[0482] -2V1-CH2-CH2-CH=CH-CH3

[0483] 1V2-CH3-CH=CH-CH2-CH2-

[0484] -FF

[0485] -OCF3-OCF3

[0486] (Linking base)

[0487] -CF2O--CF2-O-

[0488] -OCF2--O-CF2-

[0489] -1O--CH2-O-

[0490] -O1--O-CH2-

[0491] -COO--COO-

[0492] -OCO--OCO-

[0493] (Ring structure)

[0494] [Chemistry 68]

[0495]

[0496] In the examples, the properties measured are as follows.

[0497] T ni :Nemetic phase-isotropic liquid phase transition temperature (℃)

[0498] Δn: refractive index anisotropy at 20°C

[0499] η: Viscosity at 20°C (mPa·s)

[0500] γ1: Rotational viscosity at 20°C (mPa·s)

[0501] Δε: Dielectric anisotropy at 20°C

[0502] K 33 : Elastic constant K at 20℃ 33 (pN)

[0503] (Manufacturing method and evaluation method of liquid crystal display element)

[0504] (Evaluation of Pretilt Angle Change)

[0505] First, the pretilt angle of the liquid crystal display element is measured and is referred to as a pretilt angle (initial).

[0506] Next, a rectangular voltage of 30 V was applied to the liquid crystal display element at a frequency of 100 Hz, and light was continuously irradiated from a backlight for 10 hours. Then, the pretilt angle was measured and referred to as the pretilt angle (after the test).

[0507] The value obtained by subtracting the pretilt angle (after the test) from the measured pretilt angle (initial) is defined as the pretilt angle change amount (= absolute value of the pretilt angle change) [°].

[0508] The pretilt angle was measured using a pretilt angle measurement system (manufactured by Shintec Corporation, "OPTIPRO"). The magnitude of the applied voltage (30 V) was several times greater than a normal driving voltage, and this evaluation test was an accelerated test.

[0509] The closer the pretilt angle change amount is to 0 [°], the lower the possibility of display failure due to the change in the pretilt angle.

[0510] In this evaluation, the variation of 0.3[°] was set as the allowable limit range of display failure.

[0511] (Evaluation of Residual Monomer Amount)

[0512] First, a liquid crystal composition containing a polymerizable compound was injected by vacuum injection into a liquid crystal cell having a cell gap of 3.5 μm and including an ITO-attached substrate coated with a polyimide alignment film inducing vertical alignment and subjected to a rubbing treatment.

[0513] Then, the liquid crystal cell into which the liquid crystal composition containing the polymerizable compound was injected was illuminated using a fluorescent UV lamp adjusted to an illuminance of 3.5 mW / cm2 at a central wavelength of 365 nm. 2 , irradiating ultraviolet rays for 120 minutes to obtain a liquid crystal display element (wherein the evaluation of each characteristic value of the liquid crystal display element is carried out using a liquid crystal display element produced by the same method).

[0514] The residual amount [ppm] of the polymerizable compound in the liquid crystal display element after irradiation is measured under the above-mentioned irradiation conditions. The method for determining the residual amount of the polymerizable compound is described below. First, the liquid crystal display element is decomposed to obtain an acetonitrile solution containing the eluted components of the liquid crystal composition, the polymer, and the unreacted polymerizable compound. It is analyzed by high performance liquid chromatography to measure the peak area of ​​each component. The amount of the remaining polymerizable compound is determined based on the ratio of the peak area of ​​the liquid crystal compound as an indicator to the peak area of ​​the unreacted polymerizable compound. The residual amount of the polymerizable compound is determined based on this value and the amount of the polymerizable compound initially added. Among them, the detection limit of the residual amount of the polymerizable compound is 10ppm. In this evaluation, the residual amount of 100ppm is set as the allowable limit range for poor display.

[0515] (Evaluation of voltage holding ratio)

[0516] First, a liquid crystal composition containing a polymerizable compound was injected into a liquid crystal cell having a cell gap of 3.5 μm including an ITO-attached substrate having no polyimide alignment film by a vacuum injection method.

[0517] Next, after heating at 120°C for 1 hour, a fluorescent UV lamp was used and adjusted to an illuminance of 3.5 mW / cm2 at a central wavelength of 365 nm. 2 The liquid crystal display element was obtained by irradiating ultraviolet rays for 120 minutes. The measurement conditions were 1 V, 0.6 Hz, and 60°C.

[0518] (Preparation and Evaluation Results of Liquid Crystal Compositions)

[0519] Liquid crystal compositions of LC-1 and LC-2 were prepared and their physical properties were measured. The compositions of the liquid crystal compositions and their physical properties are shown in Table 1.

[0520] [Table 1]

[0521]

[0522] [Chemistry 69]

[0523]

[0524] [Chemistry 70]

[0525]

[0526] [Chemistry 71]

[0527]

[0528] (Comparative Examples 1 and 2, Examples 1 to 5)

[0529] Each polymerizable compound described below was added to 100 parts by mass of the liquid crystal composition (LC-1 and LC-2) to prepare a polymerizable liquid crystal composition. A liquid crystal display element was prepared using the polymerizable liquid crystal composition by the above method, and each value was measured.

[0530] Relative to 100 parts by mass of liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by formula (SAL-X1), 0.4 parts by mass of the compound represented by formula (SAL-X2), and 0.6 parts by mass of the compound represented by formula (RM-R1) were added, and the resulting liquid crystal composition containing a polymerizable compound was set as Comparative Example 1.

[0531] Relative to 100 parts by mass of liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by formula (SAL-X1), 0.4 parts by mass of the compound represented by formula (SAL-X2), and 0.6 parts by mass of the compound represented by formula (RM-R2) are added, and the resulting liquid crystal composition containing a polymerizable compound is set as Comparative Example 2.

[0532] Relative to 100 parts by mass of liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by formula (SAL-X1), 0.4 parts by mass of the compound represented by formula (SAL-X2), and 0.6 parts by mass of the compound represented by formula (RM-11) were added, and the resulting liquid crystal composition containing a polymerizable compound was set as Example 1.

[0533] Relative to 100 parts by mass of liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by formula (SAL-X1), 0.4 parts by mass of the compound represented by formula (SAL-X2), and 0.6 parts by mass of the compound represented by formula (RM-3) are added, and the resulting liquid crystal composition containing a polymerizable compound is set as Example 2.

[0534] Relative to 100 parts by mass of liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by formula (SAL-X1), 0.4 parts by mass of the compound represented by formula (SAL-X2), and 0.6 parts by mass of the compound represented by formula (RM-4) are added, and the resulting liquid crystal composition containing a polymerizable compound is set as Example 3.

[0535] Relative to 100 parts by mass of the liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by formula (SAL-X1), 0.4 parts by mass of the compound represented by formula (SAL-X2), 0.3 parts by mass of the compound represented by formula (RM-1), and 0.3 parts by mass of the compound represented by formula (RM-11) are added, and the resulting liquid crystal composition containing the polymerizable compound is set as Example 4.

[0536] Relative to 100 parts by mass of the liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by formula (SAL-X1), 0.4 parts by mass of the compound represented by formula (SAL-X2), 0.3 parts by mass of the compound represented by formula (RM-1), and 0.3 parts by mass of the compound represented by formula (RM-3) are added, and the resulting liquid crystal composition containing a polymerizable compound is set as Example 5.

[0537] The voltage holding ratio, the change in pretilt angle, and the remaining amount of all polymerizable compounds after ultraviolet irradiation of Comparative Examples 1 to 2 and Examples 1 to 5 are shown in Table 2 below.

[0538] [Table 2]

[0539]

[0540] It is found that the voltage holding ratios of Examples 1 to 3, which are the liquid crystal compositions of the present invention, show values ​​significantly higher than those of Comparative Examples 1 and 2. As described above, by using the compound represented by the general formula (i), screen burn-in and the like can be prevented.

[0541] Furthermore, it can be seen that the voltage holding ratios of Examples 4 and 5 show values ​​higher than that of Comparative Example 1.

[0542] As described above, it was found that even when a part of the polymerizable compound represented by the general formula (L) was replaced with a compound represented by the general formula (i), a high retention rate was exhibited.

[0543] It can be seen that the amount of change in the pretilt angle in Examples 1 to 5 is sufficiently small.

[0544] It is understood that the residual amount of the polymer compound in Examples 1 to 5 is also sufficiently small.

[0545] Furthermore, even after the polymerizable liquid crystal compositions prepared in Examples 1 to 3 were stored at -20°C for 240 hours, the nematic liquid crystal phase was maintained, and no precipitation of the polymerizable compound was observed.

[0546] From the above, it was confirmed that the liquid crystal composition of the present invention has a sufficiently high voltage holding ratio, is unlikely to cause display defects due to changes in the pretilt angle, and has no precipitation of polymerizable compounds.

[0547] (Comparative Examples 3 and 4, Examples 6 to 10)

[0548] Relative to 100 parts by mass of liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by formula (SAL-X2), 0.5 parts by mass of the compound represented by formula (SAL-X3), and 0.6 parts by mass of the compound represented by formula (RM-R3) are added, and the resulting liquid crystal composition containing a polymerizable compound is set as Comparative Example 3.

[0549] Relative to 100 parts by mass of liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by formula (SAL-X2), 0.5 parts by mass of the compound represented by formula (SAL-X3), and 0.6 parts by mass of the compound represented by formula (RM-R3) are added, and the resulting liquid crystal composition containing a polymerizable compound is set as Comparative Example 4.

[0550] Relative to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by formula (SAL-X2), 0.5 parts by mass of the compound represented by formula (SAL-X3), and 0.6 parts by mass of the compound represented by formula (RM-25) are added, and the resulting liquid crystal composition containing the polymerizable compound is set as Example 6.

[0551] To 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by formula (SAL-X2), 0.5 parts by mass of the compound represented by formula (SAL-X3), and 0.6 parts by mass of the compound represented by formula (RM-28) are added, and the resulting liquid crystal composition containing a polymerizable compound is set as Example 7.

[0552] Relative to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by formula (SAL-X2), 0.5 parts by mass of the compound represented by formula (SAL-X3), and 0.6 parts by mass of the compound represented by formula (RM-23) are added, and the resulting liquid crystal composition containing the polymerizable compound is set as Example 8.

[0553] Relative to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by formula (SAL-X2), 0.5 parts by mass of the compound represented by formula (SAL-X3), and 0.6 parts by mass of the compound represented by formula (RM-33) are added, and the resulting liquid crystal composition containing the polymerizable compound is set as Example 9.

[0554] Relative to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by formula (SAL-X2), 0.5 parts by mass of the compound represented by formula (SAL-X3), 0.3 parts by mass of the compound represented by formula (RM-25), and 0.3 parts by mass of the compound represented by formula (RM-28) are added, and the resulting liquid crystal composition containing the polymerizable compound is set as Example 10.

[0555] Relative to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by formula (SAL-X2), 0.5 parts by mass of the compound represented by formula (SAL-X3), 0.3 parts by mass of the compound represented by formula (RM-25), and 0.3 parts by mass of the compound represented by formula (RM-23) are added, and the resulting liquid crystal composition containing the polymerizable compound is set as Example 11.

[0556] The voltage holding ratio, the change in pretilt angle, and the remaining amount of all polymerizable compounds after ultraviolet irradiation of Comparative Examples 3 and 4 and Examples 6 to 11 are shown in the table.

[0557] [Table 3]

[0558] Comparative Example 3 Comparative Example 4 Liquid crystal composition LC-B LC-B SAL-X2 0.4 0.4 SAL-X3 0.5 0.5 RM-R3 0.6 RM-R4 0.6 RM-25 RM-28 RM-23 RM-33 Voltage holding rate 84.6 85.3 Pretilt angle change 3.4 2.5 Residual amount of polymerizable compounds 25 35

[0559] [Table 4]

[0560] Example 6 Example 7 Example 8 Example 9 Example 10 Embodiment 11 Liquid crystal composition LC-B LC-B LC-B LC-B LC-B LC-B SAL-X2 0.4 0.4 0.4 0.4 0.4 0.4 SAL-X3 0.5 0.5 0.5 0.5 0.5 0.5 RM-R3 RM-R4 RM-25 0.6 0.3 0.3 RM-28 0.6 0.3 RM-23 0.6 0.3 RM-33 0.6 Voltage holding rate 97.5 97.2 97.8 96.5 96.5 93.8 Pretilt angle change 0.1 0.1 0.2 0.1 0.1 0.1 Residual amount of polymerizable compounds 55 43 23 70 34 32

[0561] It is found that the voltage holding ratios of Examples 6 to 9, which are polymerizable liquid crystal compositions of the present invention, show values ​​significantly higher than those of Comparative Examples 3 and 4. As described above, by using the compound represented by the general formula (i), display defects such as screen burn-in can be prevented.

[0562] It can be seen that the voltage holding ratios of Examples 10 and 11 also show values ​​higher than those of Comparative Examples 3 and 4.

[0563] As described above, it is understood that even when two or more compounds represented by the general formula (i) are used, a high voltage holding ratio is exhibited.

[0564] It can be seen that the amount of change in the pretilt angle in Examples 6 to 11 is sufficiently small.

[0565] It is understood that the residual amount of the polymer compound in Examples 6 to 11 is also sufficiently small.

[0566] Furthermore, even after the polymerizable liquid crystal compositions prepared in Examples 6 to 11 were stored at -20°C for 240 hours, the nematic liquid crystal phase was maintained, and no precipitation of the polymerizable compound was observed.

[0567] From the above, it was confirmed that by using the polymerizable liquid crystal composition of the present invention, a liquid crystal display element having a sufficiently high voltage holding ratio, hardly causing display failure due to a change in the pretilt angle, and having no residual polymerizable compound can be obtained.

Claims

1. A polymerizable liquid crystal composition comprising a liquid crystal composition and one or more polymerizable compounds represented by general formula (i), and An alignment aid having a chemical structure different from that of the polymerizable compound represented by the general formula (i) and having an adsorption group; [Chemistry 1] Where, X i1 , X i2 , X i3 , X i4 , X i5 , X i6 , X i7 , X i8 , X i9 , X i10 , X i11 and X i12 each independently represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, Selected from X i1 ~X i12 At least two of the above are independently an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a halogen atom, P i1 and P i2 Each independently represents any one of the following formula (RI) to formula (R-IX), [Chemistry 2] In the formula, R 21 , R 31 , R 41 , R 51 and R 61 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, W represents a single bond, -O- or a methylene group, T represents a single bond or -COO-, p, t and q each independently represent 0, 1 or 2, Sp i1 and Sp i2 each independently represents a single bond or an alkylene group having 1 to 15 carbon atoms, wherein one or more -CH2- in the alkylene group may be substituted by -O-, -OCO- or -COO- in a manner that the oxygen atom is not directly adjacent thereto, n i1 represents 0, 1 or 2, L i1 and L i2 Each independently represents a single bond, -OCH2-, -CH2O-, -C2H4-, -OC2H4O-, -COO-, -OCO-, -CH=CR a -COO-, -CH=CR a -OCO-, -COO-CR a =CH-, -OCO-CR a =CH-, -(CH2) z -COO-, -(CH2) z -OCO-, -OCO-(CH2) z -、-COO-(CH2) z -, -CH=CH-, -CF2O-, -OCF2- or -C≡C-, where R a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and z represents an integer of 1 to 4, When there are multiple X i5 , X i6 , X i7 , X i8 and / or L i2 In the case of , they may be the same or different; The alignment aid is a compound having a polymerizable group for polymerization, a mesogen group similar to a liquid crystal molecule, an adsorption group capable of interacting with a member directly in contact with the liquid crystal layer, and an alignment inducing group for inducing the alignment of the liquid crystal molecules; The mesogen is represented by the general formula (AL1), The adsorbent group is selected from the following adsorbent groups: The orientation inducing group is represented by the general formula (AK), The adsorption group is bonded to the mesogen group, and The alignment inducing group is bonded to the mesogen group; Liquid crystal base: In the formula, Z AL1 represents a single bond, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CF2O-, -OCF2-, -CH=CHCOO-, -OCOCH=CH-, -CH2-CH2COO-, -OCOCH2-CH2-, -CH=C(CH3)COO-, -OCOC(CH3)=CH-, -CH2-CH(CH3)COO-, -OCOCH(CH3)-CH2-, -OCH2CH2O-, or an alkylene group having 1 to 20 carbon atoms; wherein, One or two or more non-adjacent -CH2- in the alkylene group are optionally substituted by -O-, -COO- or -OCO-; m AL1 Indicates an integer from 1 to 5; A AL1 represents a divalent cyclic group; A AL1 One or more hydrogen atoms in the cyclic group represented by may be replaced by a halogen group, an adsorbent group, a P AP1 -Sp AP1 -replace; P AP1 A group selected from the group represented by the following general formula (AP-1) to general formula (AP-9), [Chemistry 21] In the formula, R AP1 and R AP2 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms; wherein one or more -CH2- in the alkyl group are optionally substituted by -O- or -CO-, and one or more hydrogen atoms in the alkyl group are optionally substituted by a halogen atom or a hydroxyl group; W AP1 represents a single bond, -O-, -COO- or -CH2-; t AP1 Represents 0, 1, or 2; *Indicates the same as Sp AP1 Connect key; Sp AP1 represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, wherein one or two or more non-adjacent -CH2- groups in the alkylene group are optionally and independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-; Bonded to A AL1 The * represents the connection bond with the orientation-inducing group; The * bonded to the benzene ring indicates the bond to the adsorbent group; Adsorption group: Wherein, * represents the connection bond with the mesogen group; Orientation-inducing group: [Chemistry 20] R AK1 -*(AK) In the formula, R AK1 It represents a linear or branched alkyl group having 1 to 20 carbon atoms; wherein one or more -CH2- in the alkyl group are optionally and independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- when the oxygen atom is not directly connected, and one or more hydrogen atoms in the alkyl group are optionally and independently replaced by halogen groups.

2. The polymerizable liquid crystal composition according to claim 1, wherein In the general formula (i), selected from X i5 , X i6 , X i7 , X i8 , X i9 , X i10 , X i11 and X i12 At least two of the groups independently represent an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a halogen atom.

3. The polymerizable liquid crystal composition according to claim 1 or 2, wherein: In the general formula (i), selected from X i5 , X i6 , X i7 , X i8 , X i9 , X i10 , X i11 and X i12 At least two of the groups are independently an alkyl group having 1 to 18 carbon atoms or a halogen atom.

4. The polymerizable liquid crystal composition according to claim 1, wherein: In the general formula (i), n i1 is 0, selected from X i9 , X i10 , X i11 and X i12 At least one of the groups is independently an alkyl group having 1 to 18 carbon atoms.

5. The polymerizable liquid crystal composition according to claim 1, wherein: In the general formula (i), n i1 is 1 or 2, selected from X i5 , X i6 , X i7 , X i8 , X i9 , X i10 , X i11 and X i12 At least one of the groups is independently an alkyl group having 1 to 18 carbon atoms.

6. The polymerizable liquid crystal composition according to claim 1, wherein: In the general formula (i), n i1 is 0, selected from X i9 , X i10 , X i11 and X i12 The two of them are each independently an alkyl group having 1 to 3 carbon atoms or a halogen atom.

7. The polymerizable liquid crystal composition according to claim 1, wherein: In the general formula (i), n i1 is 1 or 2, selected from X i5 , X i6 , X i7 and X i8 Two of them are independently an alkyl group having 1 to 18 carbon atoms, a halogen atom, or selected from X i9 , X i10 , X i11 and X i12 Two of them are alkyl groups having 1 to 18 carbon atoms or halogen atoms.

8. The polymerizable liquid crystal composition according to claim 1, wherein: In the general formula (i), n i1 Is 0 or 1.

9. The polymerizable liquid crystal composition according to claim 1, wherein: In the general formula (i), X i12 or X i11 A hydrogen atom.

10. The polymerizable liquid crystal composition according to claim 1, wherein: In the general formula (i), L i1 and L i2 For a single key.

11. The polymerizable liquid crystal composition according to claim 1, wherein: The amount of the polymerizable compound represented by the general formula (i) added is 0.20% by mass to 1.0% by mass.

12. The polymerizable liquid crystal composition according to claim 1, comprising one or more compounds selected from the group consisting of compounds represented by general formula (N-01) to general formula (N-05), [Chemistry 3] In the formula, R 21 and R 22 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, wherein one or two or more non-adjacent -CH2- groups in the group are optionally and independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and Z 1 Each independently represents a single bond, -CH2CH2-, -OCH2-, -CH2O-, -COO-, -OCO-, -OCF2-, -CF2O-, -CH=CH-, -CF=CF- or -C≡C-, and m each independently represents 1 or 2.

13. The polymerizable liquid crystal composition according to claim 1, comprising one or more compounds selected from the group consisting of compounds represented by general formula (NU-01) to general formula (NU-08), [Chemistry 4] In the formula, R NU11 , R NU12 , R NU21 , R NU22 , R NU31 , R NU32 , R NU41 , R NU42 , R NU51 , R NU52 , R NU61 , R NU62 , R NU71 , R NU72 , R NU81 and R NU82 Each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, and one or more non-adjacent -CH2- groups in the group are optionally and independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-. 14 . A liquid crystal display element using the polymerizable liquid crystal composition according to claim 1 . 15 . A liquid crystal display element for active matrix driving, comprising the polymerizable liquid crystal composition according to claim 1 . 16 . A liquid crystal display element for a PSA mode, a PSVA mode, a PS-IPS mode or a PS-FSS mode, comprising the polymerizable liquid crystal composition according to claim 1 . 17 . The polymerizable liquid crystal composition according to claim 1 , which is used in a liquid crystal display element in which at least one of a pair of substrates has no alignment film on its surface.

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