TW202039799A - Liquid crystal display element - Google Patents

Abstract

Provided is a liquid crystal display element that is excellent in terms of its liquid crystal orientation, orientation stability, high voltage holding ratio, and voltage holding ratio stability. The liquid crystal display element according to the present invention is characterised by comprising two substrates and a liquid crystal layer provided between said two substrates, the liquid crystal layer including liquid crystal molecules and a polymer of polymerisable monomers, the residual amount of the polymerisable monomers in the liquid crystal layer being 200 ppm or less. Moreover, the residual amount of the polymerisable monomers in the liquid crystal layer is preferably 10 ppm or more. In addition, the polymerisable monomers preferably include a polymerisable monomer A having an adsorbing group.

Description

Liquid crystal display element

The present invention relates to a liquid crystal display element.

In the past, in the VA mode liquid crystal display, in order to induce the vertical alignment of the liquid crystal molecules when no voltage is applied, and to realize the horizontal alignment of the liquid crystal molecules when a voltage is applied, a polyimide functioning as an alignment film is provided on the electrodes ( PI) membrane. However, the production of the PI film requires a huge cost. In recent years, a method for realizing the alignment of liquid crystal molecules despite the omission of the PI film has been studied (for example, refer to Patent Document 1). Patent Document 1 here discloses that by reducing the amount of residual monomers in a liquid crystal layer containing a liquid crystal compound (liquid crystal molecule) and a polymer of a polymerizable compound (polymerizable monomer), the voltage retention rate (VHR) and Ion density (ID). [Prior Technical Literature] [Patent Literature]

Patent Document 1: International Publication No. 2016/143601

[The problem to be solved by the invention]

However, according to the investigation by the inventors of the present case, it was found that the improvement effect of the voltage retention ratio according to the residual monomer amount described in the Example of Patent Document 1 is still insufficient, and there is room for further improvement. The present invention was made in view of this point of view, and its object is to provide a liquid crystal display element that is excellent in liquid crystal alignment, alignment stability, high voltage retention, and stability of voltage retention. [Technical means to solve the problem]

Such an objective is achieved by the present invention of the following (1) to (12). (1) A liquid crystal display element including two substrates, and A liquid crystal layer arranged between the two substrates, The liquid crystal layer contains liquid crystal molecules and polymers of polymerizable monomers, In the liquid crystal layer, the residual amount of the polymerizable monomer is 200 ppm or less. (2) The liquid crystal display element according to the above (1), wherein the residual amount of the polymerizable monomer in the liquid crystal layer is 10 ppm or more. (3) The liquid crystal display element of (1) or (2) above, wherein the polymerizable monomer includes a polymerizable monomer A having an adsorption group. (4) The liquid crystal display element according to the above (3), wherein the residual amount of the polymerizable monomer A in the liquid crystal layer is 100 ppm or less. (5) The liquid crystal display element according to any one of (1) to (4) above, wherein the polymerizable monomer includes a polymerizable monomer B that does not have an adsorption group. (6) The liquid crystal display element according to the above (5), wherein the residual amount of the polymerizable monomer B in the liquid crystal layer is 100 ppm or less.

（式（P）中，R^p1 表示氫原子、氟原子、氰基、碳原子數1～15之烷基或－Sp^p2 －P^p2 [上述烷基中所存在之1個或不相鄰之2個以上之－CH₂ －可分別獨立地被－CH＝CH－、－C≡C－、－O－、－CO－、－COO－或－OCO－取代，上述烷基中所存在之1個或2個以上之氫原子可分別獨立地被氰基、氟原子或氯原子取代]， P^p1 及P^p2 分別獨立地表示下述通式（P^p1 －1）～式（P^p1 －9）之任一者，

[式中，R^p11 及R^p12 分別獨立地表示氫原子、碳原子數1～5之烷基或碳原子數1～5之鹵化烷基，W^p11 表示單鍵、－O－、－COO－、－OCO－或－CH₂ －，t^p11 表示0、1或2，於分子内存在複數個R^p11 、R^p12 、W^p11 及／或t^p11 之情形時，其等可相同，亦可不同，*表示鍵結鍵]， Sp^p1 及Sp^p2 分別獨立地表示單鍵或間隔基， Z^p1 及Z^p2 分別獨立地表示單鍵、－O－、－S－、－CH₂ －、－OCH₂ －、－CH₂ O－、－CO－、－C₂ H₄ －、－COO－、－OCO－、－OCOOCH₂ －、－CH₂ OCOO－、－OCH₂ CH₂ O－、－CO－NR^ZP1 －、－NR^ZP1 －CO－、－SCH₂ －、－CH₂ S－、－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 －、－CF₂ O－、－OCF₂ －、－CF₂ CH₂ －、－CH₂ CF₂ －、－CF₂ CF₂ －或－C≡C－[式中，R^ZP1 分別獨立地表示氫原子或碳原子數1～4之烷基，於分子内存在複數個R^ZP1 之情形時，其等可相同，亦可不同]， A^p1 、A^p2 及A^p3 分別獨立地表示選自由基（a^p ）～基（c^p ）所組成之群中的基[下述基（a^p ）、基（b^p ）及基（c^p ）中所存在之氫原子可分別獨立地被鹵素原子、碳原子數1～8之烷基或碳原子數1～8之烯基、氰基或－Sp^p2 －P^p2 取代]， （a^p ）1,4－伸環己基[該基中所存在之1個－CH₂ －或不相鄰之2個以上之－CH₂ －可被－O－取代]， （b^p ）1,4－伸苯基[該基中所存在之1個－CH＝或不相鄰之2個以上之－CH＝可被－N＝取代]，及 （c^p ）萘－2,6－二基、萘－1,4－二基、萘－1,5－二基、1,2,3,4－四氫萘－2,6－二基、十氫萘－2,6－二基、菲－2,7－二基或蒽－2,6－二基[該等基中所存在之1個－CH＝或不相鄰之2個以上之－CH＝可被－N＝取代]， m^p1 表示0、1、2或3， 於分子内存在複數個Z^p1 、A^p2 、Sp^p2 及／或P^p2 之情形時，其等可相同，亦可不同，A^p3 於m^p1 為0且A^p1 為上述基（c^p ）之情形時，表示單鍵）。(7) The liquid crystal display element according to (5) or (6) above, wherein the polymerizable monomer B is represented by the following general formula (P).

(In formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group with 1 to 15 carbon atoms, or -Sp ^p2 -P ^p2 [one of the above alkyl groups or non-adjacent ones Two or more -CH ₂ -can be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and 1 of the above-mentioned alkyl groups One or more hydrogen atoms may be independently substituted by cyano, fluorine or chlorine atoms], P ^p1 and P ^p2 each independently represent the following general formulas (P ^p1 -1) to formula (P ^p1 -9 ) Any one of them,

[In the formula, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a halogenated alkyl group with 1 to 5 carbon atoms, and W ^p11 represents a single bond, -O-, -COO- , -OCO- or -CH ₂ -, t ^p11 represents 0, 1 or 2, and when there are multiple R ^p11 , R ^p12 , W ^p11 and/or t ^p11 in the molecule, they can be the same or different , * Represents a bonding bond], Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer, Z ^p1 and Z ^p2 each independently represent a single bond, -O-, -S-, -CH ₂ -, -OCH _{2 -, - CH 2 O -} , - CO -, - C 2 H 4 -, - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO- NR ^ZP1 －, －NR ^ZP1 －CO－, ^－SCH ₂ －, －CH ₂ S－, －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 －,－(CH ₂ ) ₂ －COO－,－(CH ₂ ) ₂ －OCO－, －OCO－(CH ₂ ) ₂ －,－(C=O)－O－(CH ₂ ) ₂ －,－CH =CH-, -CF=CF-, -CF=CH-, -CH=CF-, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ －, －CF ₂ CF ₂ － or －C≡C－[In the formula, R ^ZP1 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and when there are plural R ^ZP1 in the molecule, which Etc. may be the same or different], A ^p1 , A ^p2 and A ^p3 each independently represent a group selected from the group consisting of radicals (a ^p ) to group (c ^p ) [the following groups (a ^p ), The hydrogen atoms present in the group (b ^p ) and the group (c ^p ) can be independently replaced by a halogen atom, an alkyl group with 1 to 8 carbon atoms, an alkenyl group with 1 to 8 carbon atoms, a cyano group, or -Sp ^p2 -P ^p2 substitution], (a ^p ) 1,4-cyclohexylene [1 -CH ₂ -or ₂ or more non-adjacent -CH ₂ -in the group can be substituted by -O- ], (b ^p ) 1,4-phenylene [1 -CH= or 2 or more non-adjacent -CH= can be substituted by -N= in the group], and (c ^p ) Naphthalene-2,6-diyl, naphthalene-1 ,4-diyl, naphthalene-1,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decalin-2,6-diyl, phenanthrene-2,7 －Diyl or anthracene-2,6-diyl [1 of these groups -CH= or 2 or more non-adjacent -CH= can be substituted by -N=], m ^p1 represents 0, 1, 2 or 3, when there are a plurality of Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 in the molecule, they can be the same or different. A ^p3 is 0 in m ^p1 and A ^p1 is the above In the case of base (c ^p ), it means a single bond).

（式中，R^AP1 及R^AP2 分別獨立地表示氫原子、碳原子數1～5之烷基或碳原子數1～10之鹵化烷基[該烷基中之1個或2個以上之－CH₂ －可被－O－或－CO－取代，上述烷基中之1個或2個以上之氫原子可分別獨立地被鹵素原子或羥基取代， W^AP1 表示單鍵、－O－、－COO－、－OCO－或－CH₂ －， t^AP1 表示0、1或2， *表示鍵結鍵）。(8) The liquid crystal display element according to any one of the above (1) to (7), wherein the polymerizable monomer is selected from the following general formulas (AP-1) to (AP-9) The cohesive base in the group.

(In the formula, R ^AP1 and R ^AP2 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a halogenated alkyl group with 1 to 10 carbon atoms [one or more of the alkyl groups- CH ₂ -may be substituted by -O- or -CO-, one or more of the hydrogen atoms in the above alkyl group may be independently substituted by halogen atoms or hydroxyl groups, W ^AP1 represents a single bond, -O-,- COO-, -OCO- or -CH ₂ -, t ^AP1 means 0, 1 or 2, * means bonding bond).

(9) The liquid crystal display element according to any one of (1) to (8) above, wherein the liquid crystal molecules have a negative dielectric anisotropy (Δε). (10) The liquid crystal display element of any one of (1) to (9) above, which is used for active matrix driving. (11) The liquid crystal display element according to any one of (1) to (10) above, which is a PSA type, PSVA type, VA type, IPS type, FFS type or ECB type. (12) The liquid crystal display element according to any one of (1) to (11) above, wherein at least one of the two substrates does not have an alignment film. [Effects of Invention]

According to the present invention, it is possible to provide a liquid crystal display device having excellent characteristics (especially voltage retention) by optimizing the residual amount of polymerizable monomer in the liquid crystal layer.

Hereinafter, the liquid crystal display element of the present invention will be described in detail based on preferred embodiments. (Liquid crystal composition) The liquid crystal composition used in the present invention is used to form the liquid crystal layer of the liquid crystal display element. The liquid crystal composition of the present embodiment contains liquid crystal molecules whose dielectric anisotropy (Δε) is a negative value, and an alignment aid (polymerizable monomer A) having a function of spontaneously aligning the liquid crystal molecules. ((Alignment aid)) The alignment aid has the following functions: members (electrodes (such as ITO), substrates (such as glass substrates, acrylic substrates, transparent substrates, flexible substrates, etc.) that directly contact the liquid crystal layer containing the liquid crystal composition, and resin layers ( For example, color filters, alignment films, overcoats, etc.) and insulating films (such as inorganic material films, SiNx, etc.) interact to cause the vertical alignment of the liquid crystal molecules contained in the liquid crystal layer.

The alignment aid preferably has a polymerizable group for polymerization, a mesogen group similar to liquid crystal molecules, an adsorption group (polar group) that can interact with a member directly abutting the liquid crystal layer, and causes alignment of liquid crystal molecules The alignment inducer. Preferably, the adsorption group and the alignment-inducing group are bonded to the mesogen, and the polymerizable group is substituted into the mesogen, the adsorption group and the alignment-inducing group directly or via spacers as needed. In particular, the polymerizability is preferably substituted by a mesogen group based on the state incorporated into the adsorption group. Hereinafter, the * at the left end and the * at the right end in the chemical formula represent bonding bonds.

式中，R^AK1 表示直鏈狀或支鏈狀之碳原子數1〜20之烷基。其中，烷基中之1個或不相鄰之2個以上之－CH₂ －可分別獨立地被－CH＝CH－、－C≡C－、－O－、－CO－、－COO－或－OCO－取代，烷基中之1個或2個以上之氫原子可分別獨立地被鹵代基（halogeno group）取代。"Orientation-inducing group" The orientation-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).

In the formula, R ^AK1 represents a linear or branched alkyl group having 1 to 20 carbon atoms. Among them, one of the alkyl groups or two or more non-adjacent -CH ₂ -s can be independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substitution, one or more hydrogen atoms in the alkyl group can be independently substituted by halogeno groups.

R ^AK1 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 more preferably represents a linear alkyl group An alkyl group with 1 to 8 carbon atoms. In addition, one of the alkyl groups or two or more non-adjacent -CH ₂ -s can be independently -CH=CH-, -C≡C-, -O-, so that oxygen atoms are not directly adjacent to each other. -CO-, -COO- or -OCO- replaced. 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. From the viewpoint of imparting so-called amphiphilicity to the alignment aid, the alignment inducing group is preferably bonded to the side opposite to the adsorption group of the mesogen.

"Polymerizable group" The polymerizable group is preferably represented by P ^AP1 -, and is bonded to the mesogen group via Sp ^AP1- (single bond or spacer). P ^{AP1 is} preferably a group selected from the group represented by the following general formulas (AP-1) to (AP-9).

In the formula, R ^AP1 and R ^AP2 each independently represent 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 two or more -CH ₂ -in the alkyl group can be substituted by -O- or -CO- in a way that oxygen atoms are not directly adjacent to each other, and one or more hydrogen atoms in the alkyl group can be Each is independently substituted by a halogen atom or a hydroxyl group. W ^AP1 represents a single bond, -O-, -COO-, -OCO- or -CH ₂ -. t ^AP1 represents 0, 1, or 2.

P ^{AP1 is} preferably a group represented by the following general formula (AP-1) ~ general formula (AP-7), and more preferably a group represented by the following general formula (AP-1) or general formula (AP-2) The base is more preferably the general formula (AP-1). Sp ^AP1 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 or branched alkylene group having 1 to 20 carbon atoms, More preferably, it represents a single bond or a linear alkylene group having 2 to 10 carbon atoms. Also, in Sp ^AP1 , one of the alkylene groups or two or more non-adjacent -CH ₂ -can be independently -CH=CH- and -C≡C so that oxygen atoms are not directly adjacent to each other. -, -O-, -CO-, -COO- or -OCO- replaced.

In the alignment aid, the number of P ^AP1 -Sp ^AP1 -is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, and still more preferably 2 or more and 4 or less, more preferably Two or three, the best is two. The hydrogen atom in p ^AP1 -Sp ^AP1 -may be substituted by a polymerizable group, an adsorbing group described later, and/or the above-mentioned alignment inducing group. P ^AP1 -Sp ^AP1 -may also be bonded to a polymerizable group, a mesogen, an adsorption group described later, and/or the above-mentioned alignment inducing group. In addition, P ^AP1 -Sp ^AP1 -is preferably bonded to a mesogen, an adsorption group described later, or the aforementioned alignment inducing group, and more preferably is bonded to a mesogen group or an adsorption group described later. Furthermore, when there are a plurality of P ^AP1 and/or Sp ^AP1 -in the molecule, they may be the same as each other or different.

"Mesogen" The mesogen is a base with a rigid part, for example, it refers to a group with more than one cyclic group, preferably a group with 2 to 4 cyclic groups, and more preferably a group with 3 to 4 cyclic groups base. Furthermore, the cyclic group may be connected via a linking group as needed. The mesogen preferably has a skeleton similar to the liquid crystal molecules (liquid crystal compound) used in the liquid crystal layer. Furthermore, in this specification, "cyclic group" refers to a group of atoms in which the constituent atoms are bonded to form a ring, including carbocyclic, heterocyclic, saturated or unsaturated cyclic structures, monocyclic, bicyclic, and polycyclic Formula structure, aromatic, non-aromatic, etc. In addition, the cyclic group may contain at least one heteroatom, and may further be substituted with at least one substituent (halogen group, polymerizable group, organic group (alkyl group, alkoxy group, aryl group, etc.)). When the cyclic group is a single ring, the mesogen group preferably contains two or more single rings.

式中，Z^{A L1} 表示單鍵、－CH＝CH－、－CF＝CF－、－C≡C－、－COO－、－OCO－、－OCOO－、－CF₂ O－、－OCF₂ －、－CH＝CHCOO－、－OCOCH＝CH－、－CH₂ －CH₂ COO－、－OCOCH₂ －CH₂ －、－CH＝C（CH₃ ）COO－、－OCOC（CH₃ ）＝CH－、－CH₂ －CH（CH₃ ）COO－、－OCOCH（CH₃ ）－CH₂ －、－OCH₂ CH₂ O－或碳原子數1〜20之伸烷基。其中，伸烷基中之1個或不相鄰之2個以上之－CH₂ －能以氧原子不直接鄰接的方式被－O－、－COO－或－OCO－取代。The mesogen group is preferably represented by, for example, general formula (AL).

In the formula, Z ^{A L1} represents a single bond, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CF ₂ O-, -OCF _2- , -CH=CHCOO-, -OCOCH=CH-, -CH ₂ -CH ₂ COO-, -OCOCH ₂ -CH ₂ -, -CH=C(CH ₃ )COO-, -OCOC(CH ₃ )=CH- , -CH ₂ -CH (CH ₃ )COO -, -OCOCH (CH ₃ ) -CH ₂ -, -OCH ₂ CH ₂ O-or alkylene with 1-20 carbon atoms. Among them, one or two or more non-adjacent -CH ₂ -in the alkylene can be substituted with -O-, -COO- or -OCO- so that oxygen atoms are not directly adjacent to each other.

A ^{A L1} and A ^{A L2} each independently represent a divalent cyclic group. One or more of the hydrogen atoms of Z ^AL1 , A ^{A L1} and A ^AL2 can be independently substituted by halogenated groups, adsorbent groups, P ^AP1 -Sp ^AP1 -or monovalent organic groups. Furthermore, in the molecule When there are a plurality of Z ^{A L1} and A ^AL1 , they may be the same as each other or different. m ^AL1 represents an integer from 1 to 5. In the general formula (AL), Z ^{AL1 is} preferably a single bond or an alkylene having 2 to 20 carbon atoms, more preferably a single bond or an alkylene having 2 to 10 carbon atoms, and more preferably a single bond, -(CH ₂ ) ₂ -or-(CH ₂ ) ₄ -. One or two or more non-adjacent -CH ₂ -in the alkylene group may be substituted with -O-, -COO- or -OCO-. Furthermore, when the purpose is to improve the linearity of a rod-shaped molecule, Z ^{AL1 is} preferably a single bond in a form in which a ring is directly connected to a ring, or a form in which the number of atoms directly connecting a ring to a ring is an even number. For example, in the case of -CH ₂ -CH ₂ COO-, the number of atoms directly connecting the ring to the ring is 4.

In the general formula (AL), A ^AL1 and A ^AL2 each independently represent a divalent cyclic group. The divalent cyclic group is preferably selected from 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1 , 3-dioxane-2,5-diyl㗁, tetrahydrothiopyran ^_ 2,5-diyl, thiophene-2,5-diyl, 1,4-bicyclo (2.2.2) octyl extending , Decahydronaphthalene-2,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridine-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-diyl, 1,4-naphthylene, benzo[1,2-b:4,5-b'] Dithiophene-2,6-diyl, benzo[1,2-b:4,5-b']diselenophene-2,6-diyl, [1]benzothiophene[3,2-b] One of the group consisting of thiophene-2,7-diyl, [1]benzoselenophene [3,2-b]selenophene-2,7-diyl and 茀-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-Cyclohexyl. Furthermore, these groups may be unsubstituted or substituted by substituents. The substituent is preferably a fluorine atom or an alkyl group having 1 to 8 carbon atoms. Furthermore, the alkyl group may be substituted with a fluorine atom or a hydroxyl group. In addition, one or two or more hydrogen atoms in the cyclic group may be substituted with a halogenated group, an adsorbing group, P ^AP1 -Sp ^AP1 -or a monovalent organic group.

In the general formula (AL), the so-called monovalent organic group is a group that constitutes a chemical structure by turning an organic compound into a form of a monovalent group, and refers to an atomic group obtained by removing one hydrogen atom from an organic compound. As the monovalent organic group, for example, 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, an alkene having 2 to 15 carbon atoms An oxy group, etc.; preferably an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms Group, more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms , Most preferably an alkyl group with 1 or 2 carbon atoms or an alkoxy group with 1 carbon atom. In addition, one of the above-mentioned alkyl, alkenyl, alkoxy, and alkenyloxy groups or two or more non-adjacent -CH ₂ -s may be substituted with -O-, -COO- or -OCO-. Furthermore, the above-mentioned monovalent organic group may have a function as the above-mentioned alignment inducing group. In the above general formula (AL), m ^{AL1 is} preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and still more preferably 2 or 3.

As a preferred form of the mesogen group, the following formulas (me-1) to (me-44) can be cited.

The general formula (AL) is the structure obtained by separating two hydrogen atoms from these compounds. In the formulas (me-1)~(me-44), one or more hydrogen atoms in the cyclohexane ring, benzene ring or naphthalene ring can be independently substituted with halogenated groups, P ^AP1- Sp ^AP1 -, a monovalent organic group (for example, an alkyl group with 1 to 15 carbon atoms, an alkoxy group with 1 to 14 carbon atoms), an adsorption group or an alignment inducing group. Among the above mesogens, the preferred form is the formula (me-8)～(me－44), and the more preferable form is the formula (me-8)～(me-10), the formula (me-12)～(me -18), formula (me-22)～(me-24), formula (me－26)～(me-27) and formula (me-29)～(me－44), and the more preferable form is formula ( me-12), (me-14), (me-16), (me-22)~(me-24), (me-29), (me-34), (me-36)~(me- 37), (me－42)~(me－44).

Among the above mesogens, the most preferred form is the following general formula (AL-1) or (AL-2), and the most preferred form is the following general formula (AL-1).

In the formula, X ^{AL101 to} X ^AL118 and X ^{AL201 to} X ^AL214 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a halo group, and P ^AP1- Sp ^AP1 -The adsorption group mentioned later or the above-mentioned alignment inducing group. Ring A ^{AL1 1,} ring A ^{AL1 2} and the ring A ^{AL 21} each independently represent a benzene ring or a cyclohexyl ring. ^X AL101 ~X AL118, ^AL214 in any one of ^X AL201 ~X adsorbing at least one or two substituents are described after. ^X AL101 ~X AL118, ^AL214 in any one or more of ^X AL201 ~X substituted with one or two above-induced alignment group. The adsorption group described later and the above-mentioned alignment inducing group may be substituted by P ^AP1 -Sp ^AP1 -. The general formula (AL-1) or the general formula (AL-2) has one or more P ^AP1 -Sp ^AP1 -in the molecule.

In the general formula (AL-1), X ^AL101 is preferably the aforementioned alignment inducing group. In the general formula (AL-1), it is preferable that at least one of X ^AL109 , X ^AL110 and X ^AL111 is an adsorbing group described later, more preferably X ^{AL1 09} and X ^AL110 are adsorbing groups or X ^AL110 is described later The adsorption group, more preferably X ^AL110, is the adsorption group described later. In the general formula (AL-1), preferably at least one of X ^AL109 , X ^AL110 and X ^AL111 is P ^AP1 -Sp ^AP1 -in the adsorption group described later, or an adsorption group with a polymerizable part in the structure, More preferably, both or one of X ^AL109 and X ^{AL1 11} is P ^AP1- Sp ^AP1 -. In the general formula (AL-1) ^{in, X AL104 ~X AL108, X AL112} ~X AL116 of 1 or 2 substituents each independently, preferably an alkyl group of 1 ~ 5 carbon atoms, having a carbon number of 1 ~ 5 The alkoxy group or halo group is more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. ^{Particularly preferably} , X ^AL105 , X ^AL106 or X ^AL107 are each independently an alkyl group having 1 to 3 carbon atoms or a fluorine atom.

In the general formula (AL-2), X ^AL201 is preferably the aforementioned alignment inducing group. In the general formula (AL-2), it is preferable that at least one of X ^AL207 , X ^AL208 and X ^AL209 is the adsorption group described later, more preferably X ^AL207 and X ^AL208 are the adsorption group described later or X ^AL208 is the adsorption group described later X ^AL208 is the adsorption group described later. In the general formula (AL-2), preferably at least one of X ^AL207 , X ^AL208 and X ^AL209 is P ^AP1 -Sp ^AP1 -in the adsorption group described later, or an adsorption group with a polymerizable part in the structure, More preferably, both or one of X ^AL207 and X ^AL209 is P ^AP1- Sp ^AP1 -. In the general formula (AL-2), one or two of X ^AL202 〜X ^AL206 and X ^AL210 〜X ^AL214 are independently, preferably an alkyl group with 1 to 5 carbon atoms, and one with 1 to 5 carbon atoms The alkoxy group or halo group is more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. ^{Particularly preferably} , X ^AL204 , X ^AL205 or X ^AL206 are each independently an alkyl group having 1 to 3 carbon atoms or a fluorine atom.

"Adsorbing Group" The adsorption base is a base having a function of adsorbing with an adsorption medium, and the adsorption medium is a substrate, a film, an electrode, etc. as a layer that abuts the liquid crystal composition. Adsorption is generally divided into chemical adsorption, which forms chemical bonds (covalent bonds, ionic bonds, or metal bonds), to adsorb between the adsorption medium and the adsorbed substance, and physical adsorption other than chemical adsorption. In this specification, adsorption can be either chemical adsorption or physical adsorption, and physical adsorption is preferred. Therefore, the adsorption base is preferably a base that can be physically adsorbed with the adsorption medium, and more preferably a base that can be bonded to the adsorption medium by intermolecular force. Examples of the form of bonding to the adsorption medium by intermolecular force include forms formed by the interaction of permanent dipoles, permanent quadrupoles, dispersion forces, charge transfer forces, hydrogen bonds, and the like. As a preferable form of the adsorption group, a form that can be bonded to the adsorption medium by a hydrogen bond can be cited. In this case, the adsorbing group can also perform the function of either or both of the donor and acceptor of the proton that mediates the hydrogen bond.

The adsorbing group is preferably a group containing a "polar element having an atomic group formed by connecting a carbon atom and a heteroatom" (hereinafter, the "adsorbing group" may also be described as a "polar group"). In this specification, the so-called polar element refers to an atomic group formed by directly connecting carbon atoms and heteroatoms. 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, Furthermore, it is preferably at least one selected from the group consisting of N and O, and O is particularly preferred. In addition, in the alignment aid, the valence of the polar elements is not particularly limited to monovalent, divalent, trivalent, etc., and the number of polar elements in the adsorbent is not particularly limited. The alignment aid preferably has 1 to 8 adsorption groups in one molecule, more preferably has 1 to 4 adsorption groups, and more preferably has 1 to 3 adsorption groups. Further, the self-adsorptive group and a polymerizable group in the ligand-induced group to be removed, but the adsorption of the adsorption group include a hydrogen atom is substituted with the group P ^AP1 -Sp ^AP1 - the structure and P ^AP1 -Sp ^AP1 - of the hydrogen atoms is Replaced with -OH structure.

Adsorbent groups contain one or more polar elements, which are roughly divided into cyclic base type and chain base type. The cyclic base type includes the form of a cyclic base having a cyclic structure containing polar elements in its structure, and the chain base type does not include the form of a "cyclic base having a cyclic structure containing polar elements in its structure". . The chain base type is a form in which a linear or branched chain base has a polar element, and a part of it may also have a cyclic structure that does not contain a polar element. The so-called cyclic radical type adsorbing group means a form having a structure containing at least one polar element in the cyclic atomic arrangement. In addition, in this specification, the so-called cyclic group is as described above. Therefore, the cyclic radical type adsorbing group only needs to include the "polar element-containing cyclic group", and the whole adsorbing group may be branched or linear. On the other hand, the so-called chain-based adsorption group means that the molecule does not contain a "cyclic atomic arrangement containing polar elements", and the linear atomic arrangement (which can be branched) contains at least one polarity The form of the structure of the element.

Furthermore, in this specification, the so-called chain group refers to the atomic group that does not include the cyclic atom arrangement in the structural formula, and the atoms constituted by the linear (branchable) bonding, and refers to non-cyclic式基。 Formula base. In other words, the so-called chain group refers to a linear or branched aliphatic group, which may include either a saturated bond or an unsaturated bond. Therefore, the chain group includes, for example, an alkyl group, an alkenyl group, an alkoxy group, an ester group, an ether group, or a keto group. Furthermore, the hydrogen atoms in these groups can be substituted by at least one substituent (reactive functional group (vinyl, acrylic group, methacrylic group, etc.), chain organic group (alkane) Group, cyano, etc.)) substitution. In addition, the chain group may be either linear or branched.

As the cyclic-based adsorbing group, a heteroaryl group having 3 to 20 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 20 carbon atoms (including a condensed ring) is preferable, more preferably carbon Heteroaryl groups with 3 to 12 atoms (including condensed rings) or heteroalicyclic groups with 3 to 12 carbon atoms (including condensed rings), and more preferably 5-membered ring heteroaryl groups and 5-membered ring heterocyclic groups Alicyclic group, 6-membered ring heteroaryl group or 6-membered ring heteroalicyclic group. Furthermore, the hydrogen atoms in these ring structures may be substituted by halogenated groups, linear or branched alkyl groups or alkoxy groups having 1 to 5 carbon atoms. As the chain type adsorbing group, a hydrogen atom or -CH ₂ -in the structure is preferably a linear or branched alkyl group having 1 to 20 carbon atoms in which a polar element is substituted. Furthermore, one of the alkyl groups or two or more non-adjacent -CH ₂ -can be substituted with -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-. In addition, the chain-based adsorption group preferably contains one or two or more polar elements at its end.

The hydrogen atom in the adsorbing group may be replaced by a polymerizable group. Specific examples of polar elements include: polar elements containing oxygen atoms (hereinafter, oxygen-containing polar elements), polar elements containing nitrogen atoms (hereinafter, nitrogen-containing polar elements), and polar elements containing phosphorus atoms (hereinafter, containing Phosphorus-containing polar elements), boron-containing polar elements (hereinafter, boron-containing polar elements), silicon-containing polar elements (hereinafter, silicon-containing polar elements), or sulfur atoms-containing polar elements (hereinafter, sulfur-containing polar elements). From the viewpoint of adsorption capacity, as the polar element, a nitrogen-containing polar element or an oxygen-containing polar element is preferable, and an oxygen-containing polar element is more preferable.

The oxygen-containing polar element is preferably at least 1 selected from the group consisting of a hydroxyl group, an alkylol group, an alkoxy group, a formanyl group, a carboxyl group, an ether group, a carbonyl group, a carbonate group, and an ester group. The seed group or the group bonded to the carbon atom. The nitrogen-containing polar element is preferably at least one group selected from the group consisting of cyano group, primary amino group, secondary amino group, tertiary amino group, pyridyl group, aminomethanyl group, and urea group, or The carbon atom is connected to the group of the group. Therefore, the adsorbing group is preferably selected from a cyclic group having an oxygen-containing polar element (hereinafter, an oxygen-containing cyclic group), a cyclic group having a nitrogen-containing polar element (hereinafter, a nitrogen-containing cyclic group), and One or two or more types of chain groups of oxygen-containing polar elements (hereinafter, oxygen-containing chain groups) and chain groups with nitrogen-containing polar elements (hereinafter, nitrogen-containing chain groups) The body may contain the base.

As the oxygen-containing cyclic group, it is preferable to include any one of the following groups having an oxygen atom as an ether group in the ring structure.

In addition, the oxygen-containing cyclic group preferably includes any one of the following groups having an oxygen atom in the ring structure as a carbonyl group, a carbonate group, and an ester group.

The nitrogen-containing cyclic group preferably includes any one of the following groups.

The oxygen-containing chain group preferably contains any one of the following groups.

In the formula, R ^at1 represents an alkyl group having 1 to 5 carbon atoms. Z ^at1 represents a single bond, a linear or branched alkylene group with 1 to 15 carbon atoms, or a linear or branched alkenylene group with 2 to 18 carbon atoms. Among them, -CH ₂ -in the alkylene group or alkenylene group can be substituted with -O-, -COO-, -C(=O)-, -OCO- in such a way that oxygen atoms are not directly adjacent to each other. X ^at1 represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. Among them, -CH ₂ -in the alkyl group can be substituted by -O-, -COO-, -C(=O)-, -OCO- in such a way that oxygen atoms are not directly adjacent to each other.

式中，R^at 、R^bt 、R^ct 及R^dt 分別獨立地表示氫原子或碳原子數1〜5之烷基。The nitrogen-containing chain group preferably contains any one of the following groups.

In the formula, R ^at , R ^bt , R ^ct and R ^dt each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

式中，Sp^AT1 表示單鍵、碳原子數1〜25之直鏈狀或支鏈狀之伸烷基。其中，伸烷基中之氫原子可被－OH、－CN、－W^AT1 －Z^{AT 1} 或P^AP1 －Sp^AP1 －取代，伸烷基中之－CH₂ －能以氧原子不直接鍵結之方式被環式基、－O－、－COO－、－C（＝O）－、－OCO－、－CH＝CH－或－OCO－COO－取代。 W^AT1 表示單鍵或下述通式（WAT1）或（WAT2）。 Z^{AT 1} 表示包含極性要素之一價基。其中，Z^{AT 1} 中之氫原子可被－OH、－CN或P^AP1 －Sp^AP1 －取代。As the adsorption group, a group represented by the following general formula (AT) is preferred.

In the formula, Sp ^AT1 represents a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms. Among them, the hydrogen atom in the alkylene group can be substituted by -OH, -CN, -W ^AT1 -Z ^{AT 1} or P ^AP1 -Sp ^AP1 -, and the -CH ₂ -in the alkylene group can not be directly bonded with oxygen atom The way is replaced by cyclic group, -O-, -COO-, -C(=O)-, -OCO-, -CH=CH- or -OCO-COO-. W ^AT1 represents a single key or the following general formula (WAT1) or (WAT2). Z ^{AT 1} represents a valence base containing polar elements. Among them, the hydrogen atom in Z ^{AT 1} can be replaced by -OH, -CN or P ^AP1 -Sp ^AP1 -.

（式中，Sp^WAT1 及Sp^WAT2 分別獨立地表示單鍵、碳原子數1〜25之直鏈狀或支鏈狀之伸烷基，伸烷基中之氫原子可被－OH、－CN或P^AP1 －Sp^AP1 －取代，伸烷基中之－CH₂ －能以氧原子不直接鍵結之方式被環式基、－O－、－COO－、－C（＝O）－、－OCO－或－CH＝CH－取代）。

(In the formula, Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond, a linear or branched alkylene group with 1 to 25 carbon atoms. The hydrogen atom in the alkylene group can be replaced by -OH, -CN or P ^AP1 -Sp ^AP1 - substituted alkylene group in the -CH ₂ - can be oxygen atoms are not directly bonded to the manner cyclic group, -O -, - COO -, - C (= O) -, - OCO -Or-CH=CH-replacement).

Sp ^AT1 , Sp ^WAT1 and Sp ^WAT2 are independent of each other, and preferably represent a single bond or a linear or branched alkylene group with 1 to 20 carbon atoms, and more preferably represent a single bond or a linear carbon atom The alkylene group of 1 to 20 preferably represents a single bond or a linear alkylene group of 2 to 10 carbon atoms. In addition, in Sp ^AT1 , Sp ^WAT1, and Sp ^WAT2 , one or two or more of -CH ₂ -in the alkylene group can be independently -CH=CH-,-so that oxygen atoms are not directly bonded. C≡C-, -O-, -CO-, -COO- or -OCO- are replaced. In addition, the hydrogen atoms in Sp ^AT1 and Sp ^WAT1 can be replaced by -W ^AT1 -Z ^AT1 or P ^AP1 -Sp ^AP1 -independently, respectively.

Z ^{AT 1} represents a univalent group containing a polar element, and is preferably a group represented by the following general formula (ZAT1-1) or (ZAT1-2).

In the formula, Sp ^ZAT11 and Sp ^ZAT12 each independently represent a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms. Among them, the hydrogen atom in the alkylene group can be substituted by -OH, -CN, -Z ^ZAT11 -R ^ZAT11 or P ^AP1 -Sp ^AP1 -, and the -CH ₂ -in the alkylene group can be directly adjacent to the oxygen atom It is substituted by cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH-. Z ^ZAT11 represents a base containing polar elements. The structure represented by the ring containing Z ^ZAT12 in the general formula (ZAT1-2) represents a 5- to 7-membered ring. The hydrogen atoms in Z ^ZAT11 and Z ^ZAT12 can be replaced by -OH, -CN or P ^AP1 -Sp ^AP1 -. R ^ZAT11 and R ^ZAT12 each independently represent a hydrogen atom and a linear or branched alkyl group having 1 to 8 carbon atoms. Among them, the hydrogen atom in the alkyl group can be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -, the -CH ₂ -in the alkyl group can be cyclic group, -O- in a way that the oxygen atom is not directly bonded. , -COO-, -C(=O)-, -OCO-, -CH=CH- or -Z ^{ZAT11 -Replace} .

The group represented by the general formula (ZAT1-1) is preferably a group represented by the following general formulas (ZAT1-1-1) to (ZAT1-1-30).

In the formula, the hydrogen atom bonded to the carbon atom can be replaced by -OH, -CN or P ^AP1 -Sp ^AP1 -. Sp ^ZAT11 represents a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms. Among them, the hydrogen atom in the alkylene group can be substituted by -OH, -CN, -Z ^ZAT11 -R ^ZAT11 or P ^AP1 -Sp ^AP1 -, and the -CH ₂ -in the alkylene group can be directly adjacent to the oxygen atom It is substituted by cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH-. R ^ZAT11 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms. Among them, the hydrogen atom in the alkyl group can be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -, and the -CH ₂ -in the alkyl group can be cyclic group, -O- , -COO-, -C(=O)-, -OCO-, -CH=CH- or -Z ^{ZAT11 -Replace} .

The group represented by the general formula (ZAT1-2) is preferably a group represented by the following general formulas (ZAT1-2-1) to (ZAT1-2-9).

In the formula, the hydrogen atom bonded to the carbon atom can be substituted with a halogen atom, -OH, -CN or P ^AP1 -Sp ^AP1 -. Sp ^ZAT11 represents a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms. Among them, the hydrogen atom in the alkylene group can be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -, and the -CH ₂ -in the alkylene group can be cyclic group without the oxygen atom directly adjacent to each other, -O -, -COO-, -C(=O)-, -OCO-, -CH=CH- or -Z ^{ZAT11 -Replace} .

As the group represented by the general formula (ZAT1-1), the following groups can be cited.

In the formula, R ^tc represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or P ^AP1 -Sp ^AP1 -. Among them, the hydrogen atom in the alkyl group can be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -, and the -CH ₂ -in the alkyl group can be substituted by the cyclic group, -O-, -COO-, -C(=O)-, -OCO-, -CH=CH- or -Z ^{ZAT11 -Replace} . The hydrogen atom in the molecule can be replaced by P ^AP1- Sp ^AP1 -. * Represents the bonding key.

The alignment aid is preferably in a form in which the polar elements contained in the adsorption group or the polar elements contained in the polymerizable group are locally present. The adsorption group is an important structure for vertical alignment of liquid crystal molecules. By making the adsorption group and the polymerizable group adjacent to each other, better alignment is obtained, and it also shows good solubility to the liquid crystal composition. Specifically, the alignment aid is preferably in a form having a polymerizable group and an adsorption group on the same ring of the mesogen. This form includes: a form in which one or more polymerizable groups and one or more adsorbent groups are respectively bonded to the same ring; and at least one of more than one polymerizable groups, or at least one of more than one adsorbent groups In one, one of them is bonded to the other and has a form of a polymerizable group and an adsorption group on the same ring. Moreover, in this case, the hydrogen atom in the spacer bonded to the polymerizable group may be substituted by an adsorbent group, and further, the hydrogen atom in the adsorbent group may be substituted by the polymerizable group via the spacer.

式中，鍵結於碳原子之氫原子可被碳原子數1〜25之直鏈狀或支鏈狀之烷基、－OH、－CN、－Sp^AT1 －W^AT1 －Z^AT1 或P^AP1 －Sp^AP1 －取代。其中，烷基中之氫原子可被－OH、－CN、－Sp^AT1 －W^AT1 －Z^AT1 或P^AP1 －Sp^AP1 －取代，烷基中之－CH₂ －能以氧原子不直接鍵結之方式被環式基、－O－、－COO－、－C（＝O）－、－OCO－或－CH＝CH－取代。 R^AK1 表示與通式（AK）中之R^AK1 相同之意義。As the alignment aid (spontaneous alignment compound), a compound represented by the following general formula (SAL) is preferred.

In the formula, a hydrogen atom bonded to a carbon atom of the alkyl group carbon atoms which may be straight-chain or branched-chain of the ^{1~25, -OH, -CN, -Sp AT1 -W} AT1 -Z AT1 or P ^AP1 - Sp ^AP1 -Replace. Among them, the hydrogen atom in the alkyl group can be replaced by -OH, -CN, -Sp ^AT1 -W ^AT1 -Z ^AT1 or P ^AP1 -Sp ^AP1 -, the -CH ₂ -in the alkyl group can be directly bonded with oxygen atoms The way is replaced by cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH-. R ^AK1 means the same meaning as R ^AK1 in the general formula (AK).

A ^AL1 and A ^AL2 independently represent the same meaning as A ^AL1 and A ^AL2 in the general formula (AL). Z ^AL1 means the same meaning as Z ^AL1 in the general formula (AL). m ^AL1 means the same meaning as m ^AL1 in the general formula (AL). Sp ^AT1 means the same meaning as Sp ^AT1 in the general formula (AT). W ^AT1 means the same meaning as W ^AT1 in the general formula (AT). Z ^AT1 means the same meaning as Z ^AT1 in the general formula (AT).

The compound represented by the general formula (SAL) is preferably a compound represented by the following formulas (SAL-1.1) to (SAL-2.10).

The amount of the alignment aid contained in the liquid crystal composition is preferably about 0.01-10% by mass. From the viewpoint of aligning the liquid crystal molecules more appropriately, the more preferable lower limit is 0.05% by mass and 0.1% by mass. On the other hand, from the viewpoint of improving response characteristics, more preferable upper limit values are 7% by mass, 5% by mass, 4% by mass, 3% by mass, and 1% by mass.

式（P）中，R^p1 表示氫原子、氟原子、氰基、碳原子數1〜15之烷基或－Sp^p2 －P^p2 。其中，烷基中所存在之1個或未相鄰之2個以上之－CH₂ －可分別獨立地被－CH＝CH－、－C≡C－、－O－、－CO－、－COO－或－OCO－取代。又，烷基中所存在之1個或2個以上之氫原子可分別獨立地被氰基、氟原子或氯原子取代。((Polymerizable compound)) The liquid crystal composition used in the present invention preferably contains a polymerizable compound (polymerizable monomer B) that does not have an adsorption group (polar group). The polymerizable compound has the function of imparting a specific pretilt angle to the liquid crystal molecules. This polymerizable compound is preferably represented by the following general formula (P). Furthermore, the liquid crystal composition may contain two or more of these polymerizable compounds.

In the 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 . Among them, one or two or more non-adjacent -CH ₂ -existing in the alkyl group can be independently -CH=CH-, -C≡C-, -O-, -CO-, -COO -Or-OCO-replace. In addition, one or two or more hydrogen atoms present in the alkyl group may be independently substituted with a cyano group, a fluorine atom, or a chlorine atom.

（式中，R^p11 及R^p12 分別獨立地表示氫原子、碳原子數1〜5之烷基或碳原子數1〜5之鹵化烷基，W^{p 11} 表示單鍵、－O－、－COO－、－OCO－或－CH₂ －，t^p11 表示0、1或2，於分子內存在複數個R^p11 、R^p12 、W^p11 及／或t^p11 之情形時，其等可相同，亦可不同）。P ^p1 and P ^p2 each independently represent any of the following general formulas (P ^p1 -1) to (P ^p1 -9).

(In the formula, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a halogenated alkyl group with 1 to 5 carbon atoms, and W ^{p 11} represents a single bond, -O-, -COO －, －OCO－ or －CH ₂ －, t ^p11 represents 0, 1 or 2. When there are multiple R ^p11 , R ^p12 , W ^p11 and/or t ^p11 in the molecule, they can be the same or different).

Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer. Z ^p1 and Z ^p2 each independently represent a single bond, -O-, -S-, -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CO-, -C ₂ H ₄ -, -COO- , －OCO－, －OCOOCH ₂ －, －CH ₂ OCOO－, －OCH ₂ CH ₂ O－, －CO－NR ^ZP1 －, －NR ^ZP1 －CO－, ^－SCH ₂ －, －CH ₂ S－,－ 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-,-(CH ₂ ) ₂ -COO-,-(CH ₂ ) ₂ -OCO-,- OCO-(CH ₂ ) ₂ -, -(C=O) -O-(CH ₂ ) ₂ -, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-,- CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -or -C≡C- (where R ^{ZP1 is} independently It represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and when there are a plurality of R ^ZP1 in the molecule, they may be the same or different).

A ^p1 , A ^p2 and A ^p3 each independently represent a radical (a ^p ) to a radical (c ^p ) consisting of a radical (the following radicals (a ^p ), a radical (b ^p ) and a radical (c) The hydrogen atoms present in ^p ) may be independently substituted by halogen atoms, alkyl groups with 1 to 8 carbon atoms, alkenyl groups with 1 to 8 carbon atoms, cyano groups or -Sp ^p2 -P ^p2 ): ( a ^p ) 1,4-cyclohexylene (1 -CH ₂ -or ₂ or more non-adjacent -CH ₂ -can be substituted by -O- in the group), (b ^p )1, 4-phenylene (1 -CH= or 2 or more non-adjacent -CH= may be substituted by -N= in the group), and (c ^p ) naphthalene-2,6-diyl , Naphthalene-1,4-diyl, naphthalene-1,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decalin-2,6-diyl, phenanthrene -2,7-diyl or anthracene-2,6-di (1 -CH= or 2 or more non-adjacent -CH= in these groups can be substituted by -N=).

m ^p1 represents 0, 1, 2, or 3. When there are plural Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 in the molecule, they may be the same or different. Wherein, A ^p3 may also be a single bond when m ^p1 is 0 and A ^p1 is the aforementioned group (c ^p ). Furthermore, the alignment aid is not included in the polymerizable compound.

R ^{p1 is} preferably -Sp ^p2 -P ^p2 . P ^p1 and P ^p2 are independent of each other, preferably any one of general formula (P ^p1 -1) to formula (P ^p1-3 ), and more preferably (P ^p1 -1). Preferably, R ^p11 and R ^p12 are each independently a hydrogen atom or a methyl group. t ^{p11 is} preferably 0 or 1. W ^{p11 is} preferably a single bond, -CH ₂ -or -C ₂ H ₄ -. m ^{p1 is} preferably 0, 1, or 2, preferably 0 or 1.

Z ^p1 and Z ^p2 are independent of each other, preferably a single bond, -OCH ₂ -, -CH ₂ O-, -CO-, -C ₂ H ₄ -, -COO-, -OCO-, -COOC ₂ H _4- , -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CH=CH-, -CF ₂ -, -CF ₂ O-,-(CH ₂ ) ₂ -COO- ,-(CH ₂ ) _2- OCO -,-OCO-(CH ₂ ) ₂ -,-CH = CH-COO -,-COO-CH = CH -,-OCOCH = CH -,-COO-(CH ₂ ) ₂ -, -OCF ₂ -or -C≡C-, more preferably a single bond, -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO-, -OCO-, -COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CH=CH-,-(CH ₂ ) ₂ -COO-,-(CH ₂ ) ₂ -OCO -, -OCO- (CH ₂ ) ₂ -, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH ₂ ) ₂ -or -C≡C-.

Furthermore, it is preferable that only one of Z ^p1 and Z ^p2 existing in the molecule is -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO-, -OCO-, -COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CH=CH-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) _2- OCO-, -OCO- (CH ₂ ) ₂ -, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO- (CH ₂ ) ₂ -or -C≡C- , The others are single bonds, and it is more preferable that only one of Z ^p1 and Z ^{p2 in} the molecule is -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO- or -OCO- , The others are single bonds, and preferably all Z ^p1 and Z ^p2 existing in the molecule are single bonds. Also, it is preferable that only one of Z ^p1 and Z ^p2 existing in the molecule is selected from -CH=CH-COO-, -COO-CH=CH-, -(CH ₂ ) ₂ -COO-, -( CH ₂ ) ₂ -OCO-, -O-CO- (CH ₂ ) ₂ -, -COO- (CH ₂ ) ₂ -linking group in the group consisting of, the others are single bonds.

Sp ^{p 1} and Sp ^p2 each independently represent a single bond or a spacer group, the spacer group is preferably an alkylene group having a carbon number of 1~30. Among them, as long as the oxygen atoms are not directly connected to each other, the -CH ₂ -in the alkylene group can be substituted with -O-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡ C-, the hydrogen atom in the alkylene group can be substituted with a halogen atom. Among them, it is preferable that Sp ^p1 and Sp ^p2 are each independently a linear alkylene group having 1 to 10 carbon atoms or a single bond. A ^p1 , A ^p2 and A ^p3 are independent of each other, preferably 1,4-phenylene or 1,4-cyclohexylene, and more preferably 1,4-phenylene. In order to improve the compatibility with liquid crystal molecules (liquid crystal compounds), the 1,4-phenylene group is preferably substituted with 1 fluorine atom, 1 methyl group or 1 methoxy group.

The amount of the polymerizable compound contained in the liquid crystal composition is preferably 0.05-10% by mass, more preferably 0.1-8% by mass, still more preferably 0.1-5% by mass, and still more preferably 0.1-3% by mass, It is more preferably 0.2 to 2% by mass, more preferably 0.2 to 1.3% by mass, particularly preferably 0.2 to 1% by mass, most preferably 0.2 to 0.5% by mass.

The preferred lower limit is 0.01% by mass, 0.03% by mass, 0.05% by mass, 0.08% by mass, 0.1% by mass, 0.15% by mass, 0.2% by mass, 0.25% by mass, and 0.3% by mass. On the other hand, the preferred upper limit is 10% by mass, 8% by mass, 5% by mass, 3% by mass, 1.5% by mass, 1.2% by mass, 1% by mass, 0.8% by mass, and 0.5% by mass.

If the amount of the polymerizable compound is small, there are situations where it is difficult to show the effect of adding the polymerizable compound to the liquid crystal composition. For example, depending on the type of the liquid crystal molecule or the alignment aid, the alignment restriction force of the liquid crystal molecule is relatively high. Weakness or become weaker over time. On the other hand, if the amount of the polymerizable compound is too large, problems such as an increase in the amount of the polymerizable compound remaining after curing depending on the illuminance of ultraviolet rays, etc., time-consuming curing, and reduced reliability of the liquid crystal composition may occur. Therefore, it is preferable to set the amount of the polymerizable compound in consideration of these balances.

As a preferable example of the polymerizable compound represented by the general formula (P), the polymerizable compound represented by the following formula (P-1-1) to formula (P-1-46) can be cited.

式中，P^p11 、P^p12 、Sp^p11 及Sp^p12 表示與通式（P）中之P^p1 、P^p2 、Sp^p1 及Sp^p2 相同之意義。

In the formula, P ^p11 , P ^p12 , Sp ^p11 and Sp ^p12 represent the same meaning as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).

式中，P^p21 、P^p22 、Sp^p21 及Sp^p22 表示與通式（P）中之P^P1 、P^p2 、Sp^p1 及Sp^p2 相同之意義。Moreover, as a preferable example of the polymerizable compound represented by general formula (P), the polymerizable compound represented by the following formula (P-2-1)~formula (P-2-12) can also be mentioned.

In the formula, P ^p21 , P ^p22 , Sp ^p21 and Sp ^p22 have the same meaning as P ^P1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).

Furthermore, as a preferable example of the polymerizable compound represented by general formula (P), the polymerizable compound represented by following formula (P-3-1)~formula (P-3-15) can also be mentioned.

式中，P^p31 、P^p32 、Sp^p31 及Sp^p32 表示與通式（P）中之P^p1 、P^p2 、Sp^p1 及Sp^p2 相同之意義。

In the formula, P ^p31 , P ^p32 , Sp ^p31 and Sp ^p32 represent the same meaning as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).

In addition, as a preferable example of the polymerizable compound represented by the general formula (P), polymerizable compounds represented by the following formulas (P-4-1) to (P-4-21) can also be cited.

式中，P^p41 、P^p42 、Sp^p41 及Sp^p42 表示與通式（P）中之P^p1 、P^p2 、Sp^p1 及Sp^p2 相同之意義。

In the formula, P ^p41 , P ^p42 , Sp ^p41 and Sp ^p42 represent the same meaning as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).

((Liquid crystal molecules)) In addition to the above-mentioned polymerizable monomers, the liquid crystal composition of the present invention preferably contains one or two or more selected from general formulas (N-01), (N-02), (N-03) ), (N-04) and (N-05) represented as liquid crystal molecules. Such compounds correspond to compounds with negative anisotropy in terms of dielectric. Other compounds show that the sign of Δε is negative, and its absolute value is greater than 2. Furthermore, the 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 a substantially neutral dielectric at 25°C.

In the formula, R ²¹ and R ²² each independently represent an alkyl group with 1 to 8 carbon atoms, an alkoxy group with 1 to 8 carbon atoms, an alkenyl group with 2 to 8 carbon atoms, or 2 to 8 carbon atoms. The alkenyloxy group, one of the groups or two or more non-adjacent -CH ₂ -can be independently -CH=CH-, -C≡C-, -O-, -CO-,- Replaced by COO- or -OCO-, Z ¹ independently represents a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH-, -CF=CF- or -C≡C-, m independently represents 1 or 2 respectively.

R ^{21 is} preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. Among them, when Z ¹ represents other than a single bond, R ^{21 is} preferably an alkyl group having 1 to 3 carbon atoms. R ^{22 is} preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, More preferably, it is an alkoxy group having 1 to 4 carbon atoms.

R ²¹ and R ²² may also be alkenyl. In this case, R ²¹ and R ²² are independent of each other, and are preferably selected from the groups represented by the following formulas (R1) to (R5) (the black dots in each formula represent carbon atoms in the ring structure), and more It is preferably formula (R1) or formula (R2). Among them, the content of compounds in which R ²¹ and R ²² are alkenyl groups is preferably as small as possible, and in most cases, it is better not to contain them.

Z ^{1 is} independent and represents a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH -, -CF=CF- or -C≡C-, preferably a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, more preferably a single bond or -CH ₂ O-. When m is 1, Z ¹ is preferably a single bond. When m is 2, Z ¹ is preferably -CH ₂ CH ₂ -or -CH ₂ O-.

The fluorine atoms of the compounds represented by the general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) may also be substituted by chlorine atoms of the same halogen group. Among them, the content of compounds substituted with chlorine atoms is preferably as small as possible, and it is preferable not to contain them. The hydrogen atoms present on the rings of the compounds represented by the general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) may be further replaced by fluorine atoms or Chlorine atom substitution. Among them, the content of compounds substituted with chlorine atoms is preferably as small as possible, and it is preferable not to contain them. The compounds represented by general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) are preferably compounds in which Δε is negative and its absolute value is greater than 3. Specifically, R ^{22 is} preferably an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.

（式中，R²¹ 表示與上述相同之意義，R²³ 分別獨立地表示碳原子數1～4之烷氧基）。The compound represented by the general formula (N-01) preferably contains one or two or more selected from the general formula (N-01-1), the general formula (N-01-2), and the general formula (N-01). -3) and the compound represented by the general formula (N-01-4).

(In the formula, R ²¹ represents the same meaning as above, and R ²³ each independently represents an alkoxy group having 1 to 4 carbon atoms).

The liquid crystal composition preferably contains a polymerizable monomer, a compound represented by the general formula (N-01-1), and the general formula (N-01-4). When high VHR is necessary, that is, when high reliability is necessary, and furthermore, when it is important to obtain a liquid crystal display element 1 without display defects, it is preferable not to include the general formula ( N-01-3) the compound represented.

（式中，R²¹ 表示與上述相同之意義，R²³ 分別獨立地表示碳原子數1～4之烷氧基）。The compound represented by the general formula (N-02) preferably contains one or two or more selected from general formula (N-02-1), general formula (N-02-2), and general formula (N- 02-3) The compound indicated.

(In the formula, R ²¹ represents the same meaning as above, and R ²³ each independently represents an alkoxy group having 1 to 4 carbon atoms).

The liquid crystal composition preferably contains a polymerizable monomer and a compound represented by general formula (N-02-1). The liquid crystal composition preferably contains a polymerizable monomer and a compound represented by general formula (N-02-3). The liquid crystal composition particularly preferably contains a polymerizable monomer, the compound represented by the general formula (N-01-1), the compound represented by the general formula (N-01-4), and the general formula (N-02-1). ) Represented by the compound. The liquid crystal composition particularly preferably contains a polymerizable monomer, a compound represented by general formula (N-01-1), a compound represented by general formula (N-01-4), and general formula (N-02-3). ) Represented by the compound.

（式中，R²¹ 表示與上述相同之意義，R²³ 表示碳原子數1～4之烷氧基）。As the compound represented by the general formula (N-03), it is preferable to contain one or two or more compounds represented by the general formula (N-03-1).

(In the formula, R ²¹ represents the same meaning as above, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms).

The liquid crystal composition is preferably a combination of a polymerizable monomer and a compound represented by general formula (N-03-1). The liquid crystal composition particularly preferably contains a polymerizable monomer, a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4), and a general formula (N-03-1) at the same time. ) Represented by the compound.

（式中，R²¹ 表示與上述相同之意義，R²³ 表示碳原子數1～4之烷氧基）。The compound represented by general formula (N-04) preferably contains one or two or more compounds represented by general formula (N-04-1).

(In the formula, R ²¹ represents the same meaning as above, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms).

The liquid crystal composition particularly preferably contains a polymerizable monomer, a compound represented by general formula (N-01-1), a compound represented by general formula (N-01-4), and general formula (N-04-1). ) Represented by the compound.

The compound represented by general formula (N-05) is preferably selected from compounds represented by formula (N-05-1) to formula (N-05-3).

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

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

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

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

The lower limit value of the preferable content of the compound represented by the general formula (N-05) is 0 mass%, 2 mass%, 5 mass%, 8 mass%, and 10 mass% relative to the total amount of the liquid crystal composition % Is 13% by mass, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, and 13% by mass.

The liquid crystal composition particularly preferably contains 0.1 to 15% by mass of polymerizable monomers, 1 to 20% by mass of the compound represented by the general formula (N-01-1), and 1 to 30% by mass of the general formula (N The compound represented by -01-4) contains 1-20% by mass of the compound represented by the general formula (N-04-1).

（式中，R²¹ 及R²² 表示與上述相同之意義）。The liquid crystal composition may further contain one or more compounds represented by the general formula (N-06).

(In the formula, R ²¹ and R ^{22 have} the same meaning as above).

（式中，R^NU11 、R^NU12 、R^NU21 、R^NU22 、R^NU31 、R^NU32 、R^NU41 、R^NU42 、R^NU51 、R^NU52 、R^NU61 及R^NU62 分別獨立地表示碳原子數1～8之烷基、碳原子數1～8之烷氧基、碳原子數2～8之烯基或碳原子數2～8之烯氧基，該基中之1個或不相鄰之2個以上之－CH₂ －亦可分別獨立地被－CH＝CH－、－C≡C－、－O－、－CO－、－COO－或－OCO－取代）。The compound represented by the general formula (N-06) can be used when adjusting various physical properties, and can be used to obtain large refractive index anisotropy (Δn), high Tni, and large Δε. The lower limit value of the preferred content of the compound represented by the general formula (N-06) is 0 mass%, 2 mass%, 5 mass%, 8 mass%, and 10 mass% relative to the total amount of the liquid crystal composition % Is 13% by mass, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferred content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, and 10% by mass , Is 5% by mass. The liquid crystal composition preferably contains one or two or more compounds selected from the group consisting of compounds represented by general formula (NU-01) to general formula (NU-06).

(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 and R ^NU62 each independently represent the number of carbon atoms from 1 to 8 Alkyl group, alkoxy group with 1 to 8 carbon atoms, alkenyl group with 2 to 8 carbon atoms or alkenyloxy group with 2 to 8 carbon atoms, one of the groups or two or more non-adjacent groups -CH ₂ -may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-).

If described in more detail, R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 and R ^NU62 are independent, preferably the number of carbon atoms 1 to 5 alkyl group, 1 to 5 alkoxy group, or 2 to 3 alkenyl group, more preferably 1 to 5 alkyl group or 2 to 3 carbon atom base. When the response speed is important, at least one of R ^NU11 , R ^NU21 , R ^NU31 , R ^NU41 , R ^NU51 and R ^NU61 is preferably an alkenyl group with 2 to 3 carbon atoms. The preferred content of the compound having such an alkenyl group is 10% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, and 40% by mass or more relative to the total amount of the liquid crystal composition , Is 45% by mass or more, and is 50% by mass or more. When high VHR is important, the preferred content of the compound having an alkenyl group is 40% by mass or less, 35% by mass or less, and 30% by mass or less.

In order to have both high speed and high reliability, it is preferable to use only the compound represented by the general formula (NU-01) as the compound having an alkenyl group. In this case, it is preferable that R ^NU11 is an alkyl group having 2 to 4 carbon atoms, and R ^NU12 is an alkenyl group having 2 to 3 carbon atoms. In order to have both high speed and high reliability, it is preferable to use compounds represented by general formula (NU-01) and general formula (NU-05) as the compound having an alkenyl group. In this case, R ^NU11 is preferably The alkyl group having 2 to 4 carbon atoms and R ^NU12 is an alkenyl group having 2 to 3 carbon atoms. ^Furthermore , it is preferable that R ^NU51 is an alkenyl group having 2 to 3 carbon atoms, and R ^NU52 is an alkyl group having 2 to 3 carbon atoms.

In order to have both high speed and high reliability, it is preferable to use compounds represented by general formula (NU-01), general formula (NU-05), and general formula (NU-04) as the compound having an alkenyl group. In this case, it is preferable that R ^NU11 is an alkyl group having 2 to 4 carbon atoms, and R ^NU12 is an alkenyl group having 2 to 3 carbon atoms. In addition, R ^NU51 and R ^NU41 are each independent, preferably an alkenyl group having 2 to 3 carbon atoms, and R ^NU52 and R ^NU42 are each independent, preferably an alkyl group having 2 to 3 carbon atoms.

The liquid crystal composition preferably contains compounds represented by general formula (NU-01) and general formula (NU-02). The liquid crystal composition preferably contains a compound represented by general formula (NU-01) and general formula (NU-03). The liquid crystal composition preferably contains a compound represented by general formula (NU-04) and general formula (NU-05). The liquid crystal composition preferably contains compounds represented by general formula (NU-05) and general formula (NU-06).

The liquid crystal composition preferably contains compounds represented by general formula (NU-01) and general formula (NU-05). The liquid crystal composition preferably contains compounds represented by general formula (NU-01) and general formula (NU-06). The liquid crystal composition preferably contains a compound represented by general formula (NU-01), general formula (NU-05), and general formula (NU-06).

The content of the compound represented by the general formula (NU-01) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and still more preferably 25 to 45% by mass. The content of the compound represented by the general formula (NU-02) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 5 to 20% by mass. The content of the compound represented by the general formula (NU-03) is preferably from 0 to 20% by mass, more preferably from 0 to 15% by mass, and still more preferably from 0 to 10% by mass.

The content of the compound represented by the general formula (NU-04) is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass. The content of the compound represented by the general formula (NU-05) is preferably 0 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 3 to 20% by mass. 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 still more preferably 3 to 10% by mass.

The liquid crystal composition of the present invention is a compound having a triphenyl structure or a tetraphenyl structure and a dielectric anisotropy Δε greater than +2, that is, it may contain one or more compounds with a positive dielectric anisotropy as Liquid crystal molecules. Furthermore, the 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 whose dielectric property is approximately neutral at 25°C. The compound can be used in combination according to desired properties such as solubility at low temperature, transition temperature, electrical reliability, and refractive index anisotropy. In particular, the polymerizable monomer can be used in a liquid crystal composition containing a polymerizable compound. The reactivity of the body accelerates.

The preferred lower limit of the content of the compound having a triphenyl structure or a tetraphenyl structure and having a dielectric anisotropy Δε greater than +2 relative to the total amount of the liquid crystal composition is 0.1% by mass, 0.5% by mass, and 1% by mass , Is 1.5% by mass, 2% by mass, 2.5% by mass, 3% by mass, 4% by mass, 5% by mass, and 10% by mass. The upper limit of the preferred content is 20% by mass, 15% by mass, 10% by mass, 9% by mass, 8% by mass, 7% by mass, and 6% by mass relative to the total amount of the liquid crystal composition. , Is 5% by mass, 4% by mass, and 3% by mass.

As a compound having a triphenyl structure or a tetraphenyl structure and a dielectric anisotropy greater than +2 that can be used in a liquid crystal composition, it is preferable to contain, for example, those represented by formulas (M-8.51) to (M-8.54) Compounds, compounds represented by formula (M-7.1) to formula (M-7.4), compounds represented by formula (M-7.11) to formula (M-7.14), formula (M-7.21) to formula (M-7.24) ) Represented by the compound.

In order to increase its Tni, the liquid crystal composition of the present invention may also contain formula (L-7.1) to formula (L-7.4), formula (L-7.11) to formula (L-7.13), and formula (L-7.21) to formula (L-7.23), formula (L-7.31) ~ formula (L-7.34), formula (L-7.41) ~ formula (L-7.44), formula (L-7.51) ~ formula (L-753) 4 rings And the dielectric is approximately zero (approximately in the range of -2 ~ +2) compound.

The liquid crystal composition of the present invention may contain normal nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, antioxidants, ultraviolet absorbers, light stabilizers, infrared absorbers, etc., in addition to the above-mentioned compounds. As an antioxidant, the hindered phenol represented by general formula (H-1)-general formula (H-4) is mentioned.

In general formula (H-1) to 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, and 2 to 10 carbon atoms. the number of carbon atoms, alkenyl or alkenyloxy group having 2 to 10, the groups present in the a -CH ₂ - or more non-adjacent of the two -CH ₂ - may each independently be -O- or - S- substitution, and one or two or more hydrogen atoms present in the group may be independently substituted by fluorine or chlorine atoms. More specifically, R ^{H1 is} each independently, preferably an alkyl group having 2 to 7 carbon atoms, an alkoxy group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or a carbon number of 2-7 The alkenyloxy group is more preferably an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.

In the general formula (H-4), M ^H4 represents an alkylene group with 1 to 15 carbon atoms (one or more than two of the alkylene group -CH ₂ -can also be used in such a way that the oxygen atom is not directly adjacent －O－, －CO－, －COO－, －OCO－ substituted), －OCH ₂ －, －CH ₂ O－, －COO－, －OCO－, CF ₂ O－, －OCF ₂ －, －CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -C≡C-, single Bond, 1,4-phenylene (any hydrogen atom in 1,4-phenylene can also be substituted by fluorine atom) or trans-1,4-cyclohexylene, preferably having 1 to carbon atoms 14 of alkylene. Furthermore, if volatility is considered, the number of carbon atoms is preferably a larger number. If viscosity is considered, the number of carbon atoms is preferably not too large. Therefore, ^{MH4 is} preferably 2-12 carbon atoms, more preferably It has 3 to 10 carbon atoms, more preferably 4 to 10 carbon atoms, particularly preferably 5 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.

In general formula (H-1) to general formula (H-4), one of 1,4-phenylene or two or more non-adjacent -CH= may be substituted by -N=. In addition, the hydrogen atom in 1,4-phenylene may be substituted with a fluorine atom or a chlorine atom, respectively. One of 1,4-cyclohexylene in general formula (H-2) and general formula (H-4) or two or more non-adjacent -CH ₂ -can also be -O- or -S -replace. In addition, the hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.

More specifically, as an antioxidant, the compound represented by Formula (H-11)-Formula (H-15), for example is mentioned.

When the liquid crystal composition contains an antioxidant, the lower limit is preferably 10 mass ppm or more, 20 mass ppm or more, and 50 mass ppm or more. On the other hand, the preferable upper limit is 10000 ppm by mass, 1000 ppm by mass, 500 ppm by mass, and 100 ppm by mass. The nematic-isotropic liquid phase transition temperature (Tni) of the liquid crystal composition is preferably 60°C to 120°C, more preferably 70°C to 100°C, and still more preferably 70°C to 85°C. In addition, in this specification, 60°C or higher is expressed as Tni high. In the case of LCD TV use, Tni is preferably 70-80°C, in the case of portable use, Tni is preferably 80-90°C, in the case of outdoor display such as PID (Public Information Display), Tni is more It is preferably 90 to 110°C.

The refractive index anisotropy (Δn) of the liquid crystal composition at 20°C is preferably 0.08 to 0.14, more preferably 0.09 to 0.13, and still more preferably 0.09 to 0.12. In further detail, in the case of thin cell gaps, the refractive index anisotropy (Δn) is preferably 0.10 to 0.13, and in the case of thick cell gaps, the refractive index anisotropy (Δn) is preferably 0.08～0.10. In addition, in this specification, 0.09 or more is expressed as large Δn. The rotational viscosity (γ ₁ ) of the liquid crystal composition at 20°C is preferably 50-160mPa･s, more preferably 55-160mPa･s, more preferably 60-160mPa･s, more preferably 80-150mPa･s, More preferably, it is 90～140mPa･s, particularly preferably 90～130mPa･s, most preferably 100～130mPa･s.

The dielectric anisotropy (Δε) of the liquid crystal composition at 20°C is preferably -2.0 to -8.0, more preferably -2.0 to -6.0, still more preferably -2.0 to -5.0, particularly preferably -2.5 to- 4.0, best -2.5～-3.5. Regarding the total content of the compound having an alkenyl group in the compounds constituting the liquid crystal composition, the preferred upper limit value is 10% by mass, 8% by mass, 6% by mass, 5% by mass, 4% by mass, and 3% by mass is 2% by mass, 1% by mass, and 0% by mass. In addition, the preferable range of the total content of the compound having alkenyl groups is 0-10% by mass, 0-8% by mass, 0-5% by mass, 0-4% by mass, and 0-3% by mass. It is 0 to 2% by mass. Among them, the compound represented by the general formula (NU-01) is not included.

The liquid crystal composition preferably contains a polymerizable monomer as an essential component, and further contains one or two or more selected from general formula (N-01), general formula (N-02), general formula (N-03), The compounds represented by the general formula (N-04), the general formula (N-05) and the general formula (N-06) further contain one or two or more selected from the general formula (NU-01) to (NU-06) ) Represented by the compound. The total upper limit value of the equivalent content is preferably 100% by mass, 99% by mass, 98% by mass, 97% by mass, 96% by mass, 95% by mass, 94% by mass, 93% by mass, and 92% by mass, 91% by mass, 90% by mass, 89% by mass, 88% by mass, 87% by mass, 86% by mass, 85% by mass, 84% by mass, and the total lower limit of the contents The value is preferably 78% by mass, 80% by mass, 81% by mass, 83% by mass, 85% by mass, 86% by mass, 87% by mass, 88% by mass, 89% by mass, and 90 % By mass, 91% by mass, 92% by mass, 93% by mass, 94% by mass, 95% by mass, 96% by mass, 97% by mass, 98% by mass, and 99% by mass.

The liquid crystal display element of the present invention is particularly useful for liquid crystal display elements for active matrix driving, and can be suitably used for VA type, FFS type, IPS type, PSA type, PSVA type, PS-IPS type or PS-FFS type, NPS type, PI-less type, ECB type and other liquid crystal display elements are particularly suitable for PSA type, PSVA type, VA type, IPS type, FFS type or ECB type liquid crystal display elements.

(Liquid crystal display element) The above liquid crystal composition is used to form the liquid crystal layer of a liquid crystal display element. Hereinafter, referring to FIGS. 1 and 2 as appropriate, the liquid crystal display element of this embodiment will be described. FIG. 1 is an exploded perspective view schematically showing an embodiment of a liquid crystal display element, and FIG. 2 is an enlarged plan view of the area enclosed by the line I in FIG. 1. Furthermore, in FIG. 1 and FIG. 2, for the convenience of description, the size of each part and the ratio thereof may be exaggerated and shown differently from the actual situation. In addition, the materials, dimensions, etc. shown below are just an example, and the present invention is not limited to them, and can be appropriately changed without departing from the gist.

The liquid crystal display element 1 shown in FIG. 1 includes an active matrix substrate AM and a color filter substrate CF arranged in an opposing manner, and a liquid crystal layer 4 sandwiched between the active matrix substrate AM and the color filter substrate CF. The active matrix substrate AM has a first substrate 2, a pixel electrode layer 5 provided on the surface of the first substrate 2 on the liquid crystal layer 4 side, and a first polarizing plate provided on the surface of the first substrate 2 opposite to the liquid crystal layer 4 7.

On the other hand, the color filter substrate CF has a second substrate 3, a common electrode layer 6 provided on the liquid crystal layer 4 side of the second substrate 3, and a second substrate 3 provided on the surface opposite to the liquid crystal layer 4 The polarizing plate 8 and the color filter 9 provided between the second substrate 3 and the common electrode layer 6. The liquid crystal layer 4 uses a vertical alignment type with negative dielectric anisotropy. In the liquid crystal layer 4, when no voltage is applied between the electrode layers 5 and 6, the liquid crystal molecules are aligned almost perpendicularly to the substrates AM and CF.

That is, the liquid crystal display element 1 of this embodiment has a first polarizer 7, a first substrate 2, a pixel electrode layer 5, a liquid crystal layer 4, a common electrode layer 6, a color filter 9, a second substrate 3, and a second polarizer. The plates 8 are laminated in sequence. The first substrate 2 and the second substrate 3 are respectively formed of a flexible (flexible) material such as a glass material or a plastic material. Both the first substrate 2 and the second substrate 3 may have light transmittance, or only one of them may have light transmittance. In the latter case, the other substrate can be made of an opaque material such as a metal material or a silicon material.

As shown in FIG. 2, the pixel electrode layer 5 has a plurality of gate bus lines 11 for supplying scanning signals, a plurality of data bus lines 12 for supplying display signals, and a plurality of pixel electrodes 13. Furthermore, a pair of gate bus lines 11 and 11 and a pair of data bus lines 12 and 12 are shown in FIG. 2. A plurality of gate bus lines 11 and a plurality of data bus lines 12 are arranged in a matrix to cross each other, and the unit pixels of the liquid crystal display element 1 are formed by the enclosed areas. One pixel electrode 13 is formed in each unit pixel. Furthermore, each pixel may also be composed of a plurality of sub-pixels.

The pixel electrode 13 may be formed, for example, with two stems orthogonal to each other to form a cross shape, and a plurality of branches branched from each stem and inclined at an angle of about 45° to each stem (a so-called fishbone structure). In other words, the pixel electrode 13 can also be regarded as an electrode having a slit structure formed between the branch portions. With the pixel electrode 13 of this structure, the liquid crystal molecules will be uniformly tilted toward the "four directions of the branch to the stem". Therefore, the area divided into four parts is formed in one pixel, and the viewing angle of the liquid crystal display element 1 can be enlarged.

The width L of each branch is preferably about 1 to 5 μm, more preferably about 2 to 4 μm. In addition, the distance S between adjacent branch portions is preferably about 1 to 5 μm, and more preferably about 2 to 4 μm. With this configuration, the liquid crystal molecules can be more reliably aligned in a specific direction. Between the pair of gate bus lines 11 and 11, a Cs electrode 14 is provided substantially parallel to the gate bus line 11. In addition, a thin film transistor including a source electrode 15 and a drain electrode 16 is provided near the intersection where the gate bus line 11 and the data bus line 12 cross each other. The drain electrode 16 is provided with a contact hole 17.

The gate bus line 11 and the data bus line 12 are preferably formed of, for example, Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni, or alloys containing them, and more preferably, Mo , Al or alloys containing them. In order to increase the light transmittance, the pixel electrode 13 is composed of, for example, a transparent electrode. The transparent electrode is formed by sputtering compounds such as ZnO, InGaZnO, SiGe, GaAs, IZO (Indium Zinc Oxide), ITO (Indium Tin Oxide), SnO, TiO, and AZTO (AlZnSnO). The average thickness of the transparent electrode is preferably about 10 to 200 nm. In addition, in order to reduce resistance, a transparent electrode can be formed in the form of a polycrystalline ITO film by firing an amorphous ITO film.

On the other hand, the common electrode layer 6 has, for example, a plurality of striped common electrodes (transparent electrodes) arranged together. The common electrode may be formed in the same manner as the pixel electrode 13. The color filter 9 can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. In the pigment dispersion method, the curable coloring composition for color filters is supplied on the second substrate 3 in a specific pattern, and then cured by heating or light irradiation. This operation is performed for the three colors of red, green, and blue, whereby the color filter 9 can be obtained. Furthermore, the color filter 9 may be arranged on the side of the first substrate 2.

In addition, from the viewpoint of preventing light leakage, the liquid crystal display element 1 may be provided with a black matrix (not shown). The black matrix is preferably formed in a portion corresponding to the thin film transistor. Furthermore, the black matrix can be arranged on the second substrate 3 side together with the color filter 9, or on the first substrate 2 side together with the color filter 9, or the black matrix can be separately arranged on the first substrate 2 side. On the substrate 2 side, the color filter 9 is arranged on the second substrate 3 side. In addition, the black matrix may be formed by overlapping the colors of the color filter 9 to reduce the transmittance.

The active matrix substrate AM and the color filter substrate CF are attached to each other by a sealing material (sealing material) composed of an epoxy-based thermosetting composition or an acrylic UV-curing composition, etc. Together. Furthermore, spacers that maintain the same distance between the active matrix substrate AM and the color filter substrate CF may also be arranged. Examples of the spacer include granular spacers such as glass particles, plastic particles, and alumina particles, and resin spacers formed by photolithography. The average separation distance between the active matrix substrate AM and the color filter substrate CF (ie, the average thickness of the liquid crystal layer 4) is preferably about 1-100 μm.

The first polarizing plate 7 and the second polarizing plate 8 can be designed in such a way that the viewing angle and the contrast can be improved by adjusting the positional relationship of their transmission axes. Specifically, the first polarizing plate 7 and the second polarizing plate 8 are preferably arranged such that their transmission axes operate in a normally black mode and are orthogonal to each other. It is particularly preferable that any one of the first polarizing plate 7 and the second polarizing plate 8 is arranged such that its penetration axis and the alignment direction of the liquid crystal molecules when a voltage is applied are approximately 45°.

Furthermore, when the first polarizing plate 7 and the second polarizing plate 8 are used, it is preferable to adjust the refractive index anisotropy (∆n) of the liquid crystal layer 4 and the average thickness of the liquid crystal layer 4 so that the contrast becomes the maximum. product. Furthermore, the liquid crystal display element 1 may be equipped with the retardation film for expanding the viewing angle. Furthermore, in the liquid crystal display element 1, at least one of the active matrix substrate AM and the color filter substrate CF is provided with an alignment film such as a polyimide alignment film on the liquid crystal layer 4 side so that the liquid crystal layer 4 is in contact. In other words, in the present invention, by using the liquid crystal composition as described above, at least one of the active matrix substrate AM and the color filter substrate CF may not have an alignment film.

(Method of manufacturing liquid crystal display element) Next, the manufacturing method of this liquid crystal display element 1 is demonstrated. The manufacturing method of the liquid crystal display element of this embodiment has: a preparation step [1], which prepares a substrate and a liquid crystal composition; an assembly step [2], which assembles each component; and a polymerization step [3], which uses an alignment aid And at least one of the polymerizable compound is polymerized. [1] Preparation steps First, the active matrix substrate AM, the color filter substrate CF, and the above-mentioned liquid crystal composition are prepared.

[2] Assembly steps Then, along the edge of at least one of the active matrix substrate AM and the color filter substrate CF, a dispenser is used to draw the sealing material into a closed-loop bank shape. After that, a specific amount of the liquid crystal composition is dropped onto the inner side of the sealing material, and the active matrix substrate AM and the color filter substrate CF are arranged to face each other so as to contact the liquid crystal composition under reduced pressure. In this drop filling (ODF: One Drop Fill) method, the optimum filling amount must be dropped according to the size of the liquid crystal display element 1. The above-mentioned liquid crystal composition, for example, the rapid pressure change in the dripping device generated during dripping or the impact on impact is less, and the dripping can be continued stably for a long time. Therefore, the yield of the liquid crystal display element 1 can be maintained high.

In particular, small liquid crystal display elements often used in smart phones have a small optimal injection amount of liquid crystal composition, so it is difficult to control the deviation amount within a certain range. However, by using the above-mentioned liquid crystal composition, even in a small liquid crystal display element, a stable and optimal injection amount can be accurately dropped. In addition, the ODF method can suppress the occurrence of drip marks when the liquid crystal composition is dropped onto the substrate. Furthermore, the so-called dripping mark refers to the phenomenon that the traces of the liquid crystal composition dripped appear white when the display is black. Then, the sealing material is cured by ultraviolet (active energy rays) irradiation and heating. Furthermore, depending on the type of the sealing material, the sealing material may be cured only by either ultraviolet irradiation or heating.

[3] Polymerization step Next, by irradiating the liquid crystal composition with active energy rays such as ultraviolet rays or electron beams, at least one of the alignment aid and the polymerizable compound is polymerized. Thereby, a polymer layer (polymer of at least one of the alignment aid and the polymerizable compound) for controlling the alignment of the liquid crystal is formed on the interface of the liquid crystal layer 4 to obtain the liquid crystal display element 1. In order to impart a sufficient pretilt angle to the liquid crystal molecules, a moderate polymerization rate is expected. Therefore, during polymerization, it is preferable to irradiate active energy rays singly, in combination, or sequentially. When using ultraviolet light, either a polarized light source or a non-polarized light source can be used.

Furthermore, when polymerizing two substrates facing each other in contact with the liquid crystal composition as in the present embodiment, at least the substrate on the side of the irradiation surface must have proper penetration of active energy rays Sex. In addition, the polymerization can be performed in several stages as described below. Specifically, first, conditions such as electric field, magnetic field, or temperature are adjusted to change the alignment state of liquid crystal molecules. In this state, the liquid crystal composition is irradiated with active energy rays to polymerize at least one of the alignment aid and the polymerizable compound. Then, without applying an electric or magnetic field, the liquid crystal composition is irradiated with active energy rays to polymerize the remaining unpolymerized polymer (remaining monomer).

Especially when ultraviolet rays are used, it is preferable to apply an AC electric field to the liquid crystal composition while irradiating ultraviolet rays. The frequency of the AC applied is preferably about 10 Hz to 10 kHz, more preferably about 60 Hz to 10 kHz. The applied AC voltage is selected depending on the desired pretilt angle of the liquid crystal display element 1. That is, by adjusting the applied AC voltage, the pretilt angle of the liquid crystal display element 1 can be controlled. The pretilt angle imparted to the liquid crystal molecules is preferably about 85 to 89.5°, more preferably about 87.5 to 89°. By adjusting the pretilt angle of the liquid crystal molecules within this range, the response speed of the liquid crystal display element 1 can be sufficiently increased, and the decrease in contrast can be prevented.

The temperature when irradiated with ultraviolet rays is preferably within a temperature range that maintains the liquid crystal state of the liquid crystal composition. The specific temperature is preferably a temperature close to room temperature, that is, typically about 15 to 35°C. As a lamp that generates ultraviolet rays, metal halide lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, fluorescent tubes, etc. can be used. In addition, the ultraviolet rays to be irradiated are preferably ultraviolet rays having a wavelength that is not the absorption wavelength region of the liquid crystal composition, and it is more preferable to cut off a specific wavelength and use it as necessary.

The intensity of the irradiated ultraviolet rays is preferably about 0.1 mW/cm ^{2 to} 100 W/cm ² , more preferably about 2 mW/cm ^{2 to} 50 W/cm ² . Furthermore, it is also possible to irradiate ultraviolet rays while changing the intensity. The energy of the irradiated ultraviolet rays can be adjusted appropriately, preferably about 10 mJ/cm ² ˜500 J/cm ² , more preferably about 100 mJ/cm ² ˜200 J/cm ² . In addition, the time for irradiating ultraviolet rays is appropriately selected according to its intensity, and is preferably about 10 to 3600 seconds, and more preferably about 10 to 600 seconds.

Furthermore, in the assembly step [2], the vacuum injection method can also be used instead of the drop injection (ODF) method. For example, in the vacuum injection method, first, the sealing material is screen-printed along the edge of at least one of the active matrix substrate AM and the color filter substrate CF while leaving the injection port. After that, the sealing material is thermally cured by bonding and heating the two substrates AM and CF. Then, the liquid crystal composition is injected into the space partitioned by the sealing material between the two substrates AM and CF through the injection port under vacuum, and the injection port is sealed. Then, move to [3] polymerization step. The liquid crystal display element 1 obtained in the above manner is preferably a PSA type, PSVA type, VA type, IPS type, FFS type, or ECB type liquid crystal display element, and more preferably a PSA type liquid crystal display element.

In the present invention, there is an aspect of "adjusting the residual amount of polymerizable monomers (alignment aids and/or polymerizable compounds) in the liquid crystal layer 4, that is, the amount of unreacted polymerizable monomers below 200 ppm." Feature. If the residual amount of the polymerizable monomer in the liquid crystal layer 4 exceeds 200 ppm and increases, the voltage holding ratio (VHR) of the liquid crystal display element 1 drastically decreases. In contrast, by making the residual amount of polymerizable monomer in the liquid crystal layer 4 less than 200 ppm, the adverse effect on the liquid crystal molecules caused by the residual polymerizable monomer (residual monomer) can be suppressed, and the liquid crystal display can be prevented The voltage holding rate of element 1 is reduced. The residual amount of the polymerizable monomer may be 200 ppm or less, but it is preferably 150 ppm or less, and more preferably 100 ppm or less. By adjusting the residual amount of the polymerizable monomer within this range, the decrease in the voltage holding ratio of the liquid crystal display element 1 can be further reduced.

When the liquid crystal composition contains both the alignment aid (polymerizable monomer A) and the polymerizable compound (polymerizable monomer B) as the polymerizable monomer, it is preferable to set the total residual amount of them as The above range. Furthermore, when both the alignment aid and the polymerizable compound are contained, the individual residual amount of the alignment aid and the polymerizable compound is preferably 100 ppm or less, more preferably 75 ppm or less, and still more preferably 50 ppm or less. Furthermore, when the liquid crystal composition contains only one of an alignment aid and a polymerizable compound as a polymerizable monomer, the residual amount is preferably 100 ppm or less, more preferably 85 ppm or less.

From the viewpoint of preventing the voltage retention rate of the liquid crystal display element 1 from decreasing, the residual amount of the polymerizable monomer is preferably as low as possible. On the other hand, from the viewpoint of suppressing damage to the liquid crystal molecules (host compound) caused by irradiated active energy rays, it is preferable to positively leave a certain amount of polymerizable monomer in the liquid crystal layer 4. Therefore, the residual amount of the polymerizable monomer in the liquid crystal layer 4 also has a lower limit value, and the specific residual amount is preferably 10 ppm or more, more preferably 20 ppm or more, and still more preferably 30 ppm or more. By leaving the polymerizable monomer in the liquid crystal layer 4 in this amount, the damage to the liquid crystal molecules caused by the adverse effects of active energy rays can be suppressed more reliably, and therefore, the voltage retention rate of the liquid crystal display element 1 can also be reduced. reduce.

When the liquid crystal composition contains only one of an alignment aid and a polymerizable compound as a polymerizable monomer, it is preferable to set the residual amount in the above-mentioned range. Furthermore, when the liquid crystal composition contains both an alignment aid and a polymerizable compound as polymerizable monomers, the total residual amount of them is preferably 20 ppm or more, more preferably 40 ppm or more, and still more preferably 60 ppm the above.

Also, by leaving a certain amount (a small amount) of polymerizable monomers, for example, when the liquid crystal display element 1 is used, by the action of light from the backlight, even if free radicals are generated in the liquid crystal layer 4, the free radicals are polymerized Capture of polymerizable groups of sexual monomers. Therefore, it is difficult to generate damage to the liquid crystal molecules caused by free radicals. Therefore, the voltage retention rate of the liquid crystal display element 1 can also be reduced over time. Furthermore, the remaining polymerizable monomer is deactivated by capturing free radicals by itself. Therefore, as long as the amount is the above-mentioned certain amount, direct damage to the liquid crystal molecules of the polymerizable monomer is unlikely to be a problem. In short, although the liquid crystal molecules closer to the substrate provided on the backlight side are more likely to generate free radicals under the influence of the light from the backlight, the alignment aid (polymerizable monomer A) with adsorption groups In the case where it remains in the liquid crystal layer 4, it is considered that the remaining polymerizable monomer is also likely to be excessively present near the surface (interface with the liquid crystal layer) of the substrate. Therefore, even if the residual amount of the polymerizable monomer is small, the decrease in the voltage holding ratio of the liquid crystal display element 1 can be effectively suppressed. When considering the radical trapping ability of the polymerizable monomer, the polymerizable group is preferably the above-mentioned polymerizable group having an unsaturated bond, and more preferably a (meth)acryloyl group.

The residual amount of the polymerizable monomer in the liquid crystal layer 4 can be determined by setting the intensity, wavelength, energy, and irradiation time of the active energy rays (ultraviolet rays) irradiated to the liquid crystal composition, or the type and added amount of the polymerizable monomer. Adjustment. As mentioned above, the liquid crystal display element of this invention was demonstrated based on embodiment, but this invention is not limited to this, Each structure may be substituted by arbitrary structures which have the same function, and other arbitrary structures may be added. [Example]

Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited to these. The characteristics measured for the liquid crystal composition are as follows. Tni: nematic phase-isotropic liquid phase transition temperature (℃) Δn: Refractive index anisotropy at 293 K Δε: Dielectric conductivity at 293 K γ1: Rotational viscosity at 293 K (mPa·s) K11: Elastic constant of diffusion at 293 K (pN) K33: Bending spring constant (pN) at 293 K

In addition, the following abbreviations are used for the description of the compounds used in each example and each comparative example. The n in the abbreviation is a natural number. (Side chain) -n -C _n H _2n+1 : Linear alkyl group with n carbon atoms n- C _n H _2n+1 -: Linear alkyl group with n carbon atoms -On- -OC _n H _2n+1 : Straight-chain alkoxy group with carbon number n-V1 -CH=CH-CH ₃ : Propylene group V- CH ₂ =CH-: Vinyl 1V2-CH ₃ -CH=CH-CH ₂ －CH ₂ －: Pentenyl

(Link structure) -nO- -C _n H _2n O- (ring structure)

The composition and physical properties of the liquid crystal mixtures LC-1 and LC-2 are shown in Table 1 below. [Table 1] LC-1 LC-2 Liquid crystal molecules [mass%] 3-Cy-Cy-2 16.5 16.5 3-Cy-Cy-4 3 4.5 3-Cy-Cy-V1 8.5 3-Cy-Ph-O1 15 4.5 3-Ph-Ph-1 9 3-Cy-Ph-Ph-2 8 6.5 1V2－Ph－Ph－1 6 3－Cy－1O－Ph5－O1 8.5 3－Cy－Cy－1O－Ph5－O2 17 3－Cy－Ph5－O2 15.5 3－Ph－Ph5－O2 6.5 3－Cy－Cy－Ph5－O1 3.5 3－Cy－Cy－Ph5－O2 12.5 2－Cy－Ph－Ph5－O2 6.5 5.5 3-Cy-Ph-Ph5-O2 8 10 3-Cy-Ph-Ph5-O4 8.5 total 100 100 Property value Tni[℃] 75 74 Δn 0.112 0.104 Δε -3.0 －2.8 γ ₁ [mPa·s] 122 107 K ₁₁ [pN] 14.1 14.7 K ₃₃ [pN] 13.9 14.2

As the alignment aid (polymerizable monomer A), the following alignment aids (SA1) to (SA6) were used.

As the polymerizable compound (polymerizable monomer B), the following polymerizable compounds (PSA1) to (PSA4) were used.

1. Preparation of liquid crystal composition (Example 1) The alignment aid (SA2) is mixed so that the liquid crystal mixture LC-1 becomes 0.7% by mass, and is heated and melted to prepare a liquid crystal composition. Therefore, no polymerizable compound was mixed in the liquid crystal composition of Example 1. (Examples 2-21, Comparative Examples 1-5) The liquid crystal composition was prepared in the same manner as in Example 1, except that the types and addition amounts of the liquid crystal mixture, alignment aid, and polymerizable compound were changed as shown in Table 2.

2. Fabrication of the liquid crystal cell. First, make "the first substrate (common electrode substrate) with a transparent electrode layer and no alignment film" and "a pixel electrode layer with a transparent pixel electrode driven by an active device, but without The second substrate of the alignment film (pixel electrode substrate)". Then, after dropping the liquid crystal composition on the first substrate, it was pinched by the second substrate, and the sealing material was cured under normal pressure at 110° C. for 2 hours to obtain a liquid crystal cell with a cell gap of 3.2 μm. Next, with a voltage of 100 Hz and 10 V applied to the liquid crystal cell, a high-pressure mercury lamp is used to irradiate ultraviolet rays through a filter that cuts off ultraviolet rays having a wavelength of 325 nm or less. At this time, adjust so that the illuminance (intensity) measured under the condition of the center wavelength of 365nm is 100mW/cm ² , and irradiate ultraviolet rays with a cumulative light amount of 10J/cm ² . Let this ultraviolet irradiation condition be irradiation condition 1. Utilize the ultraviolet ray irradiation in irradiation condition 1 to impart a pretilt angle to the liquid crystal molecules in the liquid crystal cell.

Next, for the liquid crystal cell, the fluorescent UV lamp manufactured by Toshiba Lighting Technology Co., Ltd. is used, and the illuminance (intensity) measured under the condition of the center wavelength of 313nm is adjusted to 3mW/cm ² , and the cumulative light quantity is 10J/cm ² (less). Either 20J/cm ² (medium) or 50J/cm ² (more) to irradiate ultraviolet rays. Thus, a liquid crystal display element is obtained. Let this ultraviolet irradiation condition be irradiation condition 2. The UV irradiation in irradiation condition 2 reduces the residual amount of unreacted polymerizable monomers (alignment aids and polymerizable compounds) in the liquid crystal cell. Furthermore, using each liquid crystal composition, two liquid crystal cells were produced.

3. Measurement and evaluation 3-1. Determination of the residual amount of polymerizable monomer With respect to the obtained liquid crystal cell, the amount (ppm) of the polymerizable monomer remaining in the liquid crystal layer was measured in the following manner. First, the liquid crystal cell is decomposed to dissolve the liquid crystal molecules, polymer of polymerizable monomer and unreacted polymerizable monomer in acetonitrile. Then, the acetonitrile solution containing the eluted components was analyzed by a high performance liquid chromatograph, and the peak area of each eluted component was measured. Then, based on the ratio of the peak area of the liquid crystal molecules as an index to the peak area of the unreacted polymerizable monomer, the amount of the remaining polymerizable monomer is determined. The value obtained therefrom and the amount of polymerizable monomer (initial amount) added when preparing the liquid crystal composition determine the residual amount of polymerizable monomer.

3-2. Evaluation of vertical alignment Regarding the obtained liquid crystal cell, alignment unevenness such as vertical alignment and dripping marks were observed using a polarizing microscope, and the evaluation was performed based on the following criteria. [Evaluation criteria] S: Vertical alignment evenly over the entire surface A: Only has very few alignment defects, but to an allowable level B: There is an alignment defect, which is not tolerable C: Poor alignment is very bad

3－3. Evaluation of the initial value of voltage holding rate (VHR) For the obtained liquid crystal cell, VHR (%) was measured using a voltage retention measurement system (manufactured by Toyo Technology Co., Ltd., "LCM-2 type"), and evaluated based on the following criteria. In addition, the measurement conditions were 60°C, a frequency of 60 Hz, and an applied voltage of 1V. [Evaluation criteria] S: more than 99% and below 100% A: More than 98% and less than 99% B: More than 95% and below 98% C: Below 95%

3-4. Evaluation of the change of voltage holding ratio (VHR) with the passage of time Regarding the obtained liquid crystal cell, the light of brightness 8500cd/m ² is continuously irradiated without passing through the polarizing plate, so that the surface temperature becomes 50℃. After 45 days passed, VHR was measured in the same manner as described above, and the evaluation was performed based on the following criteria. [Evaluation Criteria] S: Decrease less than 10% from the initial value A: Decrease by more than 10% and less than 15% from the initial value B Decrease by more than 15% and less than 20% from the initial value C: Relatively From the initial value, reduce by more than 20%

3-5. Evaluation of pretilt angle stability For the obtained liquid crystal cell, a pretilt angle measurement system (manufactured by SINTEC, "OPTIPRO") was used to measure the pretilt angle of the liquid crystal molecules. Set this pretilt angle as the initial value. Next, a rectangular voltage with a frequency of 100 Hz and 30 V was applied to the liquid crystal cell, and the backlight was continuously illuminated for 10 hours. Then, measure the pretilt angle again and set it as the pretilt angle (post-test value). Furthermore, the voltage of 30V is several times larger than the normal driving voltage, which is an accelerated test. The value obtained by subtracting the pretilt angle (value after the test) from the measured pretilt angle (initial value) is the pretilt angle change amount (= the absolute value of the pretilt angle change) [°], and the evaluation is based on the following criteria. The closer the pretilt angle change amount is to 0[°], the lower the possibility of poor display caused by the pretilt angle change. [Evaluation criteria] S: Change within 0.1° (almost no display defects) A: Over 0.1° and within 0.3 change (it is difficult to cause display defects) B: More than 0.3° and changes within 0.5° (producing many display defects) C: Change of more than 0.5° (the display is poor and it is not tolerable) The above results are shown in Table 2 below.

[Table 2]

In the example where the residual amount of each polymerizable monomer was set to 100 ppm or less (especially 50 ppm or less), there was no reduction in vertical alignment, and the VHR or tilt stability was also good. The residual amount of each polymerizable monomer can be suppressed by adjusting the cumulative amount of ultraviolet light. In contrast, in Comparative Examples 2, 4, and 5 in which the residual amount of each polymerizable monomer exceeded 100 ppm, VHR was significantly reduced. In addition, in Comparative Examples 1 and 3 in which the residual amount of each polymerizable monomer exceeded 0 ppm, the cumulative amount of ultraviolet light was too much, causing damage to the liquid crystal molecules, and it is thought that this resulted in a decrease in VHR. According to the above results, it can be seen that the vertical alignment, VHR, and tilt stability of each embodiment are better than those of the comparative examples. In the liquid crystal cell without the alignment film, the vertical alignment of the liquid crystal molecules is achieved, so it is more suitable. In addition, in an embodiment where the residual amount of each polymerizable monomer is 10 ppm or more (especially 30 ppm or more), the change (decrease with time) of VHR over time can also be suppressed.

1: liquid crystal display element AM: active matrix substrate CF: Color filter substrate 2: The first substrate 3: The second substrate 4: Liquid crystal layer 5: Pixel electrode layer 6: Common electrode layer 7: The first polarizer 8: The second polarizer 9: Color filter 11: Gate bus line 12: Data bus line 13: Pixel electrode 14: Cs electrode 15: Source electrode 16: Drain electrode 17: Contact hole

Fig. 1 is an exploded perspective view schematically showing an embodiment of a liquid crystal display element. [Figure 2] An enlarged top view of the area enclosed by line I in Figure 1.

Claims (12)

A liquid crystal display element, which has two substrates, and A liquid crystal layer arranged between the two substrates, The liquid crystal layer contains liquid crystal molecules and polymers of polymerizable monomers, In the liquid crystal layer, the residual amount of the polymerizable monomer is 200 ppm or less. The liquid crystal display element of claim 1, wherein, in the liquid crystal layer, the residual amount of the polymerizable monomer is 10 ppm or more. The liquid crystal display element of claim 1 or 2, wherein the polymerizable monomer includes a polymerizable monomer A having an adsorption group. The liquid crystal display element according to claim 3, wherein the residual amount of the polymerizable monomer A in the liquid crystal layer is 100 ppm or less. The liquid crystal display element of claim 1 or 2, wherein the polymerizable monomer includes a polymerizable monomer B having no adsorption group. The liquid crystal display element according to claim 5, wherein the residual amount of the polymerizable monomer B in the liquid crystal layer is 100 ppm or less. The liquid crystal display element of claim 5, wherein the polymerizable monomer B is represented by the following general formula (P),

(In formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group with 1 to 15 carbon atoms, or -Sp ^p2 -P ^p2 [one of the above alkyl groups or non-adjacent ones Two or more -CH ₂ -can be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and 1 of the above-mentioned alkyl groups One or more hydrogen atoms may be independently substituted by cyano, fluorine or chlorine atoms], P ^p1 and P ^p2 each independently represent the following general formulas (P ^p1 -1) to formula (P ^p1 -9 ) Any one of them,

[In the formula, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a halogenated alkyl group with 1 to 5 carbon atoms, and W ^p11 represents a single bond, -O-, -COO- , -OCO- or -CH ₂ -, t ^p11 represents 0, 1 or 2, and when there are multiple R ^p11 , R ^p12 , W ^p11 and/or t ^p11 in the molecule, they can be the same or different , * Represents a bonding bond], Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer, Z ^p1 and Z ^p2 each independently represent a single bond, -O-, -S-, -CH ₂ -, -OCH _{2 -, - CH 2 O -} , - CO -, - C 2 H 4 -, - COO -, - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO- NR ^ZP1 －, －NR ^ZP1 －CO－, ^－SCH ₂ －, －CH ₂ S－, －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 －,－(CH ₂ ) ₂ －COO－,－(CH ₂ ) ₂ －OCO－, －OCO－(CH ₂ ) ₂ －,－(C=O)－O－(CH ₂ ) ₂ －,－CH =CH-, -CF=CF-, -CF=CH-, -CH=CF-, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ －, －CF ₂ CF ₂ － or －C≡C－[In the formula, R ^ZP1 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and when there are plural R ^ZP1 in the molecule, which Etc. may be the same or different], A ^p1 , A ^p2 and A ^p3 each independently represent a group selected from the group consisting of radicals (a ^p ) to group (c ^p ) [the following groups (a ^p ), The hydrogen atoms present in the group (b ^p ) and the group (c ^p ) can be independently replaced by a halogen atom, an alkyl group with 1 to 8 carbon atoms, an alkenyl group with 1 to 8 carbon atoms, a cyano group, or -Sp ^p2 -P ^p2 substitution], (a ^p ) 1,4-cyclohexylene [1 -CH ₂ -or ₂ or more non-adjacent -CH ₂ -in the group can be substituted by -O- ], (b ^p ) 1,4-phenylene [1 -CH= or 2 or more non-adjacent -CH= can be substituted by -N= in the group], and (c ^p ) Naphthalene-2,6-diyl, naphthalene-1 ,4-diyl, naphthalene-1,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decalin-2,6-diyl, phenanthrene-2,7 －Diyl or anthracene-2,6-diyl [1 of these groups -CH= or 2 or more non-adjacent -CH= can be substituted by -N=], m ^p1 represents 0, 1, 2 or 3, when there are a plurality of Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 in the molecule, they can be the same or different. A ^p3 is 0 in m ^p1 and A ^p1 is the above In the case of base (c ^p ), it can be a single bond). The liquid crystal display element of claim 1 or 2, wherein the polymerizable monomer has a polymerizable group selected from the group represented by the following general formula (AP-1) to general formula (AP-9),

(In the formula, R ^AP1 and R ^AP2 each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a halogenated alkyl group with 1 to 10 carbon atoms [one or more of the alkyl groups- CH ₂ -may be substituted by -O- or -CO-, and one or more of the hydrogen atoms in the above alkyl group may be independently substituted by halogen atoms or hydroxyl groups], W ^AP1 represents a single bond, -O-, -COO-, -OCO- or -CH ₂ -, t ^AP1 represents 0, 1 or 2, * represents a bonding bond). The liquid crystal display element of claim 1 or 2, wherein the dielectric anisotropy (Δε) of the liquid crystal molecules is a negative value. For example, the liquid crystal display element of claim 1 or 2, which is used for active matrix driving. For example, the liquid crystal display element of claim 1 or 2, which is PSA type, PSVA type, VA type, IPS type, FFS type or ECB type. The liquid crystal display element of claim 1 or 2, wherein at least one of the two substrates does not have an alignment film.

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