WO2019124153A1 - Liquid crystal composition and liquid crystal display device - Google Patents

Abstract

The purpose of the present invention is to provide: a liquid crystal composition having excellent vertical alignment properties and burn-in resistance; and a liquid crystal display device using the liquid crystal composition. The present invention provides a liquid crystal composition containing: at least one spontaneously aligning monomer; and two or more polymerizable monomers, wherein the at least one spontaneously aligning monomer has a first mesogen backbone, at least one polymerizable group represented by general formula (PG1), and at least one anchoring group, and the two or more polymerizable monomers are selected from the group consisting of polymerizable monomers represented by general formula (I) and having a chemical structure different from that of the spontaneously aligning monomer.

Description

Liquid crystal composition and liquid crystal display device

The present invention relates to a liquid crystal composition containing three or more kinds of monomers and a liquid crystal display device using the same.

Generally, in liquid crystal display devices such as liquid crystal panels and liquid crystal displays, the state of alignment of liquid crystal molecules is changed by an external stimulus such as an electric field, and the change in optical characteristics accompanying this is used for display. Such a liquid crystal display element has a configuration in which liquid crystal molecules are filled in a gap between two transparent substrates, and the liquid crystal molecules are arranged in advance in a specific direction on the surface of the substrate in contact with the liquid crystal molecules. It is general to form an alignment film for making it.

However, with the problem that alignment defects occur due to scratches and dust generated on the alignment film surface in the manufacturing process of liquid crystal display elements and the size of the substrate is increased, uniform alignment over the entire surface of the substrate and long-term There is a problem in that it becomes difficult to design and control an alignment film for obtaining uniform alignment.

Therefore, in recent years, development of a liquid crystal display element which does not require an alignment film represented by a polyimide layer is required by using a liquid crystal composition containing a spontaneous alignment agent for controlling the alignment of liquid crystal molecules for the liquid crystal layer.

For example, in Patent Document 1, instead of lauryl acrylate, which has relatively weak interaction with liquid crystal molecules, a highly linear monofunctional biphenyl monomer having an octyl group and a low straight line having a stearyl group are shown. A liquid crystal composition containing a spontaneous alignment material that suppresses a decrease in voltage holding ratio by a liquid crystal composition containing a functional biphenyl monomer is described.

Further, Patent Document 2 discloses various liquid crystal compositions including a polymerizable self-orientation additive that controls the alignment of liquid crystal molecules without using an alignment film. Specifically, when a liquid crystal composition containing a low molecular weight non-polymerizable liquid crystal component and a polymerizable self alignment additive is filled in a test cell without a polyimide alignment layer (test cell without a pre alignment layer), It has a spontaneous homeotropic (perpendicular) orientation with respect to the substrate surface, this orientation is kept stable up to the clearing point, and the formed VA cell is described as reversibly switchable by applying a voltage. There is.

U.S. Patent Publication No. 2017-0123275 JP-A-2017-523289

However, a composition including two hydrophobic monomers each having a long alkyl chain and a biphenyl skeleton as shown in the above-mentioned Patent Document 1 has an interaction with liquid crystal molecules of a liquid crystal layer filled between a pair of substrates. Although it is considered to be stronger than lauryl acrylate, there arises a problem that the alignment direction of liquid crystal molecules can not be regulated due to the low adsorption power to the substrate.

Further, Patent Document 2 describes a mode in which a non-polymerizable self-orienting additive and one type of polymerizable monomer are mixed with a polymerizable self-orienting additive having an adsorptive group which is a hydroxyl group or an amino group. Therefore, it is considered that the molecular design is in consideration of the adsorption force to the substrate. However, if the adsorptive power of the polymerizable self-orienting additive with respect to the substrate is too high, the polymerizable self-orienting additive does not spread uniformly on the substrate, causing a problem of uneven alignment. Also, the state of the layer polymerized in the state where the polymerizable self-orienting additive is adsorbed to the substrate is not considered. That is, in the composition described in Patent Document 2, the composition in which the non-polymerizable self-orienting additive and the polymerizable self-orienting additive are mixed or the polymerization component is the polymerizable self-orienting additive alone or one kind of the polymerizability Because it is any of the monomers, it is difficult to form a dense layer. If the dense layer is not formed, the vertical alignment component of the self-alignment additive is not fixed, and the amount of change in the pretilt angle becomes large, which causes a problem that the image sticking property is deteriorated.

Accordingly, the problem to be solved by the present invention is to provide a liquid crystal composition excellent in vertical alignment and burn-in characteristics, and to provide a liquid crystal display device using the same.

Another problem to be solved by the present invention is to provide a liquid crystal composition excellent in three properties of vertical alignment, low temperature solubility and burn-in characteristics, and to provide a liquid crystal display device using the same. is there.

As a result of intensive investigations conducted by the present inventors, a liquid crystal composition containing one or more self-alignment polymerizable monomers and a polymerizable monomer having two or more specific chemical structures and a liquid crystal display device using the same The inventors have found that the above problems can be solved, and have completed the present invention.

The liquid crystal composition according to the present invention exhibits excellent vertical alignment to liquid crystal molecules and excellent burn-in characteristics.

The liquid crystal composition according to the present invention exhibits excellent spreadability (wet spread) with respect to a substrate.

The liquid crystal composition according to the present invention can be free from or non-uniform in orientation.

The liquid crystal display element according to the present invention exhibits no alignment unevenness or reduced alignment unevenness.

A first aspect of the present invention is one or more kinds of spontaneously orienting monomers having a mesogenic group, at least one polymerizable group represented by the general formula (PG1), and at least one adsorptive group,
It is a liquid crystal composition including two or more types of polymerizable monomers selected from the group consisting of compounds represented by the following general formula (I) having a chemical structural formula different from the spontaneously orienting monomer.

(Wherein, P ¹¹ is any group represented by the following Formula (PI) to Formula (P-IX),

(Wherein, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, and W ^p11 is a single bond, —O -, - COO- or a methylene ^{group, t pi 1} represents 0, 1 or 2, wherein one or more hydrogen atoms of the polymerizable group ^{P 11} may be substituted with the suction group).
S ¹¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - directly oxygen atom It may be substituted by -O-, -OCO- or -COO- so that it is not adjacent, and one or more hydrogen atoms of S ¹¹ may be substituted by the adsorptive group. * In the above chemical formula represents a bond. )

(In the general formula ^{(I), R 101, R} 102, R 103, R 104, R 105, R 106, R 107, R 108, R 109 and ^{R 110} are each ^{independently,} P ^{21 -S} 21 - And an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, and P ²¹ represents a group represented by the above formula (RI) to a formula (R-IX) Any group represented by),
The above S ²¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more of —CH ₂ — in the alkylene group is —O— such that oxygen atoms are not directly adjacent to each other. , -OCO- or -COO- may be substituted,
n ¹¹ represents 0, 1 or 2;
n ¹² and n ¹³ each independently represent 0 or 1;
represents n ¹¹ + n ¹² + n ¹³ = 1, 2 or 3;
A ¹¹ is a group (a), a group (b) and a group (c) shown below:
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (c) Naphthalene-2,6-diyl group, 2,7-phenanthrendiyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6 One -CH = or two or more non-adjacent -CH = in the -diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is replaced by -N = May be.)
Group (a), group (b) and group (c) are each independently an alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms. alkoxy group, a halogen, a cyano group, a nitro group, or ^P 11 ^{-S 11} - be substituted with good,
L ¹⁰ and L ¹¹ each independently represent a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —OC ₂ H ₄ O—, —COO—, —OCO—, — CH = CR ^a -COO-, -CH = CR ^a -OCO-, -COO-CR ^a = CH-, -OCO-CR ^a = CH-,-(CH ₂ ) _z -COO-,-(CH ₂ ) _{z -OCO -, - OCO- (CH} 2) z -, - COO- (CH 2) z -, - CH = CH -, - CF 2 O -, - OCF 2 - or -C≡C- (wherein And ^Ra each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, each z independently represents an integer of 1 to 4).
When a plurality of P ²¹ , S ²¹ , L ¹¹ and A ¹¹ exist, they may be the same or different. )
Since the liquid crystal composition according to the present invention contains at least three kinds of monomers having different chemical structures, it is easy to correspond to various polymerization conditions, and a polymer reaction is easy to progress, so a dense polymer network layer Can be formed. In addition, by using two or more kinds of polymerizable monomers, it is possible to include two or more kinds of monomers whose function is separated from the group of polymerizable monomers involved in the polymerization reaction and the group of polymerizable monomers contributing to the vertical alignment. Therefore, it is considered that high vertical orientation and a small amount of pretilt change can be achieved.

Hereinafter, the liquid crystal composition according to the present invention contains a spontaneous alignment monomer and a polymerizable monomer which are essential components as a polymerizable component, and a non-polymerizable liquid crystal compound as a liquid crystal component. Hereinafter, the spontaneous orientation monomer and the polymerizable monomer, which are essential components, will be described, and then the liquid crystal component contained in the liquid crystal composition will be described in detail.

<Spontaneous alignment monomer>
The spontaneous orientation monomer according to the present invention is mainly used by being added to a liquid crystal composition, and a member (electrode (for example, ITO), substrate (for example, glass substrate, acrylic) directly in contact with the liquid crystal layer containing the liquid crystal composition Interact with the substrate, transparent substrate, flexible substrate, etc., resin layer (eg, color filter, alignment film, overcoat layer, etc.), insulating film (eg, inorganic material film, It has a function of inducing homeotropic alignment or homogeneous alignment of liquid crystal molecules.

The above-mentioned spontaneously orienting monomer has a polymerizable group for polymerization, a mesogenic group similar to liquid crystal molecules, and an adsorptive group capable of interacting with members directly in contact with the liquid crystal layer, and if necessary alignment of liquid crystal molecules It is preferable to further have a bending group that induces

"Polymerizable group"
The polymerizable group according to the present invention is a group represented by general formula (PG1), and P ¹¹ is selected from the group represented by the following general formula (PI) to general formula (P-IX) Group.

(Wherein, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, and W ^p11 is a single bond, —O -, -COO- or a methylene group, and t ^p11 represents 0, 1 or 2.)
The above P ¹¹ is preferably a group selected from the group represented by the following Formula (PI) to Formula (P-IX), and is more preferably Formula (PI).

In the spontaneously orienting monomer according to the present invention, P ¹¹ -S ^11- may be bonded to a mesogenic group, an adsorptive group and / or a bending group.

In the spontaneously orienting monomer according to the present invention, the polymerizable group is preferably bonded directly to the mesogenic group, the adsorptive group or the bending group via a spacer group, or directly to the mesogenic group or the adsorptive group. Or it is more preferable to couple | bond through a spacer group.

The spacer group (Sp ¹¹ ) preferably represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and a single bond or a linear chain having 1 to 20 carbon atoms. It is more preferable to represent an alkylene group, and more preferable to represent a single bond or a linear alkylene group having 2 to 10 carbon atoms. Moreover, in the above-mentioned spacer group (Sp ¹¹ ), one or two or more non-adjacent —CH ₂ — in the alkylene group are each independently —CH = CH—, —C≡C—, — It may be substituted by O-, -CO-, -COO- or -OCO-.

In spontaneous orientation monomers according to the present invention, the polymerizable group (P ^{11 -S 11 -)} number of, preferably 1 to 5 or less, more preferably 1 to 4, 2 to 4 Is more preferably, 2 or 3 is more preferable, and 2 is even more preferable.

The hydrogen atom in P ¹¹ -S ^11- may be substituted by a polymerizable group, an adsorptive group and / or a bending group.

"Mesogen group"
The mesogenic group according to the present invention refers to a group having a rigid portion, for example, one having one or more cyclic groups, and preferably has 2 to 4 cyclic groups, and is preferably a cyclic group. Is more preferably 3 to 4. If necessary, the cyclic group may be linked by a linking group. The mesogenic group is preferably a skeleton similar to the liquid crystal compound used in the liquid crystal layer.

In the present specification, the term "cyclic group" refers to an atomic group in which the constituting atoms are cyclically bound, and includes a carbocyclic ring, a heterocyclic ring, a saturated or unsaturated cyclic structure, a single ring, a bicyclic structure and a polycyclic ring. Including formula structures, aromatics, non-aromatics, etc. Also, the cyclic group may contain at least one hetero atom, and may be further substituted by at least one substituent (halogen atom, reactive functional group, organic group (alkyl, aryl etc.). When the group is a single ring, the mesogenic group preferably contains two or more single rings.

It is preferable that the said mesogenic group is represented, for example by General formula (AL).

(Wherein, Z ^AL 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 an alkylene group having 1 to 20 carbon atoms, and in this alkylene group One or two or more non-adjacent -CH _2- may be substituted with -O-, -COO- or -OCO-,
A ^AL represents a divalent cyclic group,
One or more hydrogen atoms in Z ^AL and A ^AL may each independently be substituted with a halogen atom, an adsorptive group, P ¹¹ -S ¹¹ -or a monovalent organic group,
When a plurality of Z ^AL and A ^AL are present, they may be the same as or different from each other, and m ^AL represents an integer of 1 to 5, and * in the above formula represents * at the left end and * at the right end Represents a bond. )
In the general formula (AL), Z ^AL is preferably a single bond or an alkylene group having 2 to 20 carbon atoms, and more preferably a single bond or an alkylene group having 2 to 10 carbon atoms. One or two or more non-adjacent —CH ₂ — in the alkylene group may be substituted with —O—, —COO— or —OCO—. Furthermore, when aiming at the linearity of a rod-like molecule, it is preferable that the number of the single bond which is a form in which a ring and a ring are directly connected and the number of atoms directly connecting the ring and the ring is an even number. For example, in the case of —CH ₂ —CH ₂ COO—, the number of atoms directly linking the ring to the ring is four.

In general formula (AL), the cyclic group is 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane -2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, thiophene-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6 -Diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydro Naphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9 , 10a-octahyd Phenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b ′] dithiophene-2,6-diyl group, benzo [1,2-b: 4, 5-b '] Diselenophene-2, 6-diyl group, [1] benzothieno [3, 2-b] thiophene-2, 7-diyl group, [1] benzoselenopheno [3, 2- b] selenophen-2 It is preferable to represent one structure selected from the group consisting of 7, 7-diyl group and fluorene-2, 7-diyl group, and these structures may be unsubstituted or substituted, 1,4-phenylene Group, 1,4-cyclohexylene group, 2,6-naphthylene group or phenanthrene-2,7-diyl group is more preferable, and 1,4-phenylene group or 1,4-cyclohexylene group is preferable. In addition, one or more hydrogen atoms in the cyclic group may be substituted with a halogen atom, an adsorptive group, P ¹¹ -S ¹¹ -or a monovalent organic group.

In general formula (AL), a monovalent organic group is a group having a chemical structure constituted by the organic compound being in the form of a monovalent group, and is formed by removing one hydrogen atom from the organic compound. And 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 alkenyloxy group having 2 to 15 carbon atoms, etc. Preferred is an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms. In addition, one or two or more non-adjacent —CH ₂ — in the alkyl group, the alkenyl group, the alkoxy group and the alkenyloxy group may be substituted by —O—, —COO— or —OCO—. Furthermore, the monovalent organic group may have a role as a bending group described later.

In the above general formula (AL), m ^AL is preferably an integer of 2 to 4.

Examples of the preferred form of the mesogen group include the following formulas (me-1) to (me-42). General formula (AL) is a structure where two hydrogen atoms in these structures are eliminated.

These formulas (me-1) ~ (me -44) in the cyclohexane ring, one or more hydrogen atoms of the benzene ring or in naphthalene ring, a halogen ^atom, P 11 ^{-S 11} -, 1 monovalent organic It may be substituted by a group (eg, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorptive group or a bending group.

Among the above mesogenic groups, preferred forms are formulas (me-8) to (me-44), and more preferably formulas (me-8) to (me-10) and formulas (me-12) to (me) -18), formulas (me-22) to (me-24), formulas (me-26) to (me-27) and formulas (me-29) to (me-44), and more preferably (Me-12), (me-15) to (me-16), (me-22) to (me-24), (me-29), (me-34), (me-36) to (me -37), (me-42) to (me-44).

Among the above mesogen groups, a particularly preferred form is represented by the following general formula (AL-1) or (AL-2), and formula (AL-2) is more preferable.

(In the ^{formula, X a11 ~} X ^al18 are each independently a hydrogen atom, a halogen ^atom, P 11 ^{-S 11} -, represents an adsorption group or bend group, ring A and ring B are each independently a cyclohexane ring Or a benzene ring,
One or more of X ^a11 to X ^al 18 are substituted with the above-mentioned adsorptive group,
One or more of X ^a11 to X ^al 18 are substituted with the above-mentioned bending group,
The adsorptive group and the bending group wherein P ^{11 -S} 11 ^- may be substituted with,
Having one or more - formula (AL-1) or the each of the general formulas ^{(AL-2) P 11 -S} 11. )
In the above formula (AL-1), it is preferable that at least one or more of X ^a11 or X ^a18 to X ^a112 be substituted with an adsorptive group, and at least one or more of X ^a11 or X ^a110 Is more preferably substituted by an adsorptive group. In this case, the suction group ^P 11 ^{-S 11} - may be substituted for. In particular, when ring A is a cyclohexane ring, it is preferable that X ^a110 be substituted with an adsorptive group.

In the above formulas ^(AL-1), X ^a16 preferably more than at least one or two ^{~ X a114} is substituted with polymerizable ^{groups, X al9} or one of ^{X a111} is ^P 11 ^{-S 11} More preferably, it is substituted by-.

In the above formula (AL-1), it is preferable that at least one or more of X ^a11 to X ^a13 , X ^a6 to X ^a114 , and X ^a117 to X ^a118 be substituted with a bending group, and X ^a11 to X ^{a13, X a6 ~ X a19,} X a111 or at least one or two ^{~ X a114} or ^X a117 ^{~ X a118} it is preferably substituted in the bending group. More preferably, X ^a11 is substituted with a bending group, and any one of X ^a6 to X ^a19 or X ^a111 to X ^a114 is substituted with a bending group. In this case, it is more preferable that the number of carbon atoms in the former X ^a11 is larger than that in the latter X ^a11 . Bending group ^P 11 ^{-S 11} - may be substituted for.

In the above formula ^(AL-2), it is preferable that more than at least one or two of ^{X a11} or ^X a16 ^{~ X a110} is replaced by a suction ^{group, X a11} or ^{X a18} is substituted with an adsorptive group Is more preferred. In this case, the adsorption group ^P 11 ^{-S 11} - may be substituted for. In particular, when ring A is a cyclohexane ring, X ^a18 is preferably substituted with an adsorptive group.

In the above formula ^(AL-2), or any one or two of ^X al6 ^~ X ^a110 is ^P 11 ^{-S 11} - is preferably substituted in ^either one of ^{X AL7} or ^{X a19} is P ¹¹ -S ¹¹ - it is more preferably substituted on.

In the above formula ^(AL-2), or at least one or two of ^{X a16 ~} X ^a110 is ^P 11 ^{-S 11} - is preferably substituted in ^either one of ^{X a17} or ^{X a14} is ^{P 11} -S ¹¹ - it is more preferably substituted on.

In the above formula (AL-2), it is preferable that at least one or more of X ^a11 to X ^a17 or X ^a9 to X ^a114 be substituted with a bending group, and X ^a11 , X ^a4 to X ^a17 or X It is preferable that at least one or more of ^a19 to ^Xa112 be substituted with a bending group. X ^a11 has been substituted with a bending group, and it is more preferable that any one of ^{X al4 ~ X a17} or ^X a19 ^{~ X a112} is replaced by a bending group. In this case, it is more preferable that the number of carbon atoms in the former X ^a11 is larger than that in the latter X ^a11 . Bending group ^P 11 ^{-S 11} - may be substituted for.

"Adsorption group"
The adsorbing group according to the present invention is a group having a function of adsorbing to an adsorbent such as a substrate, a film, an electrode and the like. Adsorption is generally separated into chemical adsorption in which a chemical bond (covalent bond, ionic bond or metal bond) is formed to be adsorbed between an adsorbent and an adsorbate, or physical adsorption other than the chemical adsorption. The adsorption of the paper may be either chemical adsorption or physical adsorption, but it is preferable to adsorb with the adsorbent by physical adsorption. Therefore, the adsorptive group according to the present invention is preferably a group capable of physically adsorbing to the adsorbent, and the adsorptive group is more preferably bonded to the adsorbent by an intermolecular force. As a form couple | bonded with an adsorbent by the said intermolecular force, it has couple | bonded with the adsorbent by interaction, such as a permanent dipole, a permanent quadrupole, a dispersive power, a charge transfer force, or a hydrogen bond. As a preferable form of the adsorption group which concerns on this invention, the form which can couple | bond with an adsorbent by a hydrogen bond is mentioned. In this case, the adsorptive group according to the present invention may be a donor or acceptor of a proton that mediates a hydrogen bond, or both.

The adsorptive group according to the present invention is preferably a group containing a polar element having an atomic group in which a carbon atom and a hetero atom are linked. The polar element as used herein means an atomic group in which a carbon atom and a hetero atom are directly linked. The hetero atom is preferably at least one selected from the group consisting of N, O, S, P, B and Si, and is at least one selected from the group consisting of N, O and S. Is preferable, and at least one selected from the group consisting of N and O is preferable, and O is preferable.

In the spontaneously orienting monomer according to the present invention, the valence of the polar element according to the present invention is not particularly limited, such as monovalent, divalent or trivalent, and the number of polar elements in the adsorptive group is also particularly limited. There is nothing to do.

In the spontaneously orienting monomer according to the present invention, the number of the adsorption groups is preferably 1 to 8 in one molecule, more preferably 1 to 4 and still more preferably 1 to 3.

The adsorptive group according to the present invention excludes P ¹¹ -S ¹¹ -and a bending group.

The adsorptive group according to the present invention contains one or more polar elements, and the adsorptive group is roughly classified into cyclic group type and chain group type. A cyclic group type is a form that includes a cyclic group with a cyclic structure that includes a polar element in its structure, and a chain group type includes a cyclic group that includes a cyclic structure that includes a polar element in its structure. There is no form. The chain group is a form having a polar element in a linear or branched chain group, and a part thereof may have a cyclic structure not containing a polar element.

The form in which the adsorptive group according to the present invention contains a cyclic group means a form in which at least one polar element is contained in a cyclic atomic arrangement. The cyclic group in the present specification is as described above. Therefore, in the case where the adsorptive group according to the present invention contains a cyclic group, it only needs to contain a cyclic group containing a polar element, and the entire adsorptive group may be branched or linear. .

The adsorptive group according to the present invention is in the form of a chain group in that there is no cyclic atomic arrangement containing polar elements in the molecule, and at least one polar element can be linear (possibly branched) It means the form included. The term “chain group” as used herein refers to an atomic group in which structural atoms have no linear atomic arrangement in the structural formula and in which the constituting atoms are linearly (or may be branched) bonded, and an acyclic group. . In other words, it refers to a linear or branched aliphatic group, which may contain either a saturated bond or an unsaturated bond, including, for example, alkyl, alkenyl, alkoxy, ester, ether or ketone, etc., at least one It is a concept which may be substituted by a substituent (reactive functional group (vinyl group, acryl group, methacryl group, etc.), chain organic group (alkyl, cyano, etc.). It may be linear or branched.

The adsorptive group according to the present invention preferably has a chain group or a cyclic group. When importance is attached to the adsorptivity, a chain group is preferable, and a cyclic group is preferable from the viewpoint of the stability to the liquid crystal composition.

When the adsorptive group according to the present invention is a cyclic group, it has a heteroaromatic group having 3 to 20 carbon atoms (including a fused ring) or a heteroaliphatic group having 3 to 20 carbon atoms (including a fused ring) Is more preferable, a C 3-12 heteroaromatic group (including a fused ring) or a C 3-12 heteroaliphatic group (including a fused ring) is more preferable, and a 5-membered ring complex is more preferable. More preferably, it represents an aromatic group, a 5-membered ring heteroaliphatic group, a 6-membered ring heteroaromatic group or a 6-membered ring heteroaliphatic group, and the hydrogen atom in these ring structures is a halogen atom, the number of carbon atoms It may be substituted by 1 to 5 linear or branched alkyl groups or alkyloxy groups.

When the adsorptive group according to the present invention is a chain group, it is preferable that a hydrogen atom or -CH ₂ -in a linear or branched alkyl group having 1 to 20 carbon atoms be substituted by a polar element , One or two or more non-adjacent -CH _2- in the alkyl group are -CH = CH-, -C≡C-, -O-, -CO-, -COO-, -OCO- Or -OCO-COO- may be substituted. In the case where the adsorptive group according to the present invention is a chain group, it is preferable that the end portion contains a polar element or contains two or more polar elements.

The hydrogen atom of the adsorptive group according to the present invention may be substituted by a polymerizable group.

Specifically, the type of polar element according to the present invention includes an oxygen atom-containing polar element (hereinafter, oxygen-containing polar element), a nitrogen atom-containing polar element (hereinafter, nitrogen-containing polar element), and a phosphorus atom Element (hereinafter, phosphorus-containing polar element), polar element including boron atom (hereinafter, boron-containing polar element), polar element including silicon atom (hereinafter, silicon-containing polar element) or polar element including sulfur atom (hereinafter, including It is preferable that it is a partial structure represented by (sulfur polar element), and from the viewpoint of adsorption capacity, nitrogen-containing polar element, nitrogen-containing polar element or oxygen-containing polar element is more preferable, and oxygen-containing polar element is even more preferable.

Examples of the oxygen-containing polar elements, a hydroxyl group (-OH), alkylol group ^{(-R t} -OH; ^R t is an alkylene group), an alkoxy group (-OR; where, R represents an alkyl group), a formyl group (-CHO ), carboxyl (-COOH), an ether group ^{(-R t} oR t '-; ^however, R t, ^{R t'} represents an alkylene group or alkenylene group), carbonyl group ^{(-R t -C (= O)} -R ^t '-; ^however, R t, ^{R t'} represents an alkylene group or alkenylene group), a carbonate group (-O-C (= O) -O-) and ester groups (-COOR ^t '-; where ^{R t'} is It is preferred that at least one group selected from the group consisting of an alkylene group or an alkenylene group) or a group in which the group is linked to a carbon atom.

As the nitrogen-containing polar elements, cyano group (-CN), primary amino group (-NH ₂ ), secondary amino group (-NH-), tertiary amino group (-NRR '; however, R, R' Is at least one group selected from the group consisting of an alkyl group), pyridyl group, carbamoyl group (-CONH ₂ ) and ureido group (-NHCONH ₂ ), or a group in which the group is linked to a carbon atom Is preferred.

The phosphorus-containing polar element is at least selected from the group consisting of phosphinyl group (-CX ₂ -P (= O) H ₂ ) and phosphoric acid group (-CX ₂ -OP (= O) (OH) ₂ ). It is preferable that one group or a group in which the group is linked to a carbon atom.

The boron-containing polar element is preferably a group in which a boric acid group (—B (OH) ₂ ) is linked to a carbon atom.

As the silicon-containing polar element, -Si (OH) ₃ group or -Si (OR) (OR ') (OR''); provided that R, R' and R '' are alkyl groups, and the carbon atom is It is preferable that it is a connected group.

As the sulfur-containing polar elements, a mercapto group (-SH), sulfide groups (-S-), sulfinyl group (-S (= O) -) , a sulfonyl group _(-SO 2 -), sulfonamide group (-SO ₂ NH ₂ ), at least one group selected from the group consisting of a sulfonic acid group (—SO ₃ H) and a sulfino group (—S (= O) OH) or a group in which the group is linked to a carbon atom Is preferred.

Therefore, the adsorptive group according to the present invention is a group in which the cyclic group has an oxygen-containing polar element (hereinafter, an oxygen-containing cyclic group) and a group in which the cyclic group has a nitrogen atom polar element (hereinafter, a nitrogen-containing ring Formula group), a group in which the cyclic group has a phosphorus-containing polar element (hereinafter referred to as a phosphorus-containing cyclic group), a group in which the cyclic group has a boron-containing polar element (hereinafter referred to as a boron-containing cyclic group), cyclic A group having a silicon-containing polar element (hereinafter, a silicon-containing cyclic group), a group having a sulfur group containing a sulfur-containing polar element (hereinafter, a sulfur-containing cyclic group), a chain group having an oxygen-containing polar element (Hereinafter referred to as an oxygen-containing chain group), a chain group includes a nitrogen atom polar element (hereinafter referred to as a nitrogen-containing chain group), and a chain group includes a phosphorus-containing polar element (hereinafter referred to as , A phosphorus-containing chain group), a group in which the chain group has a boron-containing polar element (hereinafter referred to as a boron-containing chain group), a group in which the chain group has a silicon-containing polar element (hereinafter, a silicon-containing chain group) And one or more groups selected from the group consisting of a group having a sulfur-containing polar element (hereinafter, a sulfur-containing chain group) itself or a chain group preferably includes the group itself or the group, and From the viewpoint, it is more preferable to include one or more groups selected from the group consisting of an oxygen-containing cyclic group, a sulfur-containing cyclic group, an oxygen-containing chain group and a nitrogen-containing chain group.

The above oxygen-containing cyclic group preferably has an ether group or a carbonyl group in the ring, and the ether group preferably contains the following groups.

The carbonyl group preferably contains any of the following groups.

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

The above sulfur-containing cyclic group preferably contains any of the following groups.

The above-mentioned boron-containing cyclic group preferably contains any of the following groups.

The silicon-containing cyclic group preferably contains a silsesquioxane group [-(R) _n (SiO _1.5 ) _n-1 ].

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

(In the general formula, R ^at each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In the formula, Z ^at a single bond, C 1 -C 15 straight Represents a linear or branched alkylene group or a linear or branched alkenylene group having 2 to 18 carbon atoms, and in the alkylene group or -CH ₂ -of the alkenylene group, an oxygen atom is not directly adjacent And X ^at may represent an alkyl group having 1 to 5 carbon atoms, and the alkyl group of the alkyl group may have -CH _2- , -CO-, -COO-, -C (= O)-, or -OCO-. -May be substituted by -O-, -COO-, -C (= O)-, -OCO- so that oxygen atoms are not directly adjacent to each other.)
The above-mentioned nitrogen-containing chain group preferably contains the following groups.

(In the above general 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.)
The above-mentioned sulfur-containing chain group preferably contains the following groups.

The silicon-containing chain group preferably contains —Si (OH) ₃ or —Si (OR) (OR ′) (OR ′ ′), provided that R, R ′, R ′ ′ is an alkyl group). . The boron-containing chain group preferably contains -B (OH) ₂ . The above-mentioned phosphorus-containing chain group preferably contains -OP (= O) (OH) ₂ .

As the adsorptive group according to the present invention, a group represented by the following general formula (T) is preferable.

(In the above general formula (T), X ^t1 represents a linear or branched alkyl group having 1 to 18 carbon atoms or -NH _2, and the hydrogen atom in the alkyl group is a cyano group, P ¹¹ -S ¹¹ -may be substituted, or -CH _{2-of the} alkyl group is -O-, -COO-, -C (= O)-, -OCO-,-so that the oxygen atom is not directly adjacent. It may be substituted by CH = CH-,
The R ^t1 represents a hydrogen atom, and a carbon atom number of 1 to 5 alkyl groups or Z ^t1 carbon atoms which may combine with one to eight linear or branched alkylene group or Z ^t1 R 2 represents a linear or branched alkenylene group having 2 to 8 carbon atoms, and Z ^t2 represents a single bond, a linear or branched alkylene group having 1 to 18 carbon atoms, or carbon A linear or branched alkenylene group having 2 to 18 atoms is represented, and the alkylene group or -CH _{2-of the} alkenylene group is -O-, -COO-, -C so that the oxygen atom is not directly adjacent. (= O)-, -OCO- may be substituted,
Z ^t1 represents a single bond, a linear or branched alkylene group having 1 to 18 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms, and CH ₂ -may be substituted by -O-, -COO-, -C (= O)-, -OCO- so that the oxygen atom is not directly adjacent, and X ^t1 is -Z ^t2 -O-R ^at And when R ^at is an alkylene group or an alkenylene group, the hydrogen atom of Z ^t1 may be substituted and R ^t1 may be bonded to R ^t1, and W ^t0 is a linear or branched C ^1-18 C atom And the —CH ₂ — of the alkylene group is —O—, —CH = CH—, —COO—, —C (= O) — or —OCO— such that the oxygen atom is not directly adjacent to it. And may be substituted, and also the hydrogen atom of the alkylene group It may be substituted in the general formula (T),
W ^t1 represents a single bond or a linear or branched alkylene group, and the —CH ₂ — of the alkylene group is —O—, —COO—, —C (= O) so that the oxygen atom is not directly adjacent. -, -OCO- may be substituted,
n ^t1 represents an integer of 0 or more and 4 or less,
Hydrogen atoms in the molecule of the polymerizable group P ^{11 -S} 11 ^- may be substituted by, * represents a bond, mesogenic group, the polymerizable group which bonds to bend group or spacer group. )
In the above general formula (T), preferable X ^t1 represents a linear or branched alkyl group having 1 to 17 carbon atoms, -NH ₂ or -Z ^t2 -O-R ^t1 group, and the alkyl group hydrogen atom a cyano group ^in, P 11 ^{-S 11} - may be substituted by the above ^{R t1} represents a hydrogen atom, a carbon atom bonded to an alkyl group or ^{Z t1} of 1 to 5 carbon atoms 1 to represent the eight linear or branched alkylene group or Z ^t1 carbon atoms which may be coupled with 2 to 8 linear or branched alkenylene group, the Z ^t2 are single Represents a bond, a linear or branched alkylene group having 1 to 18 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms, and the alkylene group or —CH 2 of the corresponding alkenylene group ₂ - is directly adjacent oxygen atom Oddly -O -, - COO -, - C (= O) -, - OCO- may be substituted.

In the above general formula (T), as a form in which the adsorptive group (general formula (T)) may be substituted with the adsorptive group (general formula (T)), the above general formula (T) has the following general formula (t Groups represented by) are mentioned.

(In the above general formula (t), X ^t1 , Z ^t1 , W ^t1 and n ^t1 are the same as the symbols in the above general formula (T),
W ^t2 represents a single bond or a divalent to tetravalent organic group,
m ^t1 represents an integer of 1 to 3, hydrogen atoms in the molecule of the polymerizable group Pd-S 11 ^- may be substituted by, * represents a bond, mesogenic group, the polymerizable group, the bending group Or bond to a spacer group. )
“-W ^t2 -Any” in the general formula (t) indicates that W ^t2 represents a single bond to a multivalent group, and the bond is monovalent to multivalent (Any).

In the general formula (t), a divalent to tetravalent organic group is a group having a chemical structure constituted by the organic compound being in the form of a divalent to tetravalent group, and a hydrogen atom is selected from the organic compound. It refers to an atomic group formed by removing two to four.

In the above general formula (t), a divalent to tetravalent organic group -W ^t2 -Any is preferably a chain organic group, and, for example, a linear or branched C1 to C10 carbon atoms An alkylene group of (wherein —CH ₂ — of the alkylene group may be substituted with —O—, —COO—, —C (= O) —, —OCO— such that the oxygen atom is not directly adjacent), a straight chain Or branched alkylene group having 1 to 10 carbon atoms (the —CH ₂ — of the alkylene group is —O—, —COO—, —C (= O) so that oxygen atoms are not directly adjacent to each other) -, -OCO-), -PH-, -POH-, -NH-, a nitrogen atom or a phosphorus atom, etc. may be mentioned. The alkylene multivalent group is a trivalent or tetravalent group formed by removing one or two hydrogen atoms from the alkylene group, and a trivalent to tetravalent group having a free valence in a so-called hydrocarbon chain.

The group represented by the above general formula (t) is a preferred embodiment of W ^{t0 in} the general formula (T), that is, even though the adsorptive group (general formula (T)) is substituted by the adsorptive group (general formula (T)) This is one aspect of a good form, and as a preferable form of the group represented by the above general formula (t), for example, when W ^t2 is a trivalent organic group, that is, mt1 ′ is 2 and W ^t2 is nitrogen In the case of an atom or an alkylene polyvalent group, for example, the following general formula (ta) or (tb) may be mentioned.

(The formula (t-a) and in ^{(t-b), R tc} represents a hydrogen atom, a linear or branched carbon atoms 1 to 10 alkyl group or a polymerizable group ^P 11 ^{-S 11} - Represented by
Z ^t1 and Z ^{t1 ′} independently represent the same meaning as Z ^t1 in the general formula (T),
X ^t1 and X ^{t1 ′} each independently represent the same meaning as Z ^t1 in the general formula (T),
W ^t1 represents the same meaning as ^{W t1} in the general formula (T),
n ^t1 and n ^{t1 ′} independently represent the same meaning as n ^t1 in the general formula (T),
Hydrogen atoms in the molecule of the polymerizable group P ^{11 -S} 11 ^- may be substituted by, * represents a bond, mesogenic group, the polymerizable group which bonds to bend group or spacer group. )
In the general formula (t), for example, when -W ^t2 -Any is a tetravalent organic group, ie, mt1 'is 3, and -W ^t2 -Any is an alkylene multivalent group, for example, t-c).

(In the above formula (t-c), Z ^t1 , Z ^{t1 ′} and Z ^{t1 ′ ′} each independently represent the same meaning as Z ^t1 in the general formula (T),
X ^t1 , X ^{t1 ′} and X ^{t1 ′ ′} each independently represent the same meaning as X ^t1 in the general formula (T),
W ^t1 represents the same meaning as ^{W t1} in the general formula (T),
n ^{t1, n t1 'and n t1''each} independently represents the same meaning as ^{n t1} in the general formula (T), a hydrogen atom in the molecule of the polymerizable group ^P 11 ^{-S 11} - substituted And * represents a bond, which is bonded to a mesogen group, a polymerizable group, a bending group or a spacer group. )
In the above general formula (t), mt1 ′ is preferably 1 or 2, and mt1 ′ is more preferably 1. Further, among the embodiments represented by the above general formula (ta), general formula (tb) and general formula (tc), the embodiment represented by the above general formula (ta) is preferable .

In the above general formula (t), -W ^t2 -Any is preferably a single bond or a divalent to trivalent organic group, and is a single bond or a linear or branched alkylene group having 1 to 8 carbon atoms The —CH ₂ — of the alkylene group may be substituted by —O— so that the oxygen atom is not directly adjacent to it, a linear or branched alkanetriyl group having 1 to 8 carbon atoms The —CH ₂ — of the alkanetriyl group may be substituted by —O— so that the oxygen atom is not directly adjacent to it, or a linear or branched alkyl-ylidene group (—CH of the alkyl-ylidene group concerned) _2- is more preferably -O- such that the oxygen atom is not directly adjacent. For example, the following groups may be mentioned.

(In the ^{formula, R tc} represents an alkyl group or a polymerizable group of 1 to 8 carbon atoms ^{(P 11 -S} 11 -) represent, NT0 is an integer of 1-7, * a is a bond . represented) ^{Further, W} polymerizable group to a hydrogen atom of ^{t2 (P 11 -S} 11 -) may be substituted.

In the above general formula (t), mt1 preferably represents 1 or 2.

In the above general formula (T) or general formula (t), W ^t1 is a single bond or a linear or branched alkylene group having 1 to 8 carbon atoms (single bond or linear or branched alkylene And —CH ₂ — of the alkylene group represents —O—, —COO—, —C (= O) — or —OCO— such that oxygen atoms are not directly adjacent to each other. Is preferably a single bond or a linear or branched alkylene group having 1 to 7 carbon atoms (a single bond or a linear or branched alkylene group, and —CH ₂ — in the alkylene group is an oxygen More preferably, the atoms may be substituted with -O- so that they are not immediately adjacent. W ^t1 may be substituted for and bonded to a hydrogen atom of a mesogenic group, a polymerizable group or a bending group.

In the general formula (T) or the general formula (t), X ^t1 is a form not bound to Z ^t1 (chain group), and X ^t1 is a form (cyclic group) bound to Z ^t1 to form a ring Contains.

In the former form, it has 1 to 7 carbon atoms substituted with a linear or branched alkyl group having 1 to 8 carbon atoms, -NH ₂ , -Z ^t2 -O-R ^t1 group or cyano group. Linear or branched alkyl group is preferable, and a linear or branched alkyl group having 1 to 7 carbon atoms, a -Z ^t2 -O-R ^t1 group, or a carbon atom substituted with a cyano group The linear or branched alkyl group of 1 to 7 is more preferable. In the former embodiment, each R ^t1 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and the above Z ^t2 is a single bond or a straight chain having 1 to 10 carbon atoms. Linear or branched alkylene group or a linear or branched alkenylene group having 2 to 10 carbon atoms is preferable (as the alkylene group or —CH ₂ — of the alkenylene group is such that oxygen atoms are not directly adjacent to each other— O-, -COO-, -C (= O)-, -OCO- may be substituted).

In the latter form, nt1 is 1 or more, X ^t1 is -Z ^t2 -O-R ^t1 , and R ^t1 is a linear or branched alkylene group having 1 to 7 carbon atoms or 2 carbon atoms It is preferable that R 7 be a linear or branched alkenylene group and that a hydrogen atom of Z ^{t 1 be} substituted and be bonded to R ^{t 1} , for example, be represented by the following general formula (T ′) preferable.

In the above general formula (T ′), R ^{t1 ′} each independently represents a linear or branched alkylene group having 1 to 8 carbon atoms, or a linear or branched chain having 2 to 8 carbon atoms Represents an alkenylene group,
Z ^{t2 '} each independently represents a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, or a linear or branched alkenylene group having 2 to 10 carbon atoms, and the alkylene Or -CH _{2-of the} alkenylene group may be substituted with -O-, -COO-, -C (= O)-, -OCO- such that the oxygen atom is not directly adjacent to the group.
Z ^{t1 ′} represents a linear or branched alkylene trivalent group having 1 to 18 carbon atoms or a linear or branched alkenylene trivalent group having 1 to 18 carbon atoms, and the alkylene 3 And —CH ₂ — of the divalent group or the alkenylene trivalent group may be substituted by —O—, —COO—, —C (= O) — or OCO— such that the oxygen atom is not directly adjacent.
W ^t2 represents a single bond or a divalent to tetravalent organic group,
-W ^t1 -represents a single bond or a linear or branched alkylene group, and the -CH _{2-of the} alkylene group is -O-, -COO-, -C (= where the oxygen atom is not directly adjacent) O)-, -OCO- may be substituted,
n ^{t1 '} represents an integer of 1 or more and 4 or less,
m ^{t1 'represents} an integer of 1 to 3, hydrogen atoms in the molecule of the polymerizable group P ^{11 -S} 11 ^- may be substituted by, * represents a bond, mesogenic group, a polymerizable group, It bonds to a bending group or a spacer group. )
The said alkylene trivalent group means the trivalent group which can remove one hydrogen atom further from an alkylene group. The alkenylene trivalent group is a trivalent group obtained by further removing one hydrogen atom from an alkenylene group, a trivalent group having a free valence in a so-called hydrocarbon chain, such as an alkanetriyl group or an alkyl-ylidene group. Group etc.

In formula ^{(T), X t1} in the case of without being combined with ^{Z t1 (Kusarishikimoto), Z t1} is a single bond, C 1 -C 12 linear or branched alkylene group, or Represents a linear or branched alkenylene group having 2 to 12 carbon atoms, wherein -CH _{2-of the} alkylene group is substituted on -O-, -COO-, -C (= O)-, -OCO- It may be done.

In the case of a form (cyclic group) in which X ^t1 is bonded to Z ^t1 in the above general formula (T), it is as in the above general formula (T ′).

In the general formula (T), nt1 preferably represents an integer of 0 or more and 3 or less, and more preferably nt1 represents an integer of 0 or more and 2 or less.

The general formula (T) is a cyclic group represented by any one of the general formulas (T-1-1) to (T-4-1) and any one of the general formulas (T-5-1) to (T-7-1) It is preferable that it is at least one selected from the group consisting of a chain group represented by When the adsorptive group represented by the general formula (T) according to the present invention selects a cyclic group, the general formula (T-1-1) or the general formula T-2-1) is preferred. When the adsorptive group represented by the general formula (T) according to the present invention selects a chain group, the general formula (T-5-1) or the general formula T-6-1) is preferred.

(In the above general formulas (T-1-1) to (T-7-1), X ^a and X ^b each independently represent -O-, -S- or CH _2- ,
R ^t5 represents a linear or branched alkyl group having 1 to 8 carbon atoms, a cyanated alkyl group, or a linear or branched alkoxy group having 1 to 8 carbon atoms, and these alkyls At least two or more -CH _2- in the group may be substituted with -CH = CH-, -C≡C-, -O- or -NH- such that the oxygen atom is not directly adjacent.
Z ^t3 represents a single bond, a linear or branched alkylene group having 1 to 18 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms, and the alkylene group or the corresponding alkylene group -CH _{2-of the} alkenylene group may be substituted by -O-, -COO-, -C (= O)-or -OCO- so that the oxygen atom is not directly adjacent.
W ^t2 represents a single bond or a monovalent to tetravalent organic group,
W ^t1 represents a single bond or a linear or branched alkylene group,
n ^t1 represents an integer of 0 or more and 4 or less,
mt1 represents an integer of 1 to 3, hydrogen atoms in the molecule of the polymerizable group P ^{11 -S} 11 ^- may be substituted by, * represents a bond, mesogenic group, the polymerizable group, the bending group Or bond to a spacer group. )
In the above general formulas (T-1-1) to (T-4-1), it is preferable that either X ^ta or X ^tb be —O—, and X ^ta and X ^tb be —O— Is more preferred.

Specific examples of the general formulas (T-1-1) to (T-4-1) include the following groups.

(In the ^{formula, R tc} represents a hydrogen atom, C 1 -C 7 alkyl group or a polymerizable group ^P 11 ^{-S 11} - represented by a hydrogen atom in the molecule of the polymerizable group ^P 11 -S ¹¹ -may be substituted, and * represents a bond, which is bonded to a mesogenic group, a polymerizable group, a bending group or a spacer group.)
It is preferable that the general formula (T-5-1) represents the general formula (T-5-2).

(In the general formula ^{(T-5-2), W t1} represents the same meaning as ^{W t1} in the general formula ^{(T-5), R t51} and ^{R t52} are each independently, carbon atoms of 1 to Eight linear or branched alkyl groups or cyanated alkyl groups are represented, and at least two or more of —CH ₂ — in these alkyl groups are —CH = CH— such that oxygen atoms are not directly adjacent to each other. , -C≡C -, - O-, or -NH- may be substituted ^{with, R tc} represents a hydrogen atom, an alkyl group or a polymerizable group of 1 to 7 carbon atoms ^P 11 ^{-S 11} - in ^represented, n ^{t1, n t2} and ^{n t3} each independently represents 0 or 1, the hydrogen atom in the molecule ^P 11 ^{-S 11} - may be substituted for).
Specific examples of the above general formula (T-5-1) include the following groups.

(In the ^{formula, R tc} represents a hydrogen atom, C 1 -C 7 alkyl group or a polymerizable group ^P 11 ^{-S 11} - represented by a hydrogen atom in the molecule of the polymerizable group ^P 11 -S ¹¹ -may be substituted, and * represents a bond, which is bonded to a mesogenic group, a polymerizable group, a bending group or a spacer group.)

(In the ^{formula, R tc} represents a hydrogen atom, C 1 -C 7 alkyl group or a polymerizable group ^P 11 ^{-S 11} - represented by a hydrogen atom in the molecule of the polymerizable group ^P 11 -S ¹¹ may be substituted) (* represents a bond, and is bonded to a mesogen group, a polymerizable group, a bending group or a spacer group)
The following examples may be mentioned as specific examples of the above general formula (T-6-1).

(In the formula, ^{R c} is a hydrogen atom, C 1 -C 7 alkyl group or a polymerizable group ^P 11 ^{-S 11} - represented by a hydrogen atom in the molecule of the polymerizable group ^P 11 -S ¹¹ -may be substituted, and * represents a bond, which is bonded to a mesogenic group, a polymerizable group, a bending group or a spacer group.)
The following examples may be mentioned as specific examples of the above general formula (T-7-1).

(In the formula, ^{R c} is a hydrogen atom, C 1 -C 7 alkyl group or a polymerizable group ^P 11 ^{-S 11} - represented by a hydrogen atom in the molecule of the polymerizable group ^P 11 -S ¹¹ -may be substituted, and * represents a bond, which is bonded to a mesogenic group, a polymerizable group, a bending group or a spacer group.)
In the spontaneous orientation monomer according to the present invention, a mode in which the polar element contained in the adsorptive group or the polar element contained in the polymerizable group is localized is preferable. The adsorptive group is an important structure for vertically aligning the liquid crystal composition, and by the adsorptive group and the polymerizable group being adjacent to each other, better alignment can be obtained, and good to the liquid crystal composition can be obtained. It shows solubility. Specifically, a form having a polymerizable group and an adsorptive group on the same ring of the mesogen group is preferable. In this case, one or more polymerizable groups and one or more adsorptive groups are bonded to the same ring, respectively, and at least one of at least one or more adsorptive groups of one or more polymerizable groups, It includes a form in which one is bonded to the other and has a polymerizable group and an adsorptive group on the same ring. Moreover, in this case, the hydrogen atom of the spacer group (S ¹¹ ) of the polymerizable group may be substituted with the adsorptive group, and further, the hydrogen atom of the molecule of the adsorptive group is the spacer group (S ¹¹ ) of the polymerizable group It also includes the form of bonding.

In the spontaneously orienting monomer according to the present invention, at least one hydrogen atom of the polymerizable group may be substituted by an adsorptive group. A preferable form in this case is a form in which at least one hydrogen atom of the polymerization group P ¹¹ or a spacer group (S ¹¹ ) optionally linked to the polymerization group is substituted by an adsorptive group, and a more preferable form the polymerizable group (P ^{11 -S 11 -)} 1 or more hydrogen atoms in the include forms have been replaced by adsorptive group represented by the general formula (T).

For example, as a suitable form in which an adsorptive group and a polymerizable group are linked, the following formula (T-1-1.1), (T-6-1.1) or (T-5-1.1) Can be mentioned.

In the above formulae, R ^t11a , R ^t16a and R ^t151a each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ^{t151 b} and R ^{t151 c} each independently have 1 to carbon atoms 3 alkyl group, cyanated alkyl group having 1 to 3 carbon atoms,
X ^a and X ^b represent -O-, -S- or CH _2- ,
L ^t151a and L ^{t151 b} each independently represent a single bond, a methylene group, an ethylene group, a propylene group, a vinylidene group, a vinylene group, an isopropenylene group or an ethylidene group,
n ^{t11 c} , ^{nt 151 c} , ^{nt 16 c} , ^{nt 151 d} , ^{nt 151 e} , ^{nt 151 f} and ^{nt 151 g} each independently represent 0 or 1, and ^{nt 11 a} , ^{nt 11 b} , ^{nt 16 a} , ^{nt 16 b} , ^{nt 151 a} and ^{nt 151 b} Each of them independently represents an integer of 1 to 11, and * represents a bond to a mesogenic group. )
In the above formula (T-1-1.1), one of X ^{a and} X ^b is preferably -O-, and more preferably, X ^ta and X ^tb are -O-.

In the above formula (T-5-1.1), L ^t151a and L ^t151a are each independently ^preferably a methylene group, an ethylene group, a vinylidene group, a vinylene group, an ^{isopropenylene} group or an ethylidene group.

In the above formulas (T-1-1.1), (T-6-1.1) and (T-5-1.1),
^{Each of} n ^t11a , n ^t11b , n ^t16a , n ^t16b , n ^{t151 a} and n ^{t151 b} is preferably an integer of 1 to 8, and more preferably an integer of 1 to 5.

"Flexural basis"
The bending group according to the present invention has a function of inducing the alignment of liquid crystal molecules, and preferably represents a linear or branched alkylene group having 1 to 20 carbon atoms, and a linear carbon atom It is more preferable to represent an alkylene group of the number 1 to 20, and more preferable to represent a linear alkylene group having 2 to 15 carbon atoms. In addition, one or two or more non-adjacent -CH _2- in the alkylene group are each independently -CH = CH-, -C≡C-, -O-, -CO-,- It may be substituted by COO- or -OCO-.

It is preferable that the above-mentioned bending group is bonded to a mesogen group from the viewpoint that the spontaneous alignment monomer has a so-called amphiphilic property to the liquid crystal layer.

In the spontaneously orienting monomer according to the present invention, the number of the above-mentioned bending groups is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 3.

The spontaneous orientation compound according to the present invention is preferably a compound represented by the following general formula (SAL).

(Table in the general formula ^(SAL), -Sp ^{al -P} al represents a polymerizable group, T is represents an adsorptive group represented by the general formula (T), MG is the general formula (AL) It represents a mesogenic group that is, Cg is a hydrogen atom, an adsorptive group represented by the above general formula (T), the polymerizable group is a -Sp ^al -P ^al or a linear or branched carbon atoms as the bending group And represents one or more alkylene groups, and one or two or more non-adjacent —CH ₂ — in the alkylene group are each independently —CH = CH—, —C≡C—, — O -, - CO -, - COO- or -OCO- may be substituted by, Cg, any of MG and T may be substituted by ^-Sp al ^{-P al} is the polymerizable group,
n ^sal1 , n ^sal2 and nsal3 each independently represent a natural number of 1 to 5. )
(Wherein P ^al represents a group represented by general formula (PI) to general formula (P-IX)

(Wherein, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, and W ^p11 is a single bond, —O -, -COO- or a methylene group, and t ^p11 represents 0, 1 or 2.)
Represents a group represented by
Sp ^al is a single bond or a linear or branched alkylene group having a carbon atom number of 1 to 20, two or more -CH 2 that is not one or adjacent in the alkylene group _- are each independently And may be substituted by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-,
T represents an adsorptive group,
MG represents a mesogenic group,
Cg represents a hydrogen atom, the suction group, an alkylene group of the -Sp ^al -P ^al or a linear or branched having 1 to 20 carbon atoms, 2 which is not one or adjacent in the alkylene group Each of the above -CH ₂ -may be independently substituted by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-; ^-Sp al ^{-P al} all at the polymerizable groups of MG and T - may be substituted by,
n ^sal1 , n ^sal2 and nsal3 each independently represent a natural number of 1 to 5. )
The preferred spontaneously orienting monomer according to the present invention is preferably at least one selected from the group consisting of the following general formulas (al-1) to (al-3).

( ^Wherein , R ^al1 , R ^al2 , Z ^al1 , Z ^al2 , L ^al1 , L ^al2 , L ^al3 , L ^al4 , Sp ¹¹¹ , Sp ¹¹² , Sp ¹¹³ , Sp ¹¹⁴ , P ¹¹¹ , P ¹¹² , P ¹¹³ , P ^{113 114} , ^{mal 1} , ^{mal 2} , ^{mal 3} , ^{mal 4} , n ^{al 1} , n ^{al 2} , n ^{al 3} , n ^{al 4} , P ¹¹¹ and P ¹¹² are each independently of each other
R ^al1 represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 20 carbon atoms, and one or more -CH ₂ -or two or more not adjacent to each other in the alkyl group. And -CH _2- may be substituted with -O-, -OCO- or COO-, such that the oxygen atom is not directly adjacent.
R ^al2, said polymerizable group ^P 11 ^{-S 11} - represents optionally substituted adsorbing group, preferably, the polymerization group ^P 11 ^{-S 11} - Table at by even better above general formula substituted in (T) R ^al2 is at least one selected from the group consisting of general formulas (T-1-1) to (T-7-1), more preferably general formula At least one selected from the group consisting of (T-1-1), (T-2-1), (T-5-1), and (T-6-1),
Still more preferably, it is at least one selected from the group consisting of formulas (T-1-1.1), (T-6-1.1) and (T-5-1.1),
Rings A ^al1 and A ^al2 each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a 2,6-naphthylene group or a phenanthrene-2,7-diyl group,
Sp ¹¹¹ , Sp ¹¹² and Sp ¹¹³ each independently represent an alkylene group having 1 to 12 carbon atoms or a single bond, and one —CH ₂ — or _two non-adjacent ones in the alkylene group The above -CH _2- may be substituted with -O-, -OCO- or COO- so that the oxygen atom is not directly adjacent.
P ¹¹¹ , P ¹¹² , P ¹¹³ and P ¹¹⁴ each independently represent an acryl group or a methacryl group;
Z ^al1 and Z ^al2 are each independently a single bond, -O-, -CO-, ^{-CO-O-, -OCO-} , -O-CO-O-, -OCH _2- , -CH ₂ O -, -CF ₂ O-, -OCF ₂ -,-(CH ₂ ) _n ^al- , -CF ₂ CH _2- , -CH ₂ CF ₂ -,-(CF ₂ ) _n ^al- , -CH = CH- And -CF = CF-, -C≡C-, -CH = CH-COO- or OCO-CH = CH-, and the above n ^al represents an integer of 1 to 4,
L ^al1 , L ^al2 , L ^al3 and L ^al4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, or R ^al2 Here, one or more hydrogen atoms of the alkyl group may be replaced by halogen atoms,
P ¹¹¹ and P ¹¹² each independently represent 0 or 1, and ^mal 1, ^{mal 2} , ^{mal 3} and ^mal 4 each independently represent an integer of 0 to 3, and n ^{al 1} , n ^{al 2} , n ^al3 and n ^al4 each independently represent an integer of 0 to 3. )
General formula (al-2):

( ^Wherein , Z ^ad1 and Z ^ad2 are each independently a single bond, -CH = CH-, -CF = CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -OOCO _{-, - 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 C 2 -C And 20 or more alkylene groups, and one or two or more non-adjacent -CH _2- in the alkylene group may be substituted with -O-, -COO- or -OCO-,
A ^ad1 and Aa ^ad2 each independently represents a divalent 6-membered ring aromatic group or a divalent 6-membered ring aliphatic group, a divalent unsubstituted 6-membered ring aromatic group, a divalent The unsubstituted 6-membered aliphatic group or a hydrogen atom in these ring structures is substituted with an unsubstituted alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom. Preferably, a divalent unsubstituted 6-membered ring aromatic group or a group in which a hydrogen atom in this ring structure is substituted with a fluorine atom, or a divalent unsubstituted 6-membered ring aliphatic group Preferably, the hydrogen atom on the substituent is a halogen atom, an 1,4-phenylene group optionally substituted by an alkyl group or an alkoxy group, a 2,6-naphthalene group or a 1,4-cyclohexyl group, but at least one of the substituents is ^P 11 ^{-S 11} - It has been replaced,
If Z ^{ad1, A ad1} and ^{Aa ad2} is present in plural may each also being the same or different,
R ^ad1 is a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group, or ^P 11 ^{-S 11} - represents, -CH ₂ in the alkyl group - is, -O -, -OCO-, or -COO- is preferable (however, -O- is not continuous), more preferably a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or P ^11- And represents —S ¹¹ —, and —CH ₂ — in the alkyl group represents —O—, —OCO— such that oxygen atoms are not directly adjacent to each other.

Ab ^ad1, said polymerizable group ^P 11 ^{-S 11} - represents optionally substituted adsorbing group, preferably, the polymerization group ^P 11 ^{-S 11} - Table at by even better above general formula substituted in (T) R ^al2 is at least one selected from the group consisting of general formulas (T-1-1) to (T-7-1), more preferably general formula At least one selected from the group consisting of (T-1-1), (T-2-1), (T-5-1), and (T-6-1),
Still more preferably, it is at least one selected from the group consisting of formulas (T-1-1.1), (T-6-1.1) and (T-5-1.1),
P ¹¹ -S ^11- represents the above polymerizable group,
When a ^{plurality of} Z ^ad1 , Z ^ad2 , A ^ad1 , ^{mad 1} and / or A ^ad2 are present, they may be identical to or different from each other, provided that any one of A ^ad1 and A ^ad2 is at least one One P ¹¹ -S ¹¹ -is replaced by
^mad1 represents an integer of 1 to 5 and
^mad2 represents an integer of 1 to 5 and
G ^ad1 represents a divalent, trivalent or tetravalent branched structure, or a divalent, trivalent or tetravalent aliphatic or aromatic ring structure,
^mad3 represents an integer smaller by one than the valence of ^Gad1 . )
General formula (al-3);

(In the above general formula (al-3), R ^al31 represents an alkyl group having 1 to 15 carbon atoms, and in the alkyl group, one or two or more non-adjacent —CH ₂ — groups are —O— And —S—, —CH = CH— or C≡C—, and in these groups, at least one hydrogen atom may be substituted by a halogen atom,
A ^{al 31} and A ^{al 34} each independently represent 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl or phenanthrene-2,7-diyl, and at least one of these rings is at least one And each hydrogen atom is a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms In these groups, at least one hydrogen atom may be substituted with a fluorine atom or a chlorine atom,
Z ^al31 represents a single bond or alkylene having 1 to 10 carbon atoms, and in the alkylene group, one or two or more non-adjacent -CH ₂ -are -O-, -S-, -CH = CH -Or C≡C-, and in these groups, at least one hydrogen atom may be substituted by a halogen atom,
^{Sal 31} represents a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, one or two or more non-adjacent -CH ₂ -are -O-, -S-, -CH = It may be substituted by CH- or C≡C-, and in these groups, at least one hydrogen atom may be substituted by a halogen atom,
^Each of K ^al31 and K ^al32 independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or one carbon atom having at least one hydrogen atom substituted by a halogen atom (eg, a fluorine atom) Represents an alkyl group of 5,
n ^{al 31} is an integer represented by 0 to 4,
R ^al32 is a group represented by formula (al3-1) or formula (al3-2),

In the formula (al3-1) and the formula (al3-2),
S ^{al 32} and S ^{al 33} each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, one or two or more non-adjacent —CH ₂ — are —O—, -S-, -CH = CH- or C≡C- may be substituted, and in these groups, at least one hydrogen atom may be substituted by a halogen atom,
^{Sal 31} is = CH- or = N-,
X ^al31 is —OH, —NH ₂ , —OR ³ , —N (R ³ ) ₂ , a formula (X ^{al 31} ), —COOH, —SH, —B (OH) ₂ , or —Si (R ³ ) ₃ And R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and one or two or more non-adjacent —CH ₂ — groups in the alkyl group are -O-, -S-, -CH = CH- or C≡C- may be substituted, and in these groups, at least one hydrogen atom may be substituted with a halogen atom,
Formula (X ^al31 ):

(N ^{al 32} is an integer of 1 to 5)
In the above-mentioned spontaneously orienting monomer, the polar portion such as an adsorptive group or a polymerizable group which is not compatible with the liquid crystal layer and the nonpolar portion such as a mesogen group or a bending group which is easily compatible with the liquid crystal layer are segregated in the molecule. Is preferable, and it is preferable to exhibit amphiphilicity to a so-called liquid crystal layer. Therefore, it is preferable that the spontaneous orientation monomer according to the present invention has a bending group for aligning liquid crystal molecules at one end of the mesogenic group, and a structure having a polymerizable group and an adsorptive group at the other end of the mesogenic group. . Since the interface free energy is high in the vicinity of the interface between the liquid crystal layer and the substrate, a substance having in one molecule a nonpolar portion having an affinity for the liquid crystal layer and a polar portion having a low affinity for the liquid crystal layer Is considered to lower the interface free energy by being aligned on the interface.

The lower limit of the content of the spontaneous orientation monomer in the liquid crystal composition of the present invention is preferably 0.02% by mass, preferably 0.03% by mass, preferably 0.04% by mass, and more preferably 0.05% by mass. 0.06 mass% is preferable, 0.07 mass% is preferable, 0.08 mass% is preferable, 0.09 mass% is preferable, 0.1 mass% is preferable, 0.12 mass% is preferable, 0. 15 mass% is preferable, 0.17 mass% is preferable, 0.2 mass% is preferable, 0.22 mass% is preferable, 0.25 mass% is preferable, 0.27 mass% is preferable, 0.3 mass % Is preferable, 0.32% by mass is preferable, 0.35% by mass is preferable, 0.37% by mass is preferable, 0.4% by mass is preferable, 0.42% by mass is preferable, and 0.45% by mass is Preferably 0.5 mass% Preferably, preferably 0.55% by mass. The upper limit of the content of the polymerizable monomer represented by the general formula (I) in the liquid crystal composition of the present invention is preferably 2.5% by mass, preferably 2.3% by mass, and preferably 2.1% by mass. 2 mass% is preferable, 1.8 mass% is preferable, 1.6 mass% is preferable, 1.5 mass% is preferable, 1 mass% is preferable, 0.95 mass% is preferable, and 0.9 mass% is 0.85% by mass is preferable, 0.8% by mass is preferable, 0.75% by mass is preferable, 0.7% by mass is preferable, 0.65% by mass is preferable, and 0.6% by mass is preferable, 0.55 mass% is preferable, 0.5 mass% is preferable, 0.45 mass% is preferable, and 0.4 mass% is preferable.

A particularly preferable specific example of the spontaneous orientation monomer according to the present invention is a compound represented by the following general formula (al-1-1).

In the above general formula (al-1-1), R ^al3 represents a linear alkyl group having 1 to 12 carbon atoms, and in the alkyl group, one or two or more non-adjacent —CH ₂ — groups May be substituted with -O- or -CH = CH-,
L ^AL5, and ^{L AL6, L AL7} and ^{L AL8} are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom or the ^P 11 ^{-S 11} - represents, in the alkyl group, 1 Or two or more non-adjacent -CH ₂ -may be substituted with -O- or -CH = CH-,
Ring A ^al3 represents 1,4-cyclohexylene or 1,4-phenylene;
R ^ala or ^{R alb} are each independently hydrogen atom or the above ^P 11 ^{-S 11} - ^represents, at least one of the above ^{R ala} or ^{R alb P 11 -S} 11 - represents,
Z ^al3 represents a single bond, -CH ₂ -CH _2- , -CH ₂ -O- or O-CH _2- ,
R ^{al 4} represents an adsorptive group represented by the above general formula (T),
Each of P ¹¹³ and P ¹¹⁴ independently represents 0 or 1. )
In formula ^(al-1-1), one of ^{L AL7} and ^{L AL8} is, preferably represents an alkyl group having 1-5 carbon atoms.

In formula ^{(al-1-1), R ala} and ^{R alb} above ^P 11 ^{-S 11} - preferably represents a.

In the above general formula (al-1-1), R al ⁴ is a group ^{represented by any one} of the general formulas (T-1-1) to (T-7-1) or the formula (T-1-1.1), (T-6) -1.1) or (T-5-1.1) is preferred.

Examples of preferable compounds represented by the above general formula (al-1) include compounds represented by the following formulas (AL-1.1) to (AL-1.18).

Preferred examples of the compound represented by the above general formula (al-2) include compounds represented by the following formulas (AL-2.1) to (AL-2.48).

<Polymerizable monomer>
The polymerizable monomer according to the present invention includes, in the liquid crystal composition, two or more selected from the group consisting of compounds represented by the following general formula (I) having a chemical structural formula different from the above-mentioned spontaneous orientation monomer. Be

(In the general formula ^{(I), R 101, R} 102, R 103, R 104, R 105, R 106, R 107, R 108, R 109 and ^{R 110} are each ^{independently,} P ^{21 -S} 21 - And an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, and P ²¹ represents a group represented by the following formula (PI) to formula (P-IX) Any group represented by),

(Wherein, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, and W ^p11 is a single bond, —O -, -COO- or a methylene group, and t ^p11 represents 0, 1 or 2.)
The above S ²¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more of —CH ₂ — in the alkylene group is —O— such that oxygen atoms are not directly adjacent to each other. , -OCO- or -COO- may be substituted,
n ¹¹ represents 0, 1 or 2;
n ¹² and n ¹³ each independently represent 0 or 1;
represents n ¹¹ + n ¹² + n ¹³ = 1, 2 or 3;
A ¹¹ is a group (a), a group (b) and a group (c) shown below:
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (c) Naphthalene-2,6-diyl group, 2,7-phenanthrendiyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6 One -CH = or two or more non-adjacent -CH = in the -diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is replaced by -N = May be.)
Group (a), group (b) and group (c) are each independently an alkyl group having 1 to 12 carbon atoms and an alkoxy having 1 to 12 carbon atoms group, a halogen, a cyano group, a nitro group, or ^P 21 ^{-S 21} - be substituted with good,
L ¹⁰ and L ¹¹ each independently represent a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —OC ₂ H ₄ O—, —COO—, —OCO—, — CH = CR ^a -COO-, -CH = CR ^a -OCO-, -COO-CR ^a = CH-, -OCO-CR ^a = CH-,-(CH ₂ ) _z -COO-,-(CH ₂ ) _{z -OCO -, - OCO- (CH} 2) z -, - COO- (CH 2) z -, - CH = CH -, - CF 2 O -, - OCF 2 - or -C≡C- (wherein And ^Ra each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, each z independently represents an integer of 1 to 4).
When a plurality of P ²¹ , S ²¹ , L ¹¹ and A ¹¹ exist, they may be the same or different. )
When two or more kinds of polymerizable monomers are contained in the liquid crystal composition in the present invention, the tilt angle of liquid crystal molecules can be formed by the first polymerization process of the polymerizable monomer and the spontaneous alignment monomer present in the composition. It becomes easy to construct a network of polymers. In the liquid crystal composition, at least three monomers of one or more kinds of spontaneous orientation monomers and two or more kinds of polymerizable monomers, each having a different chemical structure, are present. Since the polymerization reactivities of these three monomers are different, it is considered that a monomer that can trigger the polymerization reaction can promote the reaction of other monomers in response to a wide range of reaction conditions. More specifically, in the case of polymerization by UV irradiation, the chemical structure, in particular, the mesogen skeleton that most affects the absorption of light and the substituent that binds to the mesogen skeleton differ from these three, so It is believed that the monomer with the longest absorption wavelength can promote the reaction of two or more other monomers. This is considered to facilitate formation of a polymer network of a size that can form the tilt angle of liquid crystal molecules in the first polymerization process of the polymerizable monomer and the spontaneous alignment monomer present in the composition.

The polymerizable monomer according to the present invention includes 2 to 4 polymerizable monomers selected from the group consisting of compounds represented by the above general formula (I) having a chemical structural formula different from the above-mentioned spontaneously orienting monomer. Is preferable, 2 to 3 types are more preferable, and 2 types are particularly preferable.

In the general formula ^{(I), R 101} and ^{R 110} are each ^{independently,} P ^{21 -S} 21 - is preferably. The above P ²¹ is preferably a general formula (PI).

In the above general formula (I), S ²¹ preferably represents a single bond or an alkylene group having 1 to 8 carbon atoms, and one or more of —CH ₂ — in the alkylene group is an oxygen atom It is more preferable to represent a single bond or an alkylene group having 1 to 5 carbon atoms, which may be substituted by -O-, -OCO- or -COO-, such that is not directly adjacent.

In the above general formula (I), A ¹¹ is a group selected from the group consisting of 1,4-cyclohexylene group, 1,4-phenylene group, naphthalene-2,6-diyl group and 2,7-phenanthrendiyl preferably representing, the a ¹¹ is an alkyl group having 1 to 5 carbon atoms, it may be substituted with an alkoxy group or a fluorine atom of 1 to 5 carbon atoms.

In the general formula ^{(I), L 10} and ^{L 11} are each independently a single _{bond, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - OC 2 H 4 O -, - COO It is preferable to represent-or -OCO-, and it is more preferable that L ¹⁰ and L ¹¹ represent a single bond.

When two types of polymerizable monomers are contained, one of the polymerizable monomers represented by the general formula (I) in the above general formula (I) has n ¹¹ of 0 and R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , any one of ^{R 105, R 106, R 107} , R 108 or ^{R 109} is an alkyl group having from 1 to 18 carbon ^atoms, independently ^{R 101} and ^{R 110} are ^each, P 21 ^{-S 21} - in Is preferred.

Specifically, the polymerizable monomer represented by the general formula (I) according to the present invention is represented by the following general formula (RM-1), general formula (RM-2) and general formula (RM-3) It is preferable that it is 2 or more types selected from the polymerizable monomer group.

(In the general formula (RM-1) and Formula ^{(RM-2), R 101 is,} P ^{33 -S} 33 - ^{represents, R 110 is,} P ^{44 -S} 44 - ^{represents, P 33} and ^{P 44} Each independently represents any of the above formulas (PI) to (P-IX), and each of S ³³ and S ⁴⁴ independently represents a single bond or an alkylene group having 1 to 10 carbon atoms. And one or more of —CH ₂ — in said alkylene group may be substituted by —O—, —OCO— or COO— such that the oxygen atom is not directly adjacent.
R ¹⁰² , R ¹⁰⁴ , R ¹⁰⁷ and R ¹⁰⁹ each independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a hydrogen atom,
A ¹¹ represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a naphthalene-2,6-diyl group or a 2,7-phenanthrendiyl group, and the A ¹¹ is unsubstituted or carbon It may be substituted by an alkyl group having 1 to 5 atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen (a fluorine atom or a chlorine atom),
L ¹¹ represents a single _{bond, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - COO -, - OCO -, - CH = CR a -COO -, - CH = CR a -OCO-, -COO-CR ^a = CH-, -OCO-CR ^a = CH-,-(CH ₂ ) _Y -COO-,-(CH ₂ ) _Y -OCO-, -OCO- (CH ₂ ) _Y- , -COO — (CH ₂ ) _Y— , —CH = CH—, —CF ₂ O—, —OCF ₂ — or C≡C— (wherein, each R ^a is independently a hydrogen atom or 1 to 3 carbon atoms In which Y represents an integer of 1 to 4).
Each of R ¹⁰³ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁸ independently represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a hydrogen atom. )

(In the above general formula (RM-3), X ^M1 to X ^M8 each independently represent a hydrogen atom or a fluorine atom,
S ^M2 and S ^M3 each independently represent an alkylene group having 1 to 12 carbon atoms or a single bond, and in the alkylene group, —CH ₂ — in the alkylene group is an oxygen atom as —O ₂ as the oxygen atom does not directly bond with each other -, -OCO- or OCOO- may be substituted,
R ^M2 and R ^M3 represent any one of the above formulas (P-1) to (P-15). )
The liquid crystal composition according to the present invention preferably contains at least one polymerizable monomer having a long absorption wavelength. The polymerizable monomer having a long absorption wavelength is preferably a structure having a biphenyl skeleton and having two or more (meth) acrylic functional groups, and the biphenyl skeleton may be substituted with a halogen atom, an alkyl group or an alkoxy group. Good.

In a liquid crystal composition according to the present invention, as a preferable embodiment having two or more types of polymerizable monomers represented by General Formula (I), the polymerizable monomer represented by General Formula (RM-2) includes two or more types Aspect, an aspect including the polymerizable monomer represented by the general formula (RM-1) and the polymerizable monomer represented by the general formula (RM-2), or the polymerizable monomer represented by the general formula (RM-2) And three polymerizable monomers represented by formula (RM-3).

In general, a liquid crystal display device using a liquid crystal composition containing a PSA process or a spontaneous alignment agent or a polymerizable monomer cures the spontaneously aligned monomer or the polymerizable monomer in the liquid crystal composition by irradiating light once or twice. Thus, a polymer network is formed on the substrate surface, and the tilt angle of liquid crystal molecules is controlled by the network. At that time, when a polymer network having a size capable of controlling the tilt angle of liquid crystal molecules is formed in the first light irradiation step, the amount of change in tilt angle with time in the liquid crystal display element can be reduced and burn-in can be reduced. it is conceivable that. Therefore, by using a liquid crystal composition containing one or more types of spontaneous alignment monomers and two or more types of polymerizable monomers, polymerization becomes possible in the light absorption bands of these at least three monomers. The reaction is likely to occur, and it is considered that the monomer having the longest absorption wavelength among the at least three monomers can promote the reaction of the other two or more monomers as a polymerization trigger (the so-called initiator role). . Therefore, it is preferable to include at least one polymerizable monomer having a long absorption wavelength. Specifically, an embodiment including two or more types of polymerizable monomers represented by the above general formula (RM-2), a polymerizable monomer represented by the general formula (RM-1), and the general formula (RM-2) Preferred is an embodiment including the polymerizable monomer represented by the above or an embodiment including the polymerizable monomer represented by the general formula (RM-2) and the polymerizable monomer represented by the general formula (RM-3).

On the other hand, in the case of a liquid crystal composition containing one type of spontaneous alignment monomer and one type of polymerizable monomer or a liquid crystal composition containing only the spontaneous alignment monomer, the tilt angle of liquid crystal molecules is controlled in the first light irradiation step. In order to form a polymer network of a possible size, a polymerizable monomer having a long absorption wavelength will be used, but the polymerizable monomer having a long absorption wavelength has a structure containing a large number of aromatic rings, and thus a liquid crystal composition is obtained. The desired concentration can not be added from the viewpoint of compatibility or low temperature stability. In addition, when a polymerizable monomer or a spontaneous orientation monomer having low reactivity is used, the domains constituting the polymer network become sparse, so that the tilt angle with respect to the liquid crystal molecules can not be controlled. It is considered that the stability of the tilt angle is low in the method of reinforcing the polymer network by curing the polymerizable monomer and the spontaneous orientation monomer remaining after the first light irradiation step.

In a liquid crystal composition according to the present invention, as a more preferable embodiment having two or more types of polymerizable monomers, an embodiment including two or more types of polymerizable monomers represented by the following general formula (RM-2-1), the following general formula An embodiment containing a polymerizable monomer represented by (RM-1-1) and a polymerizable monomer represented by the following general formula (RM-2-1), or represented by the following general formula (RM-2-1) And the polymerizable monomer represented by the following general formula (RM-3).

(In the above general formula (RM-1-1) and general formula (RM-2-1), P ^RM1 and P ^RM2 are each independently any one of the above formulas (PI) to (P-IX) Sp ^RM1 and Sp ^RM2 each independently represent a single bond or an alkylene group having 1 to 7 carbon atoms, and one or more of —CH ₂ — in the alkylene group is an oxygen atom It may be substituted by -O-, -OCO- or COO-, so as not to be directly adjacent to each other,
R ¹⁰² to R ¹⁰⁹ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a fluorine atom or a hydrogen atom,
R ¹¹¹ , R ¹¹² , R ¹¹³ and R ¹¹⁴ each independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a hydrogen atom. )
In the general formula (RM-1-1), it is preferable that either Sp ^RM1 or Sp ^RM2 represents an alkylene group having 1 to 7 carbon atoms, and the other represents a single bond.

In the general formula (RM-1-1), at least one of R ¹⁰² to R ¹¹⁴ preferably has an alkyl group having 1 to 4 carbon atoms or a fluorine atom, and R ¹¹¹ to R ^{114 are} At least one of them preferably has a fluorine atom.

In the general formula (RM-2-1), it is preferable that at least one of R ¹⁰² to R ¹⁰⁹ has an alkyl group having 1 to 4 carbon atoms.
<Liquid crystal composition>
The liquid crystal composition according to the present invention contains a liquid crystal component, and the liquid crystal component contains a non-polymerizable liquid crystal compound.

The liquid crystal compound as a liquid crystal component according to the present invention is a compound represented by the general formula (L), a compound represented by the general formula (J), a compound represented by the general formula (N-1), It is preferable to include one or more selected from the group consisting of a compound represented by N-2) and a compound represented by General Formula (N-3). When the liquid crystal composition as a whole exhibits negative dielectric anisotropy, a compound represented by General Formula (L), a compound represented by General Formula (N-1), and a compound represented by General Formula (N-2) It is preferable to include one or two or more compounds selected from the group consisting of the compound represented by the general formula (N-3) and the compound represented by the general formula (N-3). On the other hand, when the entire liquid crystal composition exhibits negative dielectric anisotropy, it preferably contains a compound represented by General Formula (L) and a compound represented by General Formula (J).

The liquid crystal compound according to the present invention comprises, as a first component, one or two or more compounds represented by the general formula (L) of a dielectric substantially neutral compound (the value of Δε is −2 to 2) It is preferable to contain.

The compounds represented by the above general formula (L) are as follows.

(Wherein, R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH ₂ -in the alkyl group are independently of each other -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, which may be substituted,
n ^L1 represents 0, 1, 2 or 3;
A ^L1 , A ^L2 and A ^L3 are each independently (a) 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — groups May be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , And one or more non-adjacent -CH = present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by -N =).
And the group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^L1 and ^{Z L2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 _{-, - CF 2 O -,} - CH = N-N = CH -, - CH = CH -, - represents CF = CF- or -C≡C-,
When n ^L1 is 2 or 3 and a plurality of A ^L2 is present, they may be the same or different, and when n ^L1 is 2 or 3 and a plurality of Z ^L2 is present, they may be May be the same or different. )
The liquid crystal composition according to the present invention contains a non-polymerizable liquid crystal compound, and the non-polymerizable liquid crystal compound has, as a second component, a general formula (J) of a dielectrically positive compound (Δε is larger than 2). And / or compounds represented by general formulas (N-1) to (N-3) of dielectrically negative compounds (the sign of Δε is negative and the absolute value is larger than 2) It is preferable to contain one or more kinds.

The compound represented by General Formula (J) of the dielectrically positive compound (Δε is larger than 2) is as follows.

(Wherein, R ^J1 represents an alkyl group having 1 to 8 carbon atoms, and one or two non-adjacent -CH ₂ -in the alkyl group are each independently -CH = CH-,- It may be substituted by C≡C-, -O-, -CO-, -COO- or -OCO-,
n ^J1 represents 0, 1, 2, 3 or 4;
A ^J1 , A ^J2 and A ^J3 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , And one or more non-adjacent -CH = present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by -N =).
Group (a), group (b) and group (c) are each independently a cyano group, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a trifluoro group It may be substituted by a methoxy group,
Z ^J1 and Z ^J2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O -, -COO-, -OCO- or -C≡C-,
When n ^J1 is 2, 3 or 4 and there are a plurality of A ^J2 , they may be the same or different, and n ^J1 is 2, 3 or 4 and a plurality of Z ^J1 is present If they are identical or different,
X ^J1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group. )
It is selected from the group consisting of compounds represented by general formulas (N-1) to (N-3) of the above-mentioned dielectrically negative compounds (the sign of Δε is negative and the absolute value is larger than 2) 1 type or 2 types or more are as follows.

(Wherein, R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 and R ^N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or more of the alkyl groups are Adjacent two or more -CH ₂ -may be independently substituted by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-.
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH = or two or more non-adjacent —CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by —N =. And d) represent a group selected from the group consisting of 1,4-cyclohexenylene groups, and the above groups (a), (b), (c) and (d) are each independently It may be substituted by a cyano group, a fluorine atom or a chlorine atom,
^{Z N11, Z N12, Z N21} , Z N22, Z N31 and ^{Z N32} are each independently a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O-, -COO-, -OCO-, -OCF _2- , -CF ₂ O-, -CH = N-N = CH-, -CH = CH-, -CF = CF- or -C≡C- Represent
X ^N21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents -CH ₂ -or an oxygen atom,
n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 and n ^N32 each independently represent an integer of 0 to 3, but n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are each independently When there are a plurality of A ^N11 to A ^N32 and Z ^N11 to Z ^N32 , they may be the same or different. )
The compound represented by the above general formula (L) is preferably a compound represented by the following formulas (L-1) to (L-13).

(Wherein, R ^L1 and R ^L2 each independently represent the same meaning as in general formula (L), and A ^L1 and A ^L7 each independently represent the same meaning as in general formula (L); The hydrogen atom on ^L1 and A ^L2 may be each independently substituted by a fluorine atom, and Z ^L1 has the same meaning as Z ^L2 in formula (L), and X ^L1 and X ^L2 are each independently Represents a fluorine atom or a hydrogen atom)
As a compound represented by General formula (J), the compound represented by General formula (M) and the compound represented by General formula (K) are preferable.

Here, as the compound represented by the general formula (M), one having the following structure is mentioned.

(Wherein, R ^M1 represents an alkyl group having 1 to 8 carbon atoms, and one or two non-adjacent -CH ₂ -in the alkyl group are each independently -CH = CH-,- It may be substituted by C≡C-, -O-, -CO-, -COO- or -OCO-,
n ^M1 represents 0, 1, 2, 3 or 4 and
A ^M1 and A ^M2 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S- And (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =)
And hydrogen atoms on the above groups (a) and (b) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^M1 and Z ^M2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, Represents -COO-, -OCO- or -C≡C-,
When n ^M1 is 2, 3 or 4 and there are a plurality of ^{AM 2} , they may be the same or different, and n ^M1 is 2, 3 or 4 and a plurality of Z ^M1 is present If they are identical or different,
X ^M1 and X ^M3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,
X ^M2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group.

In the general formula (M), R ^M1 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy having 2 to 8 carbon atoms Group is preferable, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferable. An alkyl group of 1 to 5 or an alkenyl group of 2 to 5 carbon atoms is further preferable, an alkyl group of 2 to 5 carbon atoms or an alkenyl group of 2 to 3 carbon atoms is further preferable, and an alkenyl group of 3 carbon atoms (Propenyl group) is particularly preferred.

When importance is attached to reliability, R ^M1 is preferably an alkyl group, and when importance is attached to decrease in viscosity, it is preferably an alkenyl group.

When the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and carbon Alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain Preferred is an alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, preferably linear.

The alkenyl group is preferably selected from the groups represented by any one of formulas (R1) to (R5). (The black dot in each formula represents a carbon atom in a ring structure to which an alkenyl group is bonded.)

A ^M1 and A ^M2 are each preferably aromatic when it is required to increase Δn independently, and in order to improve the response speed, it is preferably aliphatic, and trans-1,4 -Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2 ,, 3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6- It is preferable to represent a diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferable to represent the following structure,

It is more preferable to represent the following structure.

Z ^M1 and ^{Z M2} each _{independently -CH 2 O -, - CF 2} O -, - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CF 2 O-, More preferred is —CH ₂ CH ₂ — or a single bond, with —CF ₂ O— or a single bond being particularly preferred.

n ^M1 is preferably 0, 1, 2 or 3 and is preferably 0, 1 or 2; 0 or 1 is preferred when emphasis is placed on improvement of Δε, and 1 or 2 is preferred when T _NI is emphasized preferable.

There is no particular limitation on the types of compounds that can be combined, but they are used in combination according to the desired properties such as low temperature solubility, transition temperature, electrical reliability, birefringence and the like. The types of compounds to be used are, for example, one type, two types, and three types in one embodiment of the present invention. Furthermore, in another embodiment of the present invention, there are four types, five types, six types, and seven or more types.

In the composition of the present invention, the content of the compound represented by the general formula (M) is low temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, image sticking, It is necessary to appropriately adjust according to the required performance such as dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (M) with respect to the total amount of the liquid crystal composition of the present invention is 1 mass%, 10 mass%, 20 mass%, and 30 mass%. %, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, 80% by mass is there. The upper limit value of the preferable content is, for example, 95% by mass, 85% by mass, and 75% by mass in one form of the invention with respect to the total amount of the liquid crystal composition of the present invention. Yes, 55% by weight, 45% by weight, 35% by weight, and 25% by weight.

It is preferable to keep the viscosity of the composition of the present invention low and lower the above lower limit and lower the upper limit when a composition having a high response speed is required. Furthermore, it is preferable to keep the _TNI of the composition of the present invention high, and lower the above lower limit and lower the upper limit when a composition having good temperature stability is required. When it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the lower limit and raise the upper limit.

Next, the compound represented by general formula (K) has the following chemical structure.

(Wherein, R ^K1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently —CH-CH—, — It may be substituted by C≡C-, -O-, -CO-, -COO- or -OCO-,
n ^K1 represents 0, 1, 2, 3 or 4;
A ^K1 and A ^K2 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S- And (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =)
And hydrogen atoms on the above groups (a) and (b) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^K1 and Z ^K2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, Represents -COO-, -OCO- or -C≡C-,
When n ^K1 is 2, 3 or 4 and there are a plurality of ^{AK 2} , they may be the same or different, and n ^K1 is 2, 3 or 4 and a plurality of Z ^K1 is present If they are identical or different,
X ^K1 and X ^K3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,
X ^K2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group or a 2,2,2-trifluoroethyl group. )
In the general formula (K), R ^K1 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy having 2 to 8 carbon atoms Group is preferable, and an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms is preferable. An alkyl group of 1 to 5 or an alkenyl group of 2 to 5 carbon atoms is further preferable, an alkyl group of 2 to 5 carbon atoms or an alkenyl group of 2 to 3 carbon atoms is further preferable, and an alkenyl group of 3 carbon atoms (Propenyl group) is particularly preferred.

When importance is attached to reliability, R ^K1 is preferably an alkyl group, and when importance is attached to decrease in viscosity, it is preferably an alkenyl group.

When the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and carbon Alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain Preferred is an alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group having 2 to 5 carbon atoms. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, preferably linear.

The alkenyl group is preferably selected from the groups represented by any one of formulas (R1) to (R5). (The black dot in each formula represents a carbon atom in a ring structure to which an alkenyl group is bonded.)

A ^K1 and A ^K2 are each preferably aromatic when it is required to increase Δn independently, and is preferably aliphatic to improve the response speed, and trans-1,4 -Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2 ,, 3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6- It is preferable to represent a diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferable to represent the following structure,

It is more preferable to represent the following structure.

Z ^K1 and ^{Z K2} are each _{independently -CH 2 O -, - CF 2} O -, - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CF 2 O-, More preferred is —CH ₂ CH ₂ — or a single bond, with —CF ₂ O— or a single bond being particularly preferred.

n ^K1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, and if emphasis is placed on improvement of Δε, then 0 or 1 is preferred, and if emphasis is placed on T _NI , 1 or 2 is preferred. preferable.

There is no particular limitation on the types of compounds that can be combined, but they are used in combination according to the desired properties such as low temperature solubility, transition temperature, electrical reliability, birefringence and the like. The types of compounds to be used are, for example, one type, two types, and three types in one embodiment of the present invention. Furthermore, in another embodiment of the present invention, there are four types, five types, six types, and seven or more types.

In the composition of the present invention, the content of the compound represented by the general formula (K) is low temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, image sticking, It is necessary to appropriately adjust according to the required performance such as dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the general formula (K) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass, 10% by mass, 20% by 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, 80% by mass It is. The upper limit value of the preferable content is, for example, 95% by mass, 85% by mass, 75% by mass, and 65% by mass with respect to the total amount of the composition of the present invention. 55% by mass, 45% by mass, 35% by mass and 25% by mass.

When the viscosity of the liquid crystal composition of the present invention is kept low and a composition having a high response speed is required, it is preferable to lower the above lower limit and lower the upper limit. Furthermore, it is preferable to keep _TNI of the liquid crystal composition of the present invention high and lower the above lower limit and lower the upper limit when a composition having good temperature stability is required. When it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the lower limit and raise the upper limit.

The compound represented by the above general formula (J) is preferably a compound represented by the following formulas (M-1) to (M-18).

(In the ^{formula, X M11 ~} X ^M186 each independently represent a hydrogen atom or a fluorine ^{atom, R J1 ~} R ^J181 is independently an alkyl group having 1 to 5 carbon atoms, 2 to 5 carbon atoms Or an alkoxy group having 1 to 4 carbon atoms, X ^J11 to X ^{J 181} each represents a fluorine atom, a chlorine atom or OCF ₃ ,
Each of A ^M81 and A ^M82 is independently a 1,4-cyclohexylene group, a 1,4-phenylene group or

However, the hydrogen atom on the 1,4-phenylene group may be substituted by a fluorine atom, and ^{WM 101} to ^{WM 172} each independently represent -CH ₂ -or -O-. )

Examples of the compound represented by General Formula (N-1) according to the present invention include compounds represented by the following General Formulas (N-1a) to (N-1g).

^{(Wherein, R N11} and ^{R N12} are as defined ^{R N11} and ^{R N12} in the general formula ^{(N-1), n Na12} represents 0 or ^{1, n NB11} is 1 or ^{2, n NC11} is N ^Nd11 represents 1 or 2; n ^Ne11 represents 1 or 2; n ^Nf12 represents 1 or 2; n ^Ng11 represents 1 or 2; A ^Ne11 represents trans-1, 4 And A ^Ng11 represents a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group ^; If is ^{1, a NG11} represents cyclohexenylene ^group, when ^{n NG11} is 2, represents at least one ^{a NG11} 1,4-cyclohexenylene ^{group, Z NE11} is a single bond Represents an ethylene ^group, when ^{n NE11} is ^{1, Z NE11} if ^{.n NE11} representing the ethylene group is 2, represents at least one ^{Z NE11} ethylene group.)
The compound represented by General Formula (N-2) according to the present invention is a compound selected from the group of compounds represented by the following General Formulas (N-2-1) to (N-2-3) Is preferred.

^{(Wherein, R N211} and ^{R N212} each independently represents the same meaning as ^{R N21} and ^{R N22} in the general formula (N-2).)

^{(Wherein, R N221} and ^{R N222} each independently represents the same meaning as ^{R N21} and ^{R N22} in the general formula (N-2).)

^{(Wherein, R N231} and ^{R N232} each independently represents the same meaning as ^{R N21} and ^{R N22} in the general formula (N-2).)
The compound represented by General Formula (N-3) is preferably a compound selected from the group of compounds represented by General Formula (N-3-2).

^{(Wherein, R N321} and ^{R N322} each independently represents the same meaning as ^{R N31} and ^{R N32} in the general formula (N-3).)
When the whole liquid crystal composition containing the polymerizable monomer according to the present invention exhibits positive dielectric anisotropy, the polymerizable monomer represented by the general formula (I) and the compound represented by the general formula (J) It is preferable to include one or two or more compounds selected from and a compound represented by General Formula (L).

The upper limit of the proportion occupied by the components consisting of only the compounds represented by general formula (I), general formula (J) and general formula (L) in the whole liquid crystal composition containing the polymerizable monomer according to the present invention The values are 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass% It is preferable that they are 88 mass%, 87 mass%, 86 mass%, 85 mass%, and 84 mass%.

In addition, the lower limit of the proportion of the component composed of only the compounds represented by General Formula (I), General Formula (J) and General Formula (L) in the entire polymerizable monomer-containing liquid crystal composition according to the present invention The values are 78 mass%, 80 mass%, 81 mass%, 83 mass%, 85 mass%, 86 mass%, 87 mass%, 88 mass%, 89 mass%, 90 mass%, 91 mass%, 92 mass% 93% by weight, 94% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight.

When the whole polymerizable monomer-containing liquid crystal composition according to the present invention exhibits negative dielectric anisotropy, the polymerizable monomer represented by the general formula (I) and the compound represented by the general formula (N-1) It is preferable to include one or two or more compounds selected from and a compound represented by General Formula (L).

In the entire polymerizable monomer-containing liquid crystal composition according to the present invention, the proportion of the component constituted only of the compound represented by General Formula (I), General Formula (N-1), and General Formula (L) The upper limit value is 100 mass%, 99 mass%, 98 mass%, 97 mass%, 96 mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass %, 88% by mass, 87% by mass, 86% by mass, 85% by mass, 84% by mass.

When the liquid crystal composition according to the present invention is a negative liquid crystal composition, the dielectric anisotropy (Δε) at 20 ° C. is from −2.0 to −8.0, but from −2.1 to −6. 2 is preferable, -2.2 to -5.3 is more preferable, and -2.5 to -5.0 is more preferable. -2.7 to -4.8 are particularly preferred.

When the liquid crystal composition according to the present invention is a positive liquid crystal composition, the dielectric anisotropy (Δε) at 20 ° C. is 1.5 to 20, preferably 1.5 to 18.0. 5 to 15.0 is more preferable, 1.5 to 11 is more preferable, and 1.5 to 8 is particularly preferable.

The liquid crystal composition according to the present invention has a refractive index anisotropy (Δn) at 20 ° C. of 0.08 to 0.14, preferably 0.09 to 0.13, more preferably 0.09 to 0.12. Is particularly preferred. More specifically, in the case of a thin cell gap, it is preferably 0.10 to 0.13, and in the case of a thick cell gap, it is preferably 0.08 to 0.11.

The liquid crystal composition according to the present invention has a viscosity (η) at 10 ° C. of 10 to 50 mPa · s, preferably 10 to 45 mPa · s, and more preferably 10 to 40 mPa · s. The viscosity is preferably 35 mPa · s, more preferably 10 to 30 mPa · s, still more preferably 10 to 25 mPa · s, and particularly preferably 10 to 22 mPa · s.

The liquid crystal composition according to the present invention has a rotational viscosity (γ ₁ ) at 50 ° C. of 50 to 160 mPa · s, preferably 55 to 160 mPa · s, and more preferably 60 to 160 mPa · s, The viscosity is preferably 60 to 150 mPa · s, preferably 60 to 140 mPa · s, preferably 60 to 130 mPa · s, and more preferably 60 to 125 mPa · s.

The liquid crystal composition according to the present invention has a nematic phase-isotropic liquid phase transition temperature (T _ni ) of 60 ° C. to 120 ° C., preferably 70 ° C. to 100 ° C., particularly preferably 70 ° C. to 85 ° C. .

The liquid crystal display device using the polymerizable monomer-containing liquid crystal composition of the present invention has the remarkable feature of high-speed response, and in addition, is sufficient tilt angle obtained and there is no unreacted polymerizable monomer? Because the voltage holding ratio (VHR) is so small that there is no problem, problems such as alignment failure and display failure are sufficiently suppressed. In addition, since the tilt angle and the residual amount of the polymerizable monomer can be easily controlled, it is easy to optimize and reduce the energy cost for manufacturing, which is optimal for improvement of production efficiency and stable mass production.

The liquid crystal display device using the polymerizable monomer-containing liquid crystal composition of the present invention is particularly useful for a liquid crystal display device for driving an active matrix, and is a PSA mode, PSVA mode, VA mode, PS-IPS mode or PS-FFS mode It can use for the liquid crystal display element for.

The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. Moreover, "%" in the composition of the following example and a comparative example means "mass%." The following abbreviations are used for the description of the compounds in the examples.

The characteristics measured in the examples are as follows.

T _ni : Nematic phase-isotropic liquid phase transition temperature (° C.)
Δn: refractive index anisotropy at 20 ° C. :: viscosity at 20 ° C. (mPa · s)
γ ₁ : rotational viscosity (mPa · s) at 20 ° C
Δε: dielectric anisotropy at 20 ° C. K ₃₃ : elastic constant K _{33 at} 20 ° C. (pN)
<Ring structure>

<Side chain structure>

(However, n in the table is a natural number.)
<Connected structure>

(However, n in the table is a natural number.)
The evaluations of “low temperature storage stability”, “vertical alignment”, “pretilt angle formation” and “response characteristics” in the present example and the comparative example were performed by the following methods.

(Evaluation test of low temperature storage stability)
The liquid crystal composition was filtered with a membrane filter (PTFE 13 m-0.2 μm, manufactured by Agilent Technologies), and allowed to stand for 15 minutes under vacuum reduced pressure conditions to remove dissolved air. This was washed with acetone and weighed 0.5 g in a fully dried vial, and allowed to stand in an environment of −25 ° C. for 10 days. Then, the presence or absence of precipitation was observed visually and it determined in the following two steps.

A: Precipitation can not be confirmed.

B: precipitate after 1 week.

C: Precipitation can be confirmed.

(Evaluation test of vertical orientation)
It is driven by a first substrate (common electrode substrate) having a transparent electrode layer consisting of a transparent common electrode patterned on an insulating layer and not having an alignment film provided with a color filter layer, and an active element A second substrate (pixel electrode substrate) not having an alignment film having a pixel electrode layer having a transparent pixel electrode was produced. The liquid crystal composition was dropped on the first substrate and sandwiched between 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. At this time, the vertical alignment property and alignment unevenness such as dripping marks were observed using a polarization microscope, and evaluated in the following five steps.
S: Particularly excellent, uniformly vertical alignment A: uniform across the entire surface, uniform vertical alignment B: an acceptable level with some slight alignment defects C: an acceptable level with alignment defects D: an extremely poor alignment defect (liquid crystal Burn-in evaluation method (temporal change of pretilt angle))
First, a polyimide alignment film for inducing vertical alignment was applied to a substrate with ITO, and then the polyimide alignment film was injected by vacuum injection between liquid crystal cells (cell gap 3.5 μm) including a substrate with rubbing-treated ITO. . After that, while applying a voltage of 10 V at a frequency of 100 Hz to the liquid crystal cell injected with the liquid crystal composition, ultraviolet light was irradiated through a filter that cuts ultraviolet light of 325 nm or less using a high pressure mercury lamp. In this case, illuminance measured at the center wavelength of 365nm condition was adjusted to 100 mW / cm ^2, was irradiated with ultraviolet light at an accumulated light intensity of 10J / cm ^2. The above ultraviolet irradiation condition is referred to as irradiation condition 1. Under the irradiation condition 1, a pretilt angle is given to liquid crystal molecules in the liquid crystal cell. Here, in order to evaluate pretilt formation regardless of the presence or absence of vertical alignment, evaluation is performed in a cell with a polyimide alignment film, but when a monomer having a sufficiently high vertical alignment is used, a cell without polyimide alignment film is used. It is confirmed that the same result can be obtained by performing the same evaluation.

Then, using a fluorescent UV lamp, the illuminance was measured at a center wavelength of 313nm is adjusted to 3 mW / cm ^2, further irradiated with ultraviolet light at an accumulated light intensity 20 J / cm ^2, to obtain a liquid crystal display device . The aforementioned ultraviolet irradiation conditions are referred to as irradiation conditions 2. Under the irradiation condition 2, the residual amount of the polymerizable monomer in the unreacted liquid crystal cell under the irradiation condition 1 is reduced.

After ultraviolet irradiation, display defect (burn-in) evaluation due to change of pretilt angle was performed. First, the pretilt angle of the liquid crystal display element was measured and used as a pretilt angle (initial). The backlight was illuminated for 10 hours while applying a voltage of 100 Hz at a frequency of 100 Hz to the liquid crystal display element at a rectangular wave of 30 V. After that, the pretilt angle was measured and used as the pretilt angle (after the test). A value obtained by subtracting the pretilt angle (after the test) from the measured pretilt angle (initial) is taken as a pretilt angle change amount (= absolute value of pretilt angle change) [°]. The pretilt angle was measured using Syntech OPTIPRO. The magnitude of the voltage of 30 V is several times larger than the normal drive voltage, which is an acceleration test.

As the pretilt angle change amount approaches 0 [.degree.], The possibility of occurrence of display defects due to the change in pretilt angle becomes lower.

The measured amount of change in pretilt angle was divided into the following four stages.
S: within 0.1 ° (mostly display defects do not occur)
A: 0.1 ° or more and 0.3 or less (not likely to cause display defects)
B: 0.3 ° or more and 0.5 ° or less (a considerable display defect occurs)
C: 0.5 ° or more (display failure and unacceptable level)
(Evaluation test of response characteristics)
The cell gap of 3.2 μm used in the above (evaluation test of formation of pretilt angle) was further irradiated for 60 minutes with a UV fluorescent lamp manufactured by Toshiba Lightech Co. (illuminance at 313 nm: 1.7 mW / cm ² ). The response speed was measured for the cells obtained by this. The response speed was measured at Voff at 6 V using a DAM 703 manufactured by AUTRONIC-MELCHERS under a temperature condition of 25 ° C.

(Preparation and Evaluation of Liquid Crystal Composition)
A liquid crystal composition was prepared at a mixing ratio with the compound as shown below, and the composition was designated LC-1. The composition of the liquid crystal composition and the results of physical properties are shown below.

The nematic phase-isotropic liquid phase transition temperature (T _NI ) of LC-1 is 75 ° C., the solid phase-nematic phase transition temperature (T _CN ) is -33 ° C., and the refractive index anisotropy (Δn) is 0.11. The dielectric anisotropy (Δε) was −2.8, and the rotational viscosity (γ ₁ ) was 98 mPa · s. The refractive index anisotropy (Δn), the dielectric anisotropy (Δε), and the rotational viscosity (γ1) are all measurement results at 25 ° C. (the same applies hereinafter).

(Comparative Examples 1 to 8)
Polymerization in which 1.0 part by mass of the following spontaneous orientation monomer (P-1) and 0.3 parts by mass of a compound represented by the formula (RM-1) were added, based on 100 parts by mass of LC-1 Comparative Example 1 is a liquid crystal composition containing a monomer monomer.

Polymerization in which 1.0 part by mass of the spontaneous orientation monomer (P-1) and 0.3 parts by mass of the compound represented by the formula (RM-2) are added to 100 parts by mass of the liquid crystal composition LC-1 Example 2 is a liquid crystal composition containing a functional monomer.

Polymerization in which 1.0 part by mass of the spontaneous orientation monomer (P-1) and 0.3 parts by mass of the compound represented by the formula (RM-3) are added to 100 parts by mass of the liquid crystal composition LC-1 Example 3 is a liquid crystal composition containing a functional monomer.

Polymerization in which 1.0 part by mass of the spontaneously orienting monomer (P-1) and 0.3 parts by mass of the compound represented by the formula (RM-4) were added to 100 parts by mass of the liquid crystal composition LC-1 Example 4 is a liquid crystal composition containing a functional monomer.

Polymerization in which 0.5 parts by mass of the spontaneous orientation monomer (P-1) and 0.3 parts by mass of the compound represented by the formula (RM-2) are added to 100 parts by mass of the liquid crystal composition LC-1 Example 5 is a liquid crystal composition containing a functional monomer.

Polymerization in which 0.5 parts by mass of the spontaneously orienting monomer (P-1) and 0.6 parts by mass of the compound represented by the formula (RM-1) are added to 100 parts by mass of the liquid crystal composition LC-1 Example 6 is a liquid crystal composition containing a functional monomer.

Polymerization in which 1.0 part by mass of the spontaneous orientation monomer (P-1) and 0.6 parts by mass of the compound represented by the formula (RM-1) are added to 100 parts by mass of the liquid crystal composition LC-1 Example 7 is a liquid crystal composition containing a functional monomer.

Polymerization in which 1.0 part by mass of the spontaneously orienting monomer (P-1) and 0.6 parts by mass of the compound represented by the formula (RM-3) are added to 100 parts by mass of the liquid crystal composition LC-1 Example 8 is a liquid crystal composition containing a functional monomer.

(Examples 1 to 95)
Except that the spontaneous orientation monomers (P-1) to (P-41) shown below and the polymerizable monomers (RM-1) to (RM-16) were added to LC-1 in the amounts shown in the following table, respectively A liquid crystal composition was prepared in the same manner as in Comparative Example 1.

The chemical structures of the spontaneously orienting monomer and the polymerizable monomer used in this example are shown below. In the following structural formulae, "Me" represents a methyl group.

With respect to the low temperature storage stability of Examples 1 to 95, precipitation starts to occur in about one week in a polymerizable monomer having a long chain alkyl group as a substituent (eg, RM-9 to RM-11). In addition, the polymerizable monomers having a short chain alkyl or alkoxy group as a substituent (for example, RM-3 to RM-7, RM-12 to RM-14) had good solubility and low temperature storage stability. As for the low temperature storage property, the polymerizable monomer has a relatively high solubility, so it largely depends on the solubility of the spontaneously orienting monomer.

In addition, when a liquid crystal cell in which a liquid crystal composition containing two kinds of polymerizable monomers is enclosed is set in a polarization microscope in which a polarizer and an analyzer are disposed at right angles, and transmitted light is observed, liquid crystal molecules are vertically aligned For example, since the light can not be transmitted by the action of the polarizing plate, the cell is displayed black. When the samples of the liquid crystal compositions of the above Examples 1 to 95 were evaluated by such a test method, appropriately selecting two types of polymerizable monomers and adding them to the liquid crystal composition significantly reduced the uneven alignment, It was confirmed that they showed similar vertical orientation. Examples of the appropriate two types of polymerizable monomers include a combination of a bifunctional monomer having a hydrophobic group introduced in the mesogen side chain and a polymerizable monomer having absorption at 300 nm or more, and each monomer has an appropriate concentration. Good vertical alignment was confirmed by adding at.

On the other hand, in Comparative Examples 1, 2, 4, 5 to 7, it was confirmed that while the pretilt change amount was relatively good by adding the polymerizable monomer, the vertical alignment was low. In Comparative Example 3, although the vertical alignment was high, the pretilt change amount was large. In Comparative Examples 6 to 7, although the addition amount of one type of polymerizable monomer was increased, the vertical alignment was not improved. From these results, it was confirmed that one type of polymerizable monomer is not a monomer capable of achieving both vertical alignment and pretilt variation.

Further, in the comparative example, the orientation and tilt stability are evaluated in a composition comprising one type of spontaneous orientation monomer and one type of polymerizable monomer, but a polymerizable monomer having absorption at a long wavelength (for example, RM) When -4) was used, the tilt stability was relatively good, but the vertical alignment was inferior. In addition, when the compound (RM-3) having a hydrophobic site introduced is used as the polymerizable monomer, the vertical alignment property is good, but the polymerization by the ultraviolet light irradiation does not occur sufficiently, and the network is densely formed. As a result, the tilt stability is lowered. Furthermore, in all of Comparative Examples 1 to 8, the low temperature storage stability was inferior to that of Example.

In Examples 1, 12, 26, 42, and 50, since two types of polymerizable monomers in which a hydrophobic group is not introduced are used, it is considered that the vertical alignment results in inferiority compared to the other examples. Be On the other hand, in Examples 5, 6, 24, 27, 28, 38, 39 and 46, since the polymerizable monomer whose light absorption region is not relatively shifted to the long wavelength side is used, the polymerization is difficult to proceed, In the initial stage of the polymerization, the formation of the polymer network was insufficient, and as a result, the pretilt change amount was inferior to the other examples. From the above experimental results, high vertical alignment and a small amount of pretilt change can be achieved by appropriately selecting two kinds of functionally separated monomers of the polymerizable monomer involved in polymerization and the polymerizable monomer contributing to the vertical alignment. It is thought that can be done. In the other examples, in addition to high vertical alignment, it was confirmed that the amount of change in pretilt angle was sufficiently small, and display unevenness and burn-in were small. In particular, the polymerizable monomer having a hydrophobic group introduced therein acts as an intermediary between the spontaneously oriented monomer and the other polymerizable monomer, and the strength of the polymer is enhanced by improving the crosslink density of the polymer layer while maintaining high vertical orientation. As a result, the stability is considered to be excellent.

Moreover, when the pretilt angle which arises by superposition | polymerization by ultraviolet light irradiation was evaluated, the bifunctional monomer (For example, RM-3, RM-5, RM-6, RM-8) which introduce | transduced the hydrophobic group into the mesogen side chain, It was confirmed that an appropriate tilt angle was given to the samples to which polymerization monomers having absorption at a long wavelength (for example, RM-4 and RM-12 to RM-14) were respectively added. It was suggested that the liquid crystal display element using these had a sufficiently fast response since a sufficient pretilt angle was given.

When a liquid crystal cell was produced using a composition containing RM-1 to RM-17 used as polymerizable monomers in Examples 1 to 11, etc., the developability (wet spread) was also good.

Furthermore, even when the addition amount of the spontaneous orientation monomer in Examples 1 to 95 is replaced from 1.0 part by mass to 0.5 part by mass, respectively, the vertical alignment property and the pretilt change amount are small, and the display unevenness and the image sticking are It confirmed that it could be suppressed.

Instead of the composition LC-1, compositions composed of compounds and mixing ratios as shown below were prepared, and the liquid crystal compositions were designated LC-2 to LC-8.

(Examples 96 to 103)
It was confirmed that even when the base composition of Example 3 was replaced with LC1 to LC2, the vertical alignment and the pretilt change amount were small, and the display unevenness and the image sticking were suppressed (Example 96).
It was confirmed that even when the base composition of Example 30 was replaced with LC1 to LC3, the vertical alignment and the pretilt change amount were small, and the display unevenness and the image sticking were also suppressed (Example 97).

Even when the base composition of Example 35 was replaced with LC1 to LC4, it was confirmed that the vertical alignment and the pretilt change amount were small, and the display unevenness and the image sticking were suppressed (Example 98).

It was confirmed that even when the base composition of Example 36 was changed from LC1 to LC5 and the polymerizable compound was changed from P-6 to P-11, the vertical alignment and the pretilt change amount were small, and the display unevenness and the image sticking were suppressed ( Example 99).

Even when the base composition of Example 41 was changed from LC1 to LC6 and the polymerizable compound was changed from P-6 to P-18, it was confirmed that the vertical alignment and the pretilt change amount were small, and the display unevenness and the image sticking were suppressed ( Example 100).

Even when the base composition of Example 44 was changed from LC1 to LC7 and the polymerizable compound was changed from P-7 to P-23, it was confirmed that the vertical alignment and the pretilt change amount were small, and the display unevenness and the image sticking were suppressed ( Example 101).

It was confirmed that even when the base composition of Example 47 was changed from LC1 to LC8 and the polymerizable compound was changed from P-8 to P-30, the vertical alignment and the pretilt change amount were small, and the display unevenness and the image sticking were suppressed ( Implementation 102).

It was confirmed that the vertical alignment and the pretilt change amount were small and the display unevenness and the image sticking were suppressed even if the base composition of Example 56 was changed from LC1 to LC8 and the polymerizable compound was changed from P-10 to P-34 Example 103).

Furthermore, even when the addition amount of the spontaneous orientation monomer in Examples 96 to 103 is replaced from 1.0 part by mass to 0.5 part by mass, respectively, the vertical alignment property and the pretilt change amount are small, and the display unevenness and the image sticking are It confirmed that it could be suppressed.

(Examples 104 to 123)
0.2 parts by mass of the spontaneous orientation monomer (1) and 0.4 parts by mass of the spontaneous orientation monomer (2) shown in the following table, and the polymerizable monomers (1) and (2) in the addition amounts shown in the following table A liquid crystal composition was prepared in the same manner as in Comparative Example 1 except that each of the compositions LC-1 to LC-8 was added.

The low temperature storage property, the vertical alignment property, and the pretilt stability were evaluated by the combination of two kinds of spontaneously orienting monomers and two kinds of polymerizable monomers. By mixing two types of low solubility spontaneous orientation monomers at a low concentration, it was possible to confirm the improvement of the vertical orientation while maintaining the low temperature storage property. In addition, by mixing and using several kinds of polymerizable monomers, the concentration of the polymerizable monomer component can be increased, and the pretilt stability can be improved.

From the evaluation results of each of the examples described above, the liquid crystal composition in the examples exhibited comprehensively excellent performance as a liquid crystal display element.

(Examples 124 to 149)
A liquid crystal composition was prepared in the same manner as in Example 1 except that the spontaneously orienting monomers in Example 1 were replaced by P-1 to P-41 to P-66, respectively, and these were designated as Examples 124 to 149. . From the results of Examples 124 to 149, it was confirmed that the vertical alignment property and the pretilt change amount were small, and the display unevenness and the image sticking were suppressed even when various kinds of spontaneous alignment monomers were used.

Claims (6)

At least one kind of spontaneously orienting monomer having a first mesogen skeleton, at least one polymerizable group represented by the general formula (PG1), and at least one adsorptive group,
A liquid crystal composition comprising two or more kinds of polymerizable monomers selected from the group consisting of polymerizable monomers represented by the following general formula (I) having a chemical structure different from the spontaneously orienting monomer.

In the above formulae, P ¹¹ is a group represented by the following formulas (RI) to (R-IX),

(In the above formulas (R-I) to (R-IX), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms Or a halogenated alkyl group having 1 to 5 carbon atoms, W ¹ is a single bond, -O- or a methylene group, T ¹ is a single bond or COO-, p ¹ , t ¹ and q ¹ Are each independently 0, 1 or 2, and one or more hydrogen atoms of the polymerizable group P ¹¹ may be substituted by the adsorptive group, or the adsorptive group is represented by the general formula (PG1) The polymerizable group represented may be possessed as a substituent.)
S ¹¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - directly oxygen atom It may be substituted by the adsorptive group, -O-, -OCO- or -COO- so that it is not adjacent, and * in the chemical formula represents a bond. )

(In the above general formula (I), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ , R ¹⁰⁹ and R ¹¹⁰ are each independently P ¹¹ -S ¹¹ -Represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, and P ²¹ is a group represented by the following formula (R-I) to formula (R- Represents any of IX),

(In the above formulas (R-I) to (R-IX), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ independently of each other represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms) And W is a single bond, -O- or a methylene group, T is a single bond or -COO-, and p, t and q are each independently 0, 1 or 2.)
S ²¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more of —CH ₂ — in the alkylene group is —O—, such that oxygen atoms are not directly adjacent to each other -OCO- or -COO- may be substituted,
n ¹¹ represents 0, 1 or 2;
A ¹¹ is a group (a), a group (b) and a group (c) shown below:
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , And one or more non-adjacent -CH = present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by -N =).
Group (a), group (b) and group (c) are each independently an alkyl group having 1 to 12 carbon atoms, or 1 to 12 carbon atoms. alkoxy group, a halogen, a cyano group, a nitro group, or ^P 11 ^{-S 11} - be substituted with good,
L ¹⁰ and L ¹¹ each independently represent a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —OC ₂ H ₄ O—, —COO—, —OCO—, — CH = CR ^a -COO-, -CH = CR ^a -OCO-, -COO-CR ^a = CH-, -OCO-CR ^a = CH-,-(CH ₂ ) _z -COO-,-(CH ₂ ) _{z -OCO -, - OCO- (CH} 2) z -, - COO- (CH 2) z -, - CH = CH -, - CF 2 O -, - OCF 2 - or -C≡C- (wherein And ^Ra each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, each z independently represents an integer of 1 to 4).
When a plurality of P ²¹ , S ²¹ , L ¹¹ and A ¹¹ exist, they may be the same or different. ) The liquid crystal composition according to claim 1, wherein the adsorptive group is an atomic group having a hetero atom selected from the group consisting of N, O, S, P and Si. 3. The method according to claim 1, wherein one of the two or more polymerizable monomers represented by the general formula (I) improves the reactivity of the other polymerizable monomer represented by the general formula (I). The liquid crystal composition as described. General Formulas (N-1), (N-2) and (N-3)

(Wherein, R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 and R ^N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or more non-adjacent ones in the alkyl group And two or more of —CH ₂ — may be independently substituted by —CH = CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—, respectively.
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are each independently (a) 1,4-cyclohexylene group (one -CH _2- present in this group or adjacent thereto And two or more -CH _2- may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH = or two or more non-adjacent —CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by —N =. And d) represents a group selected from the group consisting of 1,4-cyclohexenylene groups, and the groups (a), (b), (c) and (d) are each independently cyano. It may be substituted by a group, a fluorine atom or a chlorine atom,
^{Z N11, Z N12, Z N21} , Z N22, Z N31 and ^{Z N32} are each independently a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O-, -COO-, -OCO-, -OCF _2- , -CF ₂ O-, -CH = N-N = CH-, -CH = CH-, -CF = CF- or -C≡C- Represent
X ^N21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents -CH ₂ -or an oxygen atom,
n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 and n ^N32 each independently represent an integer of 0 to 3, but n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 each represent an integer Independently, 1, 2 or 3, and when there are a plurality of A ^N11 to A ^N32 and Z ^N11 to Z ^N32 , they may be the same or different. 4. The liquid crystal composition according to any one of claims 1 to 3, containing one or two or more compounds selected from the compounds represented by). General formula (L)

(Wherein, R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently And may be substituted by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-,
n ^L1 represents 0, 1, 2 or 3;
A ^L1 , A ^L2 and A ^L3 are each independently (a) 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ groups -May be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = may be replaced by -N =) and (c) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , And one or more non-adjacent -CH = present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced by -N =).
And the group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^L1 and ^{Z L2} are each independently a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF _2- , -CF ₂ O-, -CH = N-N = CH-, -CH = CH-, -CF = CF- or -C≡C-
When n ^L1 is 2 or 3 and a plurality of A ^L2 is present, they may be the same or different, and when n ^L1 is 2 or 3 and a plurality of Z ^L2 is present, they may be Are the same as or different from each other, but the compounds represented by Formula (N-1), Formula (N-2) and Formula (N-3) are excluded. 5. The liquid crystal composition according to any one of claims 1 to 4, containing one or two or more compounds selected from the compounds represented by). One of the polymerizable monomer represented by the general formula ^{(I), n 11} is 0, and one of ^{R 102, R 103, R 104} , R 105, R 106, R 107, R 108 or ^{R 109} one or is an alkyl group having from 1 to 18 carbon ^atoms, independently ^{R 101} and ^{R 110} are ^each, P 21 ^{-S 21} - it is a liquid crystal according to any one of claims 1 to 5 Composition.