JP6828832B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

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.

In general, a liquid crystal display element such as a liquid crystal panel or a liquid crystal display changes the state of arrangement of liquid crystal molecules by an external stimulus such as an electric field, and uses the change in optical characteristics accompanying the change 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 liquid crystal molecules are arranged in advance in a specific direction on the surface of the substrate that comes into contact with the liquid crystal molecules. It is common to form an alignment film for this purpose.

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

Therefore, in recent years, there has been a demand for the development of a liquid crystal display element that does not require an alignment film represented by a polyimide layer by using a liquid crystal composition containing a spontaneous alignment agent that controls the orientation of liquid crystal molecules for the liquid crystal layer.

For example, in Patent Document 1, instead of lauryl acrylate having a relatively weak interaction with a liquid crystal molecule, a monofunctional biphenyl monomer having an octyl group and showing high linearity and a biphenyl monomer having a stearyl group showing a low straight line are shown. A liquid crystal composition containing a spontaneously oriented material that suppresses a decrease in voltage retention by using a liquid crystal composition containing a functional biphenyl monomer has been described.

Further, Patent Document 2 discloses various liquid crystal compositions containing a polymerizable self-alignment additive that controls the orientation 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-oriented additive is filled in a test cell without a polyimide oriented layer (a test cell without a pre-aligned layer), It is stated that it has a spontaneous homeotropic (vertical) orientation with respect to the substrate surface, this orientation is kept stable up to the transparent point, and the formed VA cell can be reversibly switched by applying a voltage. There is.

U.S. Patent Publication No. 2017-0123275 Special Table 2017-523289

However, the composition containing two types of hydrophobic monomers having a long alkyl chain and a biphenyl skeleton as shown in Patent Document 1 described above does not interact with the liquid crystal molecules of the liquid crystal layer packed between the pair of substrates. Although it is considered to be stronger than lauryl acrylate, there arises a problem that the orientation direction of liquid crystal molecules cannot be regulated due to its low adsorption force to the substrate.

Further, Patent Document 2 describes a mode in which a non-polymerizable self-orientation additive or one kind of polymerizable monomer is mixed with a polymerizable self-orientation additive having an adsorbing group as a hydroxyl group or an amino group. Therefore, it is considered that the molecular design takes into consideration the adsorption force to the substrate. However, if the adsorptive power of the polymerizable self-alignment additive to the substrate is too high, there arises a problem that the polymerizable self-alignment additive does not spread uniformly on the substrate, resulting in uneven orientation. Further, the state of the layer in which the polymerizable self-orientation additive is adsorbed on the substrate and polymerizes is not considered. That is, in the composition described in Patent Document 2, the composition or the polymerized component obtained by mixing the non-polymerizable self-orientation additive and the polymerizable self-orientation additive is only the polymerizable self-orientation additive or one kind of polymerizable. Since it is one of the monomers, it is difficult to form a dense layer. If a dense layer is not formed, the vertically oriented component of the self-aligning additive is not fixed, so that the amount of change in the pretilt angle becomes large, and there arises a problem that the seizure characteristic deteriorates.

Therefore, an object to be solved by the present invention is to provide a liquid crystal composition having excellent vertical orientation and seizure characteristics, and to provide a liquid crystal display element using the same.

Another problem to be solved by the present invention is to provide a liquid crystal composition having excellent three properties of vertical orientation, low temperature solubility and seizure property, and to provide a liquid crystal display element using the same. is there.

As a result of diligent studies by the present inventors, a liquid crystal composition containing one or more kinds of self-oriented polymerizable monomers and two or more kinds of polymerizable monomers having a specific chemical structure, and a liquid crystal display element using the same. , The present invention has been completed by finding that the above problems can be solved.

The liquid crystal composition according to the present invention exhibits excellent vertical orientation with respect to liquid crystal molecules and excellent seizure characteristics.

The liquid crystal composition according to the present invention exhibits excellent expandability (wetting spread) with respect to the substrate.

The liquid crystal composition according to the present invention has no orientation unevenness or can reduce orientation unevenness.

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

The first of the present invention includes one or more spontaneously oriented monomers having a mesogen group, at least one polymerizable group represented by the general formula (PG1), and at least one adsorbing group.
It is a liquid crystal composition containing two or more kinds 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 spontaneous orientation monomer.

(In the above formula, the above P ¹¹ is any group represented by the following formulas (PI) to (P-IX).

(In the formula, R^p11And R^p12Independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and W^p11Represents a single bond, -O-, -COO- or methylene group, t^p11Represents 0, 1 or 2, and the polymerizable group P ¹¹One or more hydrogen atoms of may be substituted with the adsorbent. )
S¹¹Represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one -CH in the alkylene group.₂-Or two or more -CHs that are not adjacent₂− May be substituted with −O−, −OCO− or −COO− so that oxygen atoms are not directly adjacent to each other.¹¹One or more hydrogen atoms of may be substituted with the adsorbent. * In the above chemical formula represents a bond. )

(In the above general formula (I), R¹⁰¹, R¹⁰², R¹⁰³, R¹⁰⁴, R¹⁰⁵, R^{10 6}, R¹⁰⁷, R¹⁰⁸, R¹⁰⁹And R¹¹⁰Are independent of each other, P²¹-S²¹-, Represents any of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, and the above P.²¹Is any group represented by the above formulas (RI) to (R-IX).
S above²¹Represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more -CHs in the alkylene group.₂-Can be replaced with -O-, -OCO- or -COO- so that the oxygen atoms are not directly adjacent.
n¹¹Represents 0, 1 or 2
n¹²And n¹³Independently represent 0 or 1, respectively
n¹¹+ N¹²+ N¹³= 1, 2 or 3
A¹¹The following groups (a), groups (b) and groups (c):
(A) 1,4-Cyclohexylene group (one -CH present in this group)₂-Or two or more -CHs that are not adjacent₂-May be replaced with -O-. )
(B) A 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =) and.
(C) Naphthalene-2,6-diyl group, 2,7-phenanthreneyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene- One -CH = present in the 2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or two or more non-adjacent -CH = are -N = May be replaced with.)
Representing a group selected from the group consisting of, the above groups (a), groups (b) and groups (c) are independently alkyl groups having 1 to 12 carbon atoms and 1 to 12 carbon atoms. Alkoxy group, halogen, cyano group, nitro group or P¹¹-S¹¹May be replaced with-
L¹⁰And L¹¹Are independent, single bond, -OCH₂-, -CH₂O-, -C ₂H₄-, -OC₂H₄O-, -COO-, -OCO-, -CH = CR^a-COO-, -CH = CR^a-OCO-, -COO-CR^a= CH-, -OCO-CR^a= CH-,-(CH₂)_z-COO-,-(CH₂)_z-OCO-, -OCO- (CH₂)_z-, -COO- (CH₂)_z-, -CH = CH-, -CF₂O-, -OCF₂-Or -C≡C- (in the formula, R^aEach independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, z independently represents an integer of 1 to 4 respectively. )
P²¹, S²¹, L¹¹And A¹¹When there are a plurality of them, they may be the same or different from each other. )
Since the liquid crystal composition according to the present invention contains at least three types of monomers having different chemical structures, it is easy to cope with various polymerization conditions, and the polymerization reaction is easy to proceed, so that a dense polymer network layer is formed. Can be formed. Further, by using two or more kinds of polymerizable monomers, it is possible to include two or more kinds of monomers whose functions are separated from the polymerizable monomer group involved in the polymerization reaction and the polymerizable monomer group contributing to the vertical orientation. Therefore, it is considered that high vertical orientation and a small amount of pre-tilt change can be achieved.

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

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

The spontaneously oriented monomer has a polymerizable group for polymerization, a mesogen group similar to a liquid crystal molecule, and an adsorption group capable of interacting with a member that directly contacts the liquid crystal layer, and if necessary, the orientation of the liquid crystal molecule. 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 the general formula (PG1), and P ¹¹ is selected from the group represented by the following general formulas (PI) to (P-IX). Is the basis for

(In the formula, R ^p11 and R ^p12 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and W ^p11 is a single bond, −O. -, -COO- or methylene group, t ^p11 represents 0, 1 or 2)
The P ¹¹ is preferably a group selected from the group represented by the following general formulas (PI) to (P-IX), and is preferably the general formula (PI).

In spontaneous orientation monomers according to the present invention, P ^{11 -S} 11 ^- are mesogenic groups may be bonded to an adsorptive group and / or bending group.

Further, in the spontaneously oriented monomer according to the present invention, the polymerizable group is preferably bonded to the mesogen group, the adsorbing group or the bending group directly or via a spacer group, and is directly attached to the mesogen group or the adsorbing group. Alternatively, it is more preferable to bond via a spacer group.

The spacer group (Sp ¹¹ ) preferably represents a single-bonded or linear or branched alkylene group having 1 to 20 carbon atoms, and has a single-bonded or linear carbon atom number of 1 to 20. It is more preferable to represent an alkylene group, and it is more preferable to represent a single bond or a linear alkylene group having 2 to 10 carbon atoms. Further, in the spacer group (Sp ¹¹ ), one in the alkylene group or two or more −CH ₂ − not adjacent to each other are independently −CH = CH−, −C≡C−, −. It may be replaced 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 even more preferable, 2 or 3 is even more preferable, and 2 is even more preferable.

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

"Mesogen group"
The mesogen group according to the present invention refers to a group having a rigid portion, for example, one having one or more cyclic groups, preferably having 2 to 4 cyclic groups, and a cyclic group. It is more preferable to have 3 to 4 of the cyclic groups, and if necessary, the cyclic groups may be linked by a linking group. The mesogen group preferably has a skeleton similar to that of the liquid crystal compound used for the liquid crystal layer.

In the present specification, the "cyclic group" refers to an atomic group in which constituent atoms are cyclically bonded, and is a carbocyclic ring, a heterocyclic ring, a saturated or unsaturated cyclic structure, a monocyclic or bicyclic structure, or a polycyclic ring. Includes formula structures, aromatics, non-aromatics, etc. Further, the cyclic group may contain at least one heteroatom, and may be further substituted with at least one substituent (halogen atom, reactive functional group, organic group (alkyl, aryl, etc.)). When the group is monocyclic, the mesogen group preferably contains two or more monocycles.

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

(In the formula, ^ZAL is 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, among the alkylene groups. one or not adjacent two or more -CH ₂ - is -O -, - COO- or -OCO- may be substituted with,
A ^AL represents a divalent cyclic group.
Z ^AL and one in ^{A AL} or two or more hydrogen atoms are each independently a halogen atom, an adsorption ^group, P 11 ^{-S 11} - or a monovalent organic group may be substituted with,
If Z ^AL and A ^AL is present in plural, respectively may be the being the same or different, m ^AL represents an integer of 1 to 5, the left end in the formula * and right * are Represents a join hand. )
In formula ^{(AL), Z AL} represents an alkylene group of a single bond or a C2-20 is preferred, an alkylene group of a single bond or a C2-10 is more preferred. One or two or more non-adjacent −CH ₂ −s in the alkylene group may be substituted with −O−, −COO− or −OCO−. Further, when the purpose is the linearity of the rod-shaped molecule, a single bond in which the ring and the ring are directly connected or a form in which the number of atoms directly connecting the ring and the ring is an even number is preferable. For example, in the case of −CH ₂ −CH ₂ COO−, the number of atoms directly connecting the rings is four.

In the general formula (AL), the cyclic groups are 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-Octahydrophenanthrene-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'] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselofeno [3,2-d] b] It is preferable to represent one type of structure selected from the group consisting of a selenophen-2,7-diyl group and a fluorene-2,7-diyl group, and these structures may be unsubstituted or substituted. A 1,4-phenylene group, a 1,4-cyclohexylene group, a 2,6-naphthylene group or a phenanthrene-2,7-diyl group is more preferable, and a 1,4-phenylene group or a 1,4-cyclohexylene group is preferable. .. Also, one or more hydrogen atoms of the halogen atom in the cyclic group, adsorptive group, P ^{11 -S} 11 ^- or may be substituted with a monovalent organic group.

In the general formula (AL), a monovalent organic group is a group having a chemical structure formed by the organic compound in the form of a monovalent group, and one hydrogen atom is removed from the organic compound. An atomic group, for example, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, an alkenyloxy group having 2 to 15 carbon atoms, and the like. Therefore, an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms is preferable. Further, one or two or more -CH ₂ −s in the above alkyl group, alkenyl group, alkoxy group and alkenyloxy group may be substituted with −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.

Preferred forms of the mesogen group include the following formulas (me-1) to (me-42). The general formula (AL) is a structure in which 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 with a group (for example, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorbing group or a bending group.

The preferred forms of the mesogen groups are formulas (me-8) to (me-44), and more preferably the 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), more preferably formulas. (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).

A particularly preferable form of the mesogen group is represented by the following general formula (AL-1) or (AL-2), and the formula (AL-2) is more preferable.

(In the ^formula, X ^{a11 to X AL18} are each independently a hydrogen atom, a halogen ^{atom, P} 1 1 ^{-S 11 -,} represents an adsorption group or bend group, ring A and ring B are each independently, cyclohexane Represents a ring or a benzene ring
Any one or more of X ^{a11 to} X ^al18 is substituted with the adsorbent.
Any one or more of X ^{a11 to} X ^al18 is substituted with the 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 formulas ^{(AL-1), X a11} or ^X a18 is preferably at least one ^{to X a112} or more is replaced with adsorption ^group, at least one or more ^{X a11} or ^{X a110} Is more preferably substituted with an adsorbent. In this case, the adsorbent group may be substituted with P ¹¹ − S ¹¹ −. In particular, when the ring A is a cyclohexane ring, it is preferable that X ^a110 is substituted with an adsorbent group.

In the above formula (AL-1), X^a16~ X^a114It is preferable that at least one or more of the above is substituted with a polymerizable group, and X^al9Or X^a111Either one is P ¹¹-S¹¹It is more preferable that it is replaced with −.

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 are substituted with bending groups, and X ^{a11 to} X. It is preferable that at least one or more of ^a13 , X ^{a6 to} X ^a19 , X ^{a111 to} X ^a114 or X ^{a117 to} X ^{a 118} are substituted with bending groups. It is more preferable that X ^{a1 1} 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 bending group in X ^a11 of the former has a larger number of carbon atoms than the bending group of the latter. The bending group may be substituted with P ^{1 1} − S ¹¹ −.

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

In the above formula (AL-2), X^al6~ X^a110Any one or two or more of P ¹¹-S¹¹It is preferably replaced with −, and X^al7Or X^a19Either one is P¹¹-S¹¹It is more preferable that it is replaced with −.

In the above formula ^(AL-2), or at least one or two of X ^{a16 to 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 is substituted with a bending group, and X ^a11 , X ^{a4 to} X ^{a 17} or It is preferable that at least one or more of X ^{a19 to} X ^a112 are substituted with bending groups. It is more preferable that X ^a11 is substituted with a bending group and any one of X ^{al4 to} X ^a17 or X ^{a 19 to} X ^a112 is substituted with a bending group. In this case, it is more preferable that the bending group in X ^a11 of the former has a larger number of carbon atoms than the bending group of the latter. The bending group may be substituted with P ¹¹ − S ¹¹ −.

"Adsorption group"
The adsorbent group according to the present invention is a group having a role of adsorbing with an adsorption medium such as a substrate, a membrane, and an electrode. Adsorption is generally classified into chemical adsorption that forms a chemical bond (covalent bond, ionic bond or metal bond) and adsorbs between the adsorption medium and the adsorbent, or physical adsorption other than the chemical adsorption. The adsorption of the book may be either chemical adsorption or physical adsorption, but it is preferable to adsorb with the adsorption medium by physical adsorption. Therefore, the adsorbent group according to the present invention is preferably a group that can be physically adsorbed to the adsorption medium, and it is more preferable that the adsorbent group is bonded to the adsorption medium by an intermolecular force. Examples of the form of binding to the adsorption medium by the intermolecular force include binding to the adsorption medium by interaction such as permanent dipole, permanent quadrupole, dispersion force, charge transfer force or hydrogen bond. A preferred form of the adsorbent according to the present invention is a form capable of binding to an adsorption medium by hydrogen bonding. In this case, the adsorbent group according to the present invention may be a donor or acceptor of a proton intervening a hydrogen bond, or may be both.

The adsorbent 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 referred to in the present specification means an atomic group in which a carbon atom and a hetero atom are directly linked. The heteroatom is preferably at least one selected from the group consisting of N, O, S, P, B and Si, and at least one selected from the group consisting of N, O and S. It is preferable that it is at least one selected from the group consisting of N and O, and it is preferably O.

Further, in the spontaneously oriented monomer according to the present invention, the valence of the polar elements according to the present invention is not particularly limited such as monovalent, divalent and trivalent, and the number of polar elements in the adsorbent group is also particularly limited. There is nothing.

The spontaneously oriented monomer according to the present invention preferably has 1 to 8 adsorbent groups, more preferably 1 to 4 adsorbent groups, and even more preferably 1 to 3 adsorbent groups in one molecule.

Incidentally, the adsorption group according to the present ^invention, P 11 ^{-S 11} - and bent groups are excluded.

The adsorbent group according to the present invention contains one or more polar elements, and the adsorbent group is roughly classified into a cyclic group type and a chain type group type. A cyclic base type is a form in which a cyclic group having a cyclic structure containing a polar element is included in the structure, and a chain type is a form in which a cyclic group having a cyclic structure containing a polar element is included in the structure. There is no form. The chain type group has a form having a polar element in a linear or branched chain group, and may have a cyclic structure in which a polar element is not contained in a part thereof.

The form in which the adsorbent 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, when the adsorbent group according to the present invention is in the form of containing a cyclic group, it suffices to contain only a cyclic group containing a polar element, and the adsorbent group as a whole may be branched or linear. ..

The form in which the adsorbent group according to the present invention is an open chain means that there is no cyclic atomic arrangement containing a polar element in the molecule and at least one polar element is in a linear atomic arrangement (may be branched). Means the included form. The chain group in the present specification refers to an atomic group in which constituent atoms are linearly (may be branched) bonded without a cyclic atomic arrangement in the structural formula, and refers to 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, and at least one. It is a concept that may be substituted with a substituent (reactive functional group (vinyl group, acrylic group, methacryl group, etc.), chain organic group (alkyl, cyano, etc.). Further, the chain type group of the present invention is a direct group. It may be chain-shaped or branched.

The adsorbent group according to the present invention preferably has a chain type group or a cyclic group, preferably a chain type group when the adsorption ability is important, and preferably a cyclic group from the viewpoint of stability to the liquid crystal composition.

When the adsorbing group according to the present invention is a cyclic group, 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, and a heteroaromatic group having 3 to 12 carbon atoms (including a fused ring) or a heteroaliphatic group having 3 to 12 carbon atoms (including a fused ring) is further preferable, and a 5-membered ring complex is more preferable. It is more preferable to represent an aromatic group, a 5-membered ring heteroaliphatic group, a 6-membered ring heteroarophatic group or a 6-membered ring heteroaliphatic group, and the hydrogen atom in these ring structures is a halogen atom or a carbon atom number. It may be substituted with 1 to 5 linear or branched alkyl groups or alkyloxy groups.

When the adsorbent group according to the present invention is a chain type group, it is preferable that the hydrogen atom or −CH _{2− in the} linear or branched alkyl group having 1 to 20 carbon atoms is replaced with 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- Alternatively, it may be replaced by -OCO-COO-. When the adsorbent group according to the present invention is a chain type group, it is preferable that the end portion contains a polar element or contains two or more polar elements.

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

Specifically, the types of polar elements according to the present invention include polar elements containing oxygen atoms (hereinafter, oxygen-containing polar elements), polar elements containing nitrogen atoms (hereinafter, nitrogen-containing polar elements), and polarities containing phosphorus atoms. Element (hereinafter, phosphorus-containing polar element), polar element containing boron atom (hereinafter, boron-containing polar element), polar element containing silicon atom (hereinafter, silicon-containing polar element) or polar element containing sulfur atom (hereinafter, including) It is preferably a partial structure represented by (sulfur polar element), and from the viewpoint of adsorption ability, a nitrogen-containing polar element, a nitrogen-containing polar element or an oxygen-containing polar element is more preferable, and an oxygen-containing polar element is further preferable.

Examples of the oxygen-containing polar element include a hydroxyl group (-OH) and an alkylol group (-R).^t−OH; R ^tIs an alkylene group), an alkoxy group (-OR; where R is an alkyl group), a formyl group (-CHO), a carboxyl group (-COOH), and an ether group (-R).^tOR^t’-; However, R^t, R^t’Is an alkylene group or an alkenylene group), a carbonyl group (-R)^t-C (= O) -R ^t’-; However, R^t, R^t’Is an alkylene group or an alkenylene group), a carbonate group (-OC (= O) -O-) and an ester group (-COOR).^t’-; However, R^t′ Is preferably 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.

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

The phosphorus-containing polar element is at least selected from the group consisting of a phosphinyl group (-CX _2- P (= O) H ₂ ) and a 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, _three -Si (OH) groups or -Si (OR) (OR') (OR "); however, R, R', R" are alkyl groups) as carbon atoms. It is preferably a linked 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), sulfo group _(-SO 3 H) and sulfino group (-S (= O) OH) of at least one group or the group is selected from the group consisting of is linked to a carbon atom group Is preferable.

Therefore, in the adsorption group according to the present invention, the cyclic group is a group having an oxygen-containing polar element (hereinafter, oxygen-containing cyclic group), and the cyclic group is a group having a nitrogen atomic polar element (hereinafter, nitrogen-containing ring). Cyclic group), a group in which the cyclic group has a phosphorus-containing polar element (hereinafter, phosphorus-containing cyclic group), a group in which the cyclic group has a boron-containing polar element (hereinafter, boron-containing cyclic group), a cyclic group. The group is a group having a silicon-containing polar element (hereinafter, silicon-containing cyclic group), the cyclic group is a group having a sulfur-containing polar element (hereinafter, sulfur-containing cyclic group), and the chain type group is an oxygen-containing polar element. (Hereinafter, oxygen-containing chain type group), chain type group having a nitrogen atom polar element (hereinafter, nitrogen-containing chain type group), chain type group having a phosphorus-containing polar element (hereinafter, below) , Cyclic group containing phosphorus), group having a boron-containing polar element (hereinafter, boron-containing chain group), chain group having a silicon-containing polar element (hereinafter, silicon-containing chain group) ) And the chain type group preferably contains one or more groups themselves selected from the group consisting of groups having a sulfur-containing polar element (hereinafter, sulfur-containing chain type group) or the group, and has an adsorptive capacity. From the viewpoint of the above, 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 type group and a nitrogen-containing chain type group.

The 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.

Moreover, it is preferable that the carbonyl group contains any of the following groups.

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

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

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

(In the above general formula, R^atEach independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In the above general formula, Z^atRepresents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms or a linear or branched alkenylene group having 2 to 18 carbon atoms, and represents the alkylene group or the alkenyllen. Group-CH₂− May be replaced with −O−, −COO−, −C (= O) −, −OCO− so that oxygen atoms are not directly adjacent to each other, and X ^atRepresents an alkyl group having 1 to 5 carbon atoms, and −CH of the alkyl group₂-May be replaced with -O-, -COO-, -C (= O)-, -OCO- so that the oxygen atoms are not directly adjacent to each other. )
The nitrogen-containing chain type group preferably contains the following groups.

(In the general ^{formula, R at, R bt, R} ct and ^{R dt} independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.)
The sulfur-containing chain type group preferably contains the following groups.

The silicon-containing chain type group preferably contains −Si (OH) ₃ or −Si (OR) (OR ′) (OR ″); where R, R ′ and R ″ are alkyl groups). .. The boron-containing chain type group preferably contains −B (OH) ₂ . The phosphorus-containing chain type group preferably contains −OP (= O) (OH) ₂ .

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

(In the above general formula (T), X^t1Is a linear or branched alkyl group having 1 to 18 carbon atoms or -NH.₂The hydrogen atom in the alkyl group is a cyano group, P.¹¹-S¹¹May be substituted with −, or −CH of the alkyl group₂-May be replaced with -O-, -COO-, -C (= O)-, -OCO-, -CH = CH- so that the oxygen atoms are not directly adjacent to each other.
R above^t1Is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or Z.^t1A linear or branched alkylene group having 1 to 8 carbon atoms or Z which may be bonded to^t1Represents a linear or branched alkenylene group having 2 to 8 carbon atoms which may be bonded to Z.^t2Represents 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 alkenylene group. -CH₂-May be replaced with -O-, -COO-, -C (= O)-, -OCO- so that the oxygen atoms are not directly adjacent to each other.
Z^t1Represents 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 of the alkylene group.₂-May be replaced with -O-, -COO-, -C (= O)-, -OCO- so that the oxygen atoms are not directly adjacent to each other, and X.^t1Is -Z^t2-OR^atIt is the basis and R ^atIf is an alkylene group or an alkenylene group, Z^t1Replace the hydrogen atom of R^t1May be combined with
W^t0Represents a linear or branched alkylene group having 1 to 18 carbon atoms, and −CH of the alkylene group₂− May be substituted with −O−, −CH = CH−, −COO−, −C (= O) −, −OCO− so that oxygen atoms are not directly adjacent to each other, and the hydrogen atom of the alkylene group is It may be replaced with the general formula (T).
W^t1Represents a single-bonded, linear or branched alkylene group, and -CH of the alkylene group.₂-May be replaced with -O-, -COO-, -C (= O)-, -OCO- so that the oxygen atoms are not directly adjacent to each other.
n^t1Represents an integer between 0 and 4
The hydrogen atom in the molecule is the above-mentioned polymerizable group P¹¹-S¹¹May be substituted with −, where * represents a bond and binds to a mesogen group, polymerizable group, bending group or spacer group. )
In the above general formula (T), preferable X^t1Is a linear or branched alkyl group having 1 to 17 carbon atoms, -NH.₂Or -Z^t2-OR^t1Representing a group, the hydrogen atom in the alkyl group is a cyano group, P¹¹-S¹¹It may be replaced with −, and the above R^t1Is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or Z.^t1A linear or branched alkylene group having 1 to 8 carbon atoms or Z which may be bonded to^t1Represents a linear or branched alkenylene group having 2 to 8 carbon atoms which may be bonded to Z.^t2Represents 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 alkenylene group. -CH₂-May be replaced with -O-, -COO-, -C (= O)-, -OCO- so that the oxygen atoms are not directly adjacent to each other.

In the above general formula (T), the above general formula (T) is the following general formula (t) as a form in which the adsorption group (general formula (T)) may be replaced by the adsorption group (general formula (T)). ) Can be mentioned.

(In the general formula (t), X ^t1 , Z ^t1 , W ^t1 and n ^{t 1} are the same as the symbols in the 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 with a spacer group. )
"-W ^t2- Any" in the above 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 above general formula (t), the 2 to 4 valent organic group is a group having a chemical structure formed by the organic compound in the form of a 2 to 4 valent group, and a hydrogen atom is formed from the organic compound. An atomic group obtained by removing 2 to 4 groups.

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

The group represented by the general formula (t) is a preferred embodiment of W ^t0 in the general formula (T), that is, even if the adsorption group (general formula (T)) is replaced with the adsorption group (general formula (T)). It 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 atomic or alkylene polyvalent group, for example, the following general formula (ta) or (tb) can be mentioned.

(The formula (t-a) and in ^{(t-b), R tc} represents a hydrogen atom, an alkyl group of 1 to ten several linear or branched carbon atoms 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'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'are independent of each other and have the same meaning as n ^t1 in the general formula (T), and the hydrogen atom in the molecule may be substituted with the above-mentioned polymerizable group P ¹¹ −S ¹¹ −. * Represents a bond and binds to a mesogen group, a polymerizable group, a bending group or a spacer group. )
In the general formula (t), for example, when -W ^t2- Any is a tetravalent organic group, that is, mt1'is 3, and -W ^t2- Any is an alkylene multivalent group, for example, the following general formula (t) tk) can be mentioned.

(In the above formula (t-c), Z ^t1 , Z ^t1'and Z ^t1'' independently represent the same meaning as Z ^t1 in the general formula (T).
X ^t1 , X ^t1'and X ^t1'' 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 represent the same meaning as n ^t1 in the general formula (T), and the hydrogen atom in the molecule is replaced with the above-mentioned polymerizable group P ¹¹ −S ¹¹ −. * Represents a bond and binds 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 forms represented by the general formula (ta), the general formula (tb), and the general formula (tc), the form represented by the general formula (ta) is preferable. ..

In the above general formula (t), -W ^t2- Any is preferably a single-bonded or divalent to trivalent organic group, and is a single-bonded, linear or branched alkylene group having 1 to 8 carbon atoms (1 to 8 carbon atoms). -CH 2 in the alkylene group _-. the oxygen atom may be replaced by -O- so as not immediately adjacent), linear or branched carbon atoms 1-8C alkanetriyl group (said The -CH _{2- of the} alkanetriyl group may be replaced with -O- so that the oxygen atoms are not directly adjacent to each other) or a linear or branched alkyl-iriden group (-CH of the alkyl-iriden group). ₂ − may be replaced with −O− so that oxygen atoms are not directly adjacent to each other.) Is more preferable. For example, the following groups can 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} - represents a), NT0 represents 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^t1Represents a single-bonded, linear or branched alkylene group having 1 to 8 carbon atoms (single bond, linear or branched alkylene group, and -CH of the alkylene group.₂-May be replaced with -O-, -COO-, -C (= O)-, -OCO- so that the oxygen atoms are not directly adjacent to each other. ) Is preferably represented, and represents a single bond or linear or branched alkylene group having 1 to 7 carbon atoms (single bond or linear or branched alkylene group, and −CH of the alkylene group.₂-May be replaced with -O- so that the oxygen atoms are not directly adjacent to each other. ) Is more preferable. Also W ^t1May be substituted and bonded to a hydrogen atom of a mesogen group, a polymerizable group or a bending group.

The general formula (T) or the general formula ^{(t), X t1} is a form that does not bind to ^{Z t1 (Kusarishikimoto), X t1} is a form to form a ring with ^{Z t1} (cyclic group) Includes.

In the former form, a linear or branched alkyl group having 1 to 8 carbon atoms, -NH ₂, -Z^t2-OR^t1A linear or branched alkyl group having 1 to 7 carbon atoms substituted with a group or a cyano group is preferable, and a linear or branched alkyl group having 1 to 7 carbon atoms, −Z.^t2-OR^t1A linear or branched alkyl group having 1 to 7 carbon atoms substituted with a group or a cyano group is more preferable. In the case of the former form, the above R^t1Each independently represents a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, and Z^t2Is preferably 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 (the alkylene group or the alkenylene group). -CH₂-May be replaced with -O-, -COO-, -C (= O)-, -OCO- so that the oxygen atoms are not directly adjacent to each other).

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 a linear or branched alkenylene group of up to 7 and is preferably bonded to R ^t1 by substituting the hydrogen atom of Z ^t1 , for example, it may be represented by the following general formula (T'). preferable.

(In the above general formula (T'), R ^t1'is independently a linear or branched alkylene group having 1 to 8 carbon atoms or a linear or branched alkylene group having 2 to 8 carbon atoms. Represents an alkenylene group
Z ^{t2'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. The −CH ₂₋ of the group or the alkenylene group may be replaced with −O−, −COO−, −C (= O) −, −OCO− so that oxygen atoms are not directly adjacent to each other.
Z ^{t1 'represents} alkenylene 3-valent group having a carbon number of 1 to 18 linear or branched alkylene 3 diradical or carbon atoms 1 to 18 straight-chain or branched, the alkylene 3 The valence group or alkenylene trivalent group -CH _2- may be replaced with -O-, -COO-, -C (= O)-or OCO- so that oxygen atoms are not directly adjacent to each other.
W ^t2 represents a single bond or a divalent to tetravalent organic group.
-W ^t1- represents a single-bonded or linear or branched alkylene group, and -CH _{2- of the} alkylene group is -O-, -COO-, -C (=) so that oxygen atoms are not directly adjacent to each other. O)-may be replaced with -OCO-,
n ^{t1'represents} an integer greater than or equal to 1 and less than or equal to 4.
^{mt1'represents} an integer of 1 or more and 3 or less, the hydrogen atom in the molecule may be substituted with the above-mentioned polymerizable group P ¹¹ −S ^{1 1} −, and * represents a bond, a mesogen group, a polymerizable group. , Bends or spacers. )
The alkylene trivalent group refers to a trivalent group formed by further removing one hydrogen atom from the alkylene group. The alkenylene trivalent group refers to a trivalent group formed by removing one hydrogen atom from the alkenylene group, and is a trivalent group having a free valence in a so-called hydrocarbon chain, for example, an alkanetriyl group or an alkyl-iriden. Including groups and the like.

In the above general formula (T), when X ^t1 does not bond with Z ^t1 (chain type group), Z ^{t 1} is a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms. Alternatively, it represents a linear or branched alkenylene group having 2 to 12 carbon atoms, and the -CH _{2- of the} alkylene group is changed to -O-, -COO-, -C (= O)-, or -OCO-. It may be replaced.

In the above general formula (T), X ^t1 is the same as the above general formula (T') in the case of a form (cyclic group) bonded to Z ^t1 .

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

The general formula (T) is a cyclic group represented by the general formulas (T-1-1) to (T-4-1) and 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 the chain type group represented by. When a cyclic group is selected as the adsorbent group represented by the general formula (T) according to the present invention, the general formula (T-1-1) or the general formula (T-1-1) or the general formula (from the viewpoint of adsorptivity and compatibility with the liquid crystal composition). T-2-1) is preferable. When a chain type group is selected as the adsorbent group represented by the general formula (T) according to the present invention, the general formula (T-5-1) or the general formula (T-5-1) or the general formula (from the viewpoint of adsorptivity and stability to the liquid crystal composition). T-6-1) is preferable.

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

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, 1 to 7 carbon atoms, alkyl groups or polymerizable group ^P 11 ^{-S 11} - represented by a hydrogen atom in the molecule of the polymerizable group ^P 11 -S It may be substituted with ¹¹ −, and * represents a bond and binds to a mesogen group, a polymerizable group, a bending group or a spacer group.)
The general formula (T-5-1) preferably 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 1 to carbon atoms Representing eight linear or branched alkyl or cyanated alkyl groups, at least two or more of these alkyl groups -CH ₂ − are -CH = CH- so that oxygen atoms are not directly adjacent. , -C≡C -, - O-, or -NH- may be substituted ^{with, R tc} represents a hydrogen atom, an alkyl group or a polymerizable group having 1 to 7 carbon atoms ^P 11 ^{-S 11} - in Represented, n ^t1 , n ^t2 and n ^t3 independently represent 0 or 1, and the hydrogen atom in the molecule may be replaced with P ¹¹ −S ¹¹ −).
Specific examples of the above general formula (T-5-1) include the following groups.

(In the ^{formula, R tc} represents a hydrogen atom, 1 to 7 carbon atoms, alkyl groups or polymerizable group ^P 11 ^{-S 11} - represented by a hydrogen atom in the molecule of the polymerizable group ^P 11 -S It may be substituted with ¹¹ −, and * represents a bond and binds to a mesogen group, a polymerizable group, a bending group or a spacer group.)

(In the above formula, R ^ct is represented by a hydrogen atom, an alkyl group having 1 to 7 carbon atoms or a polymerizable group P ¹¹ −S ¹¹ −, and the hydrogen atom in the molecule is the above polymerizable group P ¹¹ −S. ^It may be substituted with ¹¹ −.) (* Represents a bond and binds to a mesogen group, a polymerizable group, a bending group or a spacer group.)
Specific examples of the above general formula (T-6-1) include the following examples.

(In the formula, ^{R tc} represents a hydrogen atom, 1 to 7 carbon atoms, alkyl groups or polymerizable group ^P 11 ^{-Sp 11} - represented by a hydrogen atom in the molecule of the polymerizable group ^P 11 -SP It may be substituted with ¹¹ −, and * represents a bond and binds to a mesogen group, a polymerizable group, a bending group or a spacer group.)
Specific examples of the above general formula (T-7-1) include the following examples.

(In the formula, ^{R tc} represents a hydrogen atom, 1 to 7 carbon atoms, alkyl groups or polymerizable group ^P 11 ^{-Sp 11} - represented by a hydrogen atom in the molecule of the polymerizable group ^P 11 -Sp It may be substituted with ¹¹ −, and * represents a bond and binds to a mesogen group, a polymerizable group, a bending group or a spacer group.)
In the spontaneously oriented monomer according to the present invention, a form in which the polar element contained in the adsorbent group or the polar element contained in the polymerizable group is localized is preferable. The adsorbent group is an important structure for vertically orienting the liquid crystal composition, and the adsorbent group and the polymerizable group are adjacent to each other, so that better orientation can be obtained and good orientation to the liquid crystal composition is obtained. Shows solubility. Specifically, a form having a polymerizable group and an adsorbing group on the same ring of the mesogen group is preferable. In this case, of the form in which one or more polymerizable groups and one or more adsorbent groups are bonded on the same ring, and at least one of one or more polymerizable groups or at least one of one or more adsorbent groups. It includes a form in which one is bonded to the other and has a polymerizable group and an adsorbing group on the same ring. Further, in this case, the hydrogen atom of the spacer group (S ¹¹ ) of the polymerizable group may be substituted with the adsorbent group, and further, the hydrogen atom of the molecule of the adsorbent group may be replaced with the spacer group (S ¹¹ ) of the polymerizable group. Including the form of binding.

Further, in the spontaneously oriented monomer according to the present invention, one or more hydrogen atoms of the polymerizable group may be substituted with an adsorbent group. In this case, a preferred form includes a form in which one or more hydrogen atoms of the polymerization group P ¹¹ or, if necessary, a spacer group (S ¹¹ ) linked to the polymerization group is substituted with an adsorbent group, which is 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 preferable form in which the adsorbent group and the polymerizable group are linked, the following formulas (T-1-1.1), (T-6-1.1) or (T-5-1.1) are used. Can be mentioned.

(In the above formula, 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 ^t151b and R ^t151c independently represent 1 to 1 carbon atoms. Represents an alkyl group of 3 and an alkyl cyanide group having 1 to 3 carbon atoms.
X ^a and X ^b represent -O-, -S- or CH _2-
L ^t151a and L ^t151b 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 t11c, n t151c, n t16c} , n t151d, n t151e, n t151f and ^{n T151g} each independently represents 0 or ^{1, n t11a, n t11b,} n t1 6a, n t16b, n t151a and ^{n T151b} Independently represent an integer of 1 to 11, and * represents a bond to a mesogen group. )
In the above formula (T-1-1.1), either one of X ^{a and} X ^b is preferably −O−, and X ^ta and X ^tb are more preferably −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),
n ^t11a , n ^t11b , n ^t16a , n ^t16b , n ^t151a and n ^t151b are each independently preferably an integer of 1 to 8, and more preferably an integer of 1 to 5.

"Bending group"
The bending group according to the present invention has a function of inducing the orientation of liquid crystal molecules, and preferably represents a linear or branched alkylene group having 1 to 20 carbon atoms, and is preferably a linear carbon atom. It is more preferable to represent an alkylene group having a number of 1 to 20, and it is more preferable to represent a linear alkylene group having 2 to 15 carbon atoms. In addition, one or two or more -CH ₂ −s that are not adjacent to each other in the alkylene group are independently −CH = CH−, −C≡C−, −O−, −CO−, −. It may be replaced by COO- or -OCO-.

From the viewpoint that the spontaneously oriented monomer has so-called amphipathic properties with respect to the liquid crystal layer, the bending group is preferably bonded to a mesogen group.

The spontaneously oriented monomer according to the present invention preferably has 1 to 6 bending groups, more preferably 1 to 4 groups, and even more preferably 1 to 3 bending groups.

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

(In the above general formula (SAL), -Sp^al-P^alRepresents the polymerizable group, T represents the adsorbent group represented by the general formula (T), MG represents the mesogen group represented by the general formula (AL), Cg represents a hydrogen atom, and the general formula The adsorbent group represented by (T), the polymerizable group-Sp^al-P^alAlternatively, the bending group represents a linear or branched alkylene group having 1 to 20 carbon atoms, and one of the alkylene groups or two or more -CHs that are not adjacent to each other.₂-Can be independently replaced by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and can be any of Cg, MG and T. Is also the above-mentioned polymerizable group-Sp ^al-P^alMay be replaced with
n^sal1, N^sal2And nsal3 independently represent natural numbers 1-5. ) (P in the above formula^alIs a general formula (PI) to a general formula (P-IX).

(In the formula, R ^p11 and R ^p12 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and W ^p11 is a single bond, −O. -, -COO- or methylene group, t ^p11 represents 0, 1 or 2)
Represents the group represented by
Sp ^al represents a single-bonded or linear or branched alkylene group having 1 to 20 carbon atoms, but one of the alkylene groups or two or more -CH ₂ − not adjacent to each other are independent of each other. Then, it may be replaced by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−.
T represents an adsorbent group
MG represents a mesogen group
Cg represents a hydrogen atom, the suction group, the -Sp ^al -P ^al or a linear or branched alkylene group having 1 to 20 carbon atoms, two have not one or adjacent in the alkylene group The above −CH ₂₋ may be independently substituted by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−, and Cg, Both MG and T may be substituted with the above-mentioned polymerizable group -Sp ^al- P ^al- .
n ^sal1 , n ^sal2 and nsal3 independently represent natural numbers 1-5. )
The preferable spontaneous orientation 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).

(In the formula, R^al1, R^al2, Z^al1, Z^al2, L^al1, L^al2, L^al3, L^al4, Sp¹¹¹, Sp¹¹², Sp¹¹³, Sp¹¹⁴, P¹¹¹, P¹¹², P ¹¹³, P¹¹⁴, M^al1, M^al2, M^al3, M^al4, N^al1, N^al2, N ^al3, N^al4, P¹¹¹And P¹¹²Are independent of each other
R^al1Indicates a linear or branched alkyl group having 1 to 20 hydrogen atoms, halogen atoms, and carbon atoms, and one -CH in the alkyl group.₂-Or two or more -CHs that are not adjacent₂-May be replaced with -O-, -OCO- or COO- so that the oxygen atoms are not directly adjacent.
R^al2Is the above-mentioned polymerization group P¹¹-S¹¹Represents an adsorbent group which may be substituted with −, and preferably the above-mentioned polymerization group P.¹¹-S¹¹Represents an adsorbent group represented by the above general formula (T) which may be substituted with −, and more preferably R.^al2Is at least one selected from the group consisting of the general formulas (T-1-1) to (T-7-1), and more preferably the general formulas (T-1-1) and (T-2-1). 1), (T-5-1), at least one selected from the group consisting of (T-6-1).
Even 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).
Ring A^al1, A^al2Independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a 2,6-naphthylene group or a phenanthrene-2,7-diyl group.
Sp¹¹¹, Sp¹¹²And Sp¹¹³Represent each alkylene group or single bond having 1 to 12 carbon atoms independently of each other, and one -CH in the alkylene group.₂-Or two or more -CHs that are not adjacent₂-May be replaced with -O-, -OCO- or COO- so that the oxygen atoms are not directly adjacent.
P¹¹¹, P¹¹², P¹¹³And P¹¹⁴Represents acrylic and methacrylic groups independently of each other,
Z^al1And Z^al2Are independent of each other, single bond, -O-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH₂-, -CH₂O-, -CF₂O-, -OCF₂-,-(CH₂)_n ^al-, -CF₂CH₂-, -CH₂CF₂-,-(CF ₂)_n ^al-, -CH = CH-, -CF = CF-, -C≡C-, -CH = CH-COO- or OCO-CH = CH-, and the above n^alRepresents an integer from 1 to 4
L^al1, L^al2, L^al3And L^al4Are independent of each other, hydrogen atom, halogen atom, alkyl group having 1 to 15 carbon atoms, alkoxy group having 1 to 14 carbon atoms, or R.^al2Here, one or more hydrogen atoms of the alkyl group may be replaced by halogen atoms.
P¹¹¹And P¹¹²Represents 0 or 1 independently of each other, m^al1, M^{al 2}, M^al3And m^al4Represents integers 0 to 3 independently of each other, n^al1, N^al2, N^al3And n^al4Represent an integer from 0 to 3 independently of each other. )
General formula (al-2):

(In the equation, Z ^ad1 and Z ^ad2 are independent, 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 number of carbon atoms 2 represents 20 alkylene group, one or nonadjacent two or more -CH ₂ in the alkylene group - is -O -, - COO- or -OCO- may be substituted with,
A ^ad1 and Aa ^ad2 each independently represent a divalent 6-membered ring aromatic group or a divalent 6-membered ring aliphatic group, but are divalent, unsubstituted 6-membered ring aromatic groups and divalent. The unsubstituted 6-membered ring aliphatic group or the hydrogen atom in these ring structures is not substituted or is substituted with an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. A divalent, unsubstituted 6-membered ring aromatic group, a group in which a hydrogen atom in the ring structure is substituted with a fluorine atom, or a divalent, unsubstituted 6-membered ring aliphatic group is preferable. Preferably, the hydrogen atom on the substituent is 1,4-phenylene group, 2,6-naphthalene group or 1,4-cyclohexyl group which may be substituted with a halogen atom, an alkyl group or an alkoxy group, but at least One substituent is substituted with P ¹¹ − S ¹¹ − and
When a plurality of Z ^ad1 , A ^ad1 and Aa ^ad2 are present, they may be the same or different from each other.
R ^ad1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkyl halide group, or P ¹¹ −S ¹¹ −, and −CH ₂ − in the alkyl group is −O. -, - OCO-, or -COO- is (not a proviso -O- continuous), more preferably a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, or ^{P 11} - It represents S ¹¹ −, and −CH ₂ − in the alkyl group represents −O−, −OCO− so 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 more preferably at least one selected from the group consisting of the general formulas (T-1-1) to (T-7-1), and more preferably the general formula. It is at least one selected from the group consisting of (T-1-1), (T-2-1), (T-5-1), and (T-6-1).
Even 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-mentioned polymerizable group.
^{Z ad1, Z ad2, A ad1} , ^{if m ad1} and / or ^{A ad2} is present in plural, respectively or different and the same as each other, but any one of ^{A ad1} and ^{A ad 2} is at least one of ^P 11 ^{-S 11} - is substituted with,
^mad1 represents an integer from 1 to 5.
^mad2 represents an integer from 1 to 5.
G ^ad1 represents a divalent, trivalent or tetravalent branched structure, or a divalent, trivalent or tetravalent aliphatic or aromatic ring structure.
m ^ad3 represents an integer 1 less than the valence of G ^ad1 . )
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 -CH _2-that are not adjacent to each other are -O-. , -S-, -CH = CH- or C≡C-, and in these groups at least one hydrogen atom may be substituted with a halogen atom.
A ^al31 and A ^al34 independently represent 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl or phenanthrene-2,7-diyl, and at least one in these rings. One 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. Substituted, 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 an alkylene having 1 to 10 carbon atoms, and in the alkylene group, one or two or more -CH ₂ − not adjacent to each other 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.
S ^al31 represents a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, one or two or more -CH _2-that are not adjacent to each other are -O-, -S-, -CH =. It may be substituted with CH- or C≡C-, and in these groups, at least one hydrogen atom may be substituted with a halogen atom.
K ^al31 and K ^al32 are independently from hydrogen atom, halogen atom, alkyl group having 1 to 5 carbon atoms, or at least one hydrogen atom substituted with halogen atom (for example, fluorine atom). Represents an alkyl group of 5
n ^al31 is an integer represented by 0 to 4.
R ^al32 is a group represented by the formula (al3-1) or the formula (al3-2).

In the formula (al3-1) and the formula (al3-2),
S ^al32 and ^Sal33 are independently single-bonded or alkylene groups having 1 to 10 carbon atoms, and in the alkylene group, one or two or more -CH _2-that are not adjacent to each other are -O-, It may be substituted with −S−, −CH = CH− or C≡C−, and in these groups, at least one hydrogen atom may be substituted with a halogen atom.
S ^al31 is = CH- or = N-,
X ^al31 is -OH, -NH ₂ , -OR ³ , -N (R ³ ) ₂ , formula (X ^al31 ), -COOH, -SH, -B (OH) ₂ , or -Si (R ³ ) _3. In this alkyl group, R ³ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and one or two or more −CH ₂ − not adjacent to each other are It may be substituted with −O−, −S−, −CH = CH− or C≡C−, and in these groups, at least one hydrogen atom may be substituted with a halogen atom.
Equation (X ^al31 ):

(N ^al32 is an integer of 1 to 5.)
In the above-mentioned spontaneously oriented monomer, polar parts such as adsorption groups and polymerizable groups that are difficult to be compatible with the liquid crystal layer and non-polar parts such as mesogen groups and bending groups that are easily compatible with the liquid crystal layer are unevenly distributed in the molecule. It is preferable that the so-called liquid crystal layer exhibits amphipathic properties. Therefore, the spontaneously oriented monomer according to the present invention preferably has a structure having a bending group for orienting a liquid crystal molecule at one end of a mesogen group and a polymerizable group and an adsorbing group at the other end of the mesogen group. .. Since the interfacial free energy is high near the interface between the liquid crystal layer and the substrate, a substance having a non-polar portion having an affinity for the liquid crystal layer and a polar portion having a low affinity for the liquid crystal layer in one molecule. Is considered to reduce the interfacial free energy by lining up on the interface.

The lower limit of the content of the spontaneously oriented 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 preferably 0.05% by mass. 0.06% by mass is preferable, 0.07% by mass is preferable, 0.08% by mass is preferable, 0.09% by mass is preferable, 0.1% by mass is preferable, 0.12% by mass is preferable, and 0. It is preferably 15% by mass, preferably 0.17% by mass, preferably 0.2% by mass, preferably 0.22% by mass, preferably 0.25% by mass, preferably 0.27% by mass, and 0.3% by 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 preferable. Preferably, 0.5% by mass is preferable, and 0.55% by mass is preferable. 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% by mass is preferable, 1.8% by mass is preferable, 1.6% by mass is preferable, 1.5% by mass is preferable, 1% by mass is preferable, 0.95% by mass is preferable, and 0.9% by mass is preferable. Preferably, 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. It is preferably 0.55% by mass, preferably 0.5% by mass, preferably 0.45% by mass, and preferably 0.4% by mass.

A particularly preferable specific example of the spontaneously oriented 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 one or two or more -CH _2-that are not adjacent to each other in the alkyl group. May be replaced with -O- or -CH = CH-
L ^al5 , L ^al6 , L ^al7 and L ^al8 independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a halogen atom or the above P ¹¹ −S ¹¹ −, and in the alkyl group, 1 number or not adjacent two or more -CH ₂ - may be replaced by -O- or -CH = CH-,
Ring A ^al3 represents 1,4-cyclohexylene or 1,4-phenylene.
R ^ala or R ^album independently represent a hydrogen atom or P ¹¹ −S ¹¹ − above, and at least one of R ^ala or R ^album represents P ¹¹ −S ¹¹ − above.
Z ^AL3 is a single _{bond, -CH 2 -CH 2 -, -} CH 2 -O- or O-CH ₂ - represents,
R ^al4 represents an adsorbent group represented by the above general formula (T).
P ¹¹³ and P ¹¹⁴ independently represent 0 or 1, respectively. )
In the above general formula (al-1-1), it is preferable that one of L ^al7 and L ^al8 represents an alkyl group having 1 to 5 carbon atoms.

In the general formula (al-1-1), R ^ala and R ^alb preferably represent the above P ¹¹ −S ¹¹ −.

In the general formula (al-1-1), R ^al4 is a general formula (T-1-1) to (T-7-1) or formulas (T-1-1.1), (T-6). −1.1) or (T-5-1.1) is preferable.

Preferred compounds represented by the general formula (al-1) include compounds represented by the following formulas (AL-1.1) to (AL-1.18).

Preferred compounds represented by the 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 contains two or more kinds selected from the group consisting of compounds represented by the following general formula (I) having a chemical structural formula different from that of the spontaneously oriented monomer in the liquid crystal composition. Is done.

(In the general formula ^{(I), R 101, R} 102, R 103, R 104, R 105, R 10 6, R 107, R 108, R 109 and ^{R 110} are each ^{independently,} P 21 ^{-S 21} -, alkyl group of from 1 to 18 carbon atoms, an alkoxy group having from 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, the ^{P 21} is represented by the following formula (P-I) ~ formula (P- It is one of the groups represented by IX),

(In the formula, R^p11And R^p12Independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and W^p11Represents a single bond, -O-, -COO- or methylene group, t^p11Represents 0, 1 or 2. )
S above²¹Represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more -CHs in the alkylene group.₂-Can be replaced with -O-, -OCO- or -COO- so that the oxygen atoms are not directly adjacent.
n¹¹Represents 0, 1 or 2
n¹²And n¹³Independently represent 0 or 1, respectively
n¹¹+ N¹²+ N¹³= 1, 2 or 3
A¹¹The following groups (a), groups (b) and groups (c):
(A) 1,4-Cyclohexylene group (one -CH present in this group)₂-Or two or more -CHs that are not adjacent₂-May be replaced with -O-. )
(B) A 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =) and.
(C) Naphthalene-2,6-diyl group, 2,7-phenanthreneyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene- One -CH = present in the 2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, or two or more non-adjacent -CH = are -N = May be replaced with.)
Represents a group selected from the group consisting of, and the above groups (a), groups (b) and groups (c) are independently alkyl groups having 1 to 12 carbon atoms and alkoxy groups having 1 to 12 carbon atoms. Group, halogen, cyano group, nitro group or P²¹-S²¹May be replaced with-
L¹⁰And L¹¹Are independent, single bond, -OCH₂-, -CH₂O-, -C ₂H₄-, -OC₂H₄O-, -COO-, -OCO-, -CH = CR^a-COO-, -CH = CR^a-OCO-, -COO-CR^a= CH-, -OCO-CR^a= CH-,-(CH₂)_z-COO-,-(CH₂)_z-OCO-, -OCO- (CH₂)_z-, -COO- (CH₂)_z-, -CH = CH-, -CF₂O-, -OCF₂-Or -C≡C- (in the formula, R^aEach independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, z independently represents an integer of 1 to 4 respectively. )
P²¹, S²¹, L¹¹And A¹¹When there are a plurality of them, they may be the same or different from each other. )
When two or more kinds of polymerizable monomers are contained in the liquid crystal composition in the present invention, the tilt angle of the liquid crystal molecules can be formed by the first polymerization process of the polymerizable monomer and the spontaneously oriented monomer present in the composition. It makes it easier to construct a polymer network. In the liquid crystal composition, there are at least three monomers, one or more spontaneously oriented monomers and two or more polymerizable monomers, each having a different chemical structure. Since the polymerization reactivity of these three monomers is different, it is considered that the monomer that can trigger the polymerization reaction can accelerate 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, particularly the mesogen skeleton that most affects the absorption of light and the substituents attached to the mesogen skeleton are different from each other, and therefore, among the three monomers, It is believed that the monomer with the longest absorption wavelength can accelerate the reaction of two or more other monomers. It is considered that this makes it easier to form a network of polymers having a size capable of forming a tilt angle of the liquid crystal molecules in the initial polymerization process of the polymerizable monomer present in the composition and the spontaneously oriented monomer.

The polymerizable monomer according to the present invention contains 2 to 4 polymerizable monomers selected from the group consisting of compounds represented by the general formula (I) having a chemical structural formula different from that of the spontaneously oriented monomer. It is preferable, 2 to 3 types are more preferable, and 2 types are particularly preferable.

In the above general formula (I), it is preferable that R ¹⁰¹ and R ¹¹⁰ are independently P ²¹ − S ^{2 1} −. The P ²¹ is preferably of the 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 two or more −CH ₂ − in the alkylene group is an oxygen atom. May be substituted with -O-, -OCO- or -COO- so that they are not directly adjacent to each other, and more preferably represent a single bond or an alkylene group having 1 to 5 carbon atoms.

In the above general formula (I), A ¹¹ is a group selected from the group consisting of a 1,4-cyclohexylene group, a 1,4-phenylene group, a naphthalene-2,6-diyl group and a 2,7-phenanthylene diyl group. 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 above general formula (I), L¹⁰And L¹¹Are independent, single bond, -OCH ₂-, -CH₂O-, -C₂H₄-, -OC₂H₄It preferably represents O-, -COO- or -OCO-, L.¹⁰And L¹¹More preferably represents a single bond.

When two kinds of polymerizable monomers are contained, in the above general formula (I), one of the polymerizable monomers represented by the general formula (I) has n ¹¹ of 0 and R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , any one of ^{R 1 05, 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} - Is preferable.

The polymerizable monomer represented by the general formula (I) according to the present invention is specifically represented by the following general formulas (RM-1), general formula (RM-2) and general formula (RM-3). It is preferable that two or more kinds are selected from the group of polymerizable monomers to be subjected to.

(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} Represent each of the above formulas (PI) to (P-IX) independently, and S ³³ and S ⁴⁴ each independently represent a single bond or an alkylene group having 1 to 10 carbon atoms. , One or more -CH _2- in the alkylene group may be substituted with -O-, -OCO- or COO- so that oxygen atoms are not directly adjacent.
R ¹⁰² , R ¹⁰⁴ , R ¹⁰⁷ and R ¹⁰⁹ independently represent either 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-phenylene diyl group, wherein the A ¹¹ is unsubstituted or carbon. It may be substituted with an alkyl group having 1 to 5 atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen (fluorine atom, 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- (In the formula, ^Ra is independently hydrogen atom or carbon atom number 1 to 3 Represents the alkyl group of, and in the above formula, Y represents an integer from 1 to 4).
R ¹⁰³ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁸ 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 above general formula (RM-3), X ^{M1 to} X ^M8 independently represent a hydrogen atom or a fluorine atom, respectively.
^SM2 and ^SM3 independently represent an alkylene group or a single bond having 1 to 12 carbon atoms, and -CH _2- in the alkylene group is assumed to be an oxygen atom and -COO, assuming that the oxygen atoms do not directly bond with each other. May be replaced with −, −OCO− or OCOO−
^RM2 and ^RM3 represent any of the above equations (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 preferably contains a biphenyl skeleton and has 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 the liquid crystal composition according to the present invention, as a preferable embodiment having two or more kinds of polymerizable monomers represented by the general formula (I), two or more kinds of polymerizable monomers represented by the general formula (RM-2) are contained. Aspect, a mode containing a polymerizable monomer represented by the general formula (RM-1) and a polymerizable monomer represented by the general formula (RM-2), or a polymerizable monomer represented by the general formula (RM-2). And three aspects including the polymerizable monomer represented by the general formula (RM-3).

In general, a liquid crystal display element using a liquid crystal composition containing a PSA step or a spontaneous orientation agent or a polymerizable monomer cures the spontaneous orientation monomer or the polymerizable monomer in the liquid crystal composition by irradiating light once or twice or more. A polymer network is formed on the surface of the substrate, and the tilt angle of the liquid crystal molecules is controlled by the network. At that time, if a polymer network having a size capable of controlling the tilt angle of the liquid crystal molecules is formed in the first light irradiation step, the amount of change in the tilt angle of the liquid crystal display element over time and the seizure can be reduced. it is conceivable that. Therefore, by using a liquid crystal composition containing one or more spontaneously oriented monomers and two or more polymerizable monomers, polymerization can be performed in the light absorption zone of at least three of these monomers. It is considered that the reaction is likely to occur, and the monomer having the longest absorption wavelength among the at least three monomers can accelerate the reaction of the other two or more monomers as a polymerization trigger (the role of a so-called initiator). .. Therefore, it is preferable to contain at least one polymerizable monomer having a long absorption wavelength. Specifically, an embodiment containing two or more kinds of polymerizable monomers represented by the above general formula (RM-2), a polymerizable monomer represented by the general formula (RM-1) and a general formula (RM-2). A mode containing the polymerizable monomer represented by the above formula or a mode containing the polymerizable monomer represented by the general formula (RM-2) and the polymerizable monomer represented by the general formula (RM-3) is preferable.

On the other hand, in the case of a liquid crystal composition containing one kind of spontaneously oriented monomer and one kind of polymerizable monomer or a liquid crystal composition containing only one kind of spontaneously oriented monomer, the tilt angle of the liquid crystal molecules is controlled in the first light irradiation step. In order to form a network of polymers of a size that can be formed, a polymerizable monomer having a long absorption wavelength is used. However, the polymerizable monomer having a long absorption wavelength has a structure containing a large amount of aromatic rings and is suitable for a liquid crystal composition. The desired concentration cannot be added from the viewpoint of compatibility and low temperature stability. Further, when a polymerizable monomer or a spontaneously oriented monomer having low reactivity is used, the domain constituting the polymer network becomes sparse, so that the tilt angle with respect to the liquid crystal molecule cannot be controlled, and the light irradiation step is performed a plurality of times. The method of curing the polymerizable monomer or spontaneously oriented monomer remaining after the first light irradiation step to reinforce the polymer network is considered to have low tilt angle stability.

In the liquid crystal composition according to the present invention, as a more preferable embodiment having two or more kinds of polymerizable monomers, an embodiment containing two or more kinds of polymerizable monomers represented by the following general formula (RM-2-1), the following general formula A mode 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). There are three embodiments including the polymerizable monomer represented by the following general formula (RM-3).

(In the general formula (RM-1-1) and the general formula (RM-2-1), ^PRM1 and ^PRM2 are independently any 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 -CH ₂ − in the alkylene group has an oxygen atom. It may be replaced with -O-, -OCO- or COO- so that it is not directly adjacent.
R ^{102 to} R ¹⁰⁹ independently represent either 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 independently represent either 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-1-1), it is preferable that either one of Sp ^RM1 or Sp ^RM2 represents an alkylene group having 1 to 7 carbon atoms and the other represents a single bond.

In the above 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 above 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 includes 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), and a general formula ( It is preferable to include one or more selected from the group consisting of the compound represented by N-2) and the compound represented by the general formula (N-3). When the liquid crystal composition exhibits negative permittivity anisotropy as a whole, the compound represented by the general formula (L), the compound represented by the general formula (N-1), and the general formula (N-2) are used. It is preferable to include one or more compounds selected from the group consisting of the compound represented by the compound and the compound represented by the general formula (N-3). On the other hand, when the liquid crystal composition exhibits negative dielectric anisotropy as a whole, it is preferable to include a compound represented by the general formula (L) and a compound represented by the general formula (J).

The liquid crystal compound according to the present invention contains one or more compounds represented by the general formula (L) of a dielectrically substantially neutral compound (value of Δε is -2 to 2) as the first component. It is preferable to contain it.

The compound represented by the general formula (L) is as follows.

(Wherein, R ^L1 and R ^L2 represent each independently an alkyl group having 1 to 8 carbon atoms, one or non-adjacent two or more -CH 2 in the alkyl group _- is independently It may be replaced 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} 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 with -O-.)
(B) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -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) , 3,4-Tetrahydronaphthalene-2,6-Diyl group One -CH = or two or more non-adjacent -CH = may be replaced with -N =).
Represents a group selected from the group consisting of, and the above group (a), group (b) and group (c) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, respectively.
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 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
If n ^L1 is 2 or 3 and there are a plurality of A ^L2s , they may be the same or different, and if n ^L1 is 2 or 3 and there are a plurality of Z ^L2s , they may be the same or different. 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 a general formula (J) of a dielectrically positive compound (Δε is larger than 2) as a second component. Compounds represented by and / or dielectrically negative compounds (the sign of Δε is negative and its absolute value is greater than 2) represented by the general formulas (N-1) to (N-3). Is preferably contained in one type or two or more types.

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

(In the formula, R ^J1 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 independently −CH = CH−, −. It may be replaced 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 independent of each other.
(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 = existing in this group or two or more -CH = not adjacent to each other may be replaced with -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) , 3,4-Tetrahydronaphthalene-2,6-Diyl group One -CH = or two or more non-adjacent -CH = may be replaced with -N =).
Represents a group selected from the group consisting of, and the above groups (a), group (b) and group (c) are independently cyano groups, fluorine atoms, chlorine atoms, methyl groups, trifluoromethyl groups or trifluoro groups. It may be substituted with 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 Represents −, −COO−, −OCO− or −C≡C−
When n ^J1 is 2, 3 or 4 and there are a plurality of A ^J2s , they may be the same or different, and when n ^J1 is 2, 3 or 4 and there are a plurality of Z ^J1s. If so, they may be the same or different,
^XJ1 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 the compounds represented by the general formulas (N-1) to (N-3) of the dielectrically negative compound (the sign of Δε is negative and its absolute value is larger than 2). One type or two or more types are as follows.

(In the above formula, ^RN11 , ^RN12 , ^RN21 , ^RN22 , ^RN31 and ^RN32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or a non-alkyl group among the alkyl groups. Two or more adjacent −CH ₂ −s 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 independent of each other.
(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 = existing in this group or two or more -CH = not adjacent to each other may be replaced with -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 = existing in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. ) And (d) represent a group selected from the group consisting of 1,4-cyclohexenylene groups, and the above groups (a), group (b), group (c) and group (d) are independent of each other. It may be substituted with 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 = NN = CH-, -CH = CH-, -CF = CF- or -C≡C- Represent,
X ^N21 represents a hydrogen atom or a fluorine atom.
^TN31 represents −CH _2- or 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 ^{N3 2} are independent of each other. 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 general formula (L) is preferably a compound represented by the following formulas (L-1) to (L-13).

(In the formula, ^RL1 and ^RL2 independently represent the same meaning as the general formula (L), and A ^L1 and ^AL7 independently represent the same meaning as the general formula (L), but A. The hydrogen atoms on ^L1 and A ^L2 may be independently substituted with fluorine atoms, Z ^L1 has the same meaning as Z ^L2 in the general formula (L), and ^XL1 and ^XL2 are independent of each other. Represents a fluorine atom or a hydrogen atom.)
As the compound represented by the general formula (J), the compound represented by the general formula (M) and the compound represented by the general formula (K) are preferable.

Here, first, the compound represented by the general formula (M) includes a compound having the following structure.

^{(Wherein, R M1} represents an alkyl group having 1 to 8 carbon atoms, one or non-adjacent two or more -CH ₂ in the alkyl group - are each independently -CH = CH -, - It may be replaced by C≡C−, −O−, −CO−, −COO− or −OCO−.
n ^M1 represents 0, 1, 2, 3 or 4
^AM1 and ^AM2 are independent of each other
(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- (May be) and (b) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =).
Represents a group selected from the group consisting of, and the hydrogen atoms on the above groups (a) and (b) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ^M1 and ^{Z M2} each independently represent 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 ^AM2 , they may be the same or different, and when n ^M1 is 2, 3 or 4 and there are a plurality of Z ^M1s. If so, they may be the same or different,
X ^M1 and X ^M3 independently represent a hydrogen atom, a chlorine atom or a fluorine atom, respectively.
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), ^RM1 is 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. The group is preferable, 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. Alkyl groups having 1 to 5 or alkenyl groups having 2 to 5 carbon atoms are more preferable, alkyl groups having 2 to 5 carbon atoms or alkenyl groups having 2 to 3 carbon atoms are further preferable, and alkenyl groups having 3 carbon atoms are more preferable. (Propenyl group) is particularly preferable.

Preferably R ^M1 is an alkyl group in the case of emphasizing reliability, it is preferred when emphasizing a reduction in viscosity is 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 are used. An alkoxy group having 4 to 5 atoms is preferable, and when the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, pyran, or dioxane, a linear alkyl group having 1 to 5 carbon atoms or a linear chain is used. Alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from the groups represented by any of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure to which the alkenyl group is bonded.)

Preferably when it is desired A ^M1 and A ^M2 is to increase the Δn each independently is an aromatic, preferably to improve the response speed is an aliphatic, 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, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably 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-, -CH ₂ CH _2- or single bond is more preferred, and -CF ₂ O- or single bond is particularly preferred.

n ^M1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, 0 or 1 is preferable in the case of focusing on improvement of [Delta] _[epsilon], in the case of emphasizing _{T NI} 1 or 2 preferable.

The types of compounds that can be combined are not particularly limited, but they are used in combination according to desired performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, and three types as 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) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, seizure, and the like. It is necessary to make appropriate adjustments 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% by mass, 10% by mass, 20% by mass, and 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. is there. The upper limit 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 liquid crystal composition of the present invention in one embodiment of the present invention. Yes, it is 55% by mass, it is 45% by mass, it is 35% by mass, and it is 25% by mass.

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

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

(In the formula, ^RK1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ −s in the alkyl group are independently −CH = CH−, −. It may be replaced by C≡C−, −O−, −CO−, −COO− or −OCO−.
n ^K1 represents 0, 1, 2, 3 or 4
^AK1 and ^AK2 are independent of each other
(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- (May be) and (b) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =).
Represents a group selected from the group consisting of, and the hydrogen atoms on the above groups (a) and (b) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ^K1 and ^{Z K2} each independently represent 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−
If n ^K1 is a 2, 3 or 4 ^{A K2} there are multiple, they may be different even in the ^{same, n K1} is a 2, 3 or 4 ^{Z K1} there are multiple If so, they may be the same or different,
X ^K1 and X ^K3 independently represent a hydrogen atom, a chlorine atom or a fluorine atom, respectively.
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), ^RK1 is 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. The group is preferable, 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 having 1 to 5 or an alkenyl group having 2 to 5 carbon atoms is more preferable, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is further preferable, and an alkenyl group having 3 carbon atoms is more preferable. (Propenyl group) is particularly preferable.

Preferably R ^K1 is an alkyl group in the case of emphasizing reliability, it is preferred when emphasizing a reduction in viscosity is 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. An alkoxy group having 4 to 5 atoms is preferable, and when the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, pyran, or dioxane, a linear alkyl group having 1 to 5 carbon atoms or a straight chain is used. Alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from the groups represented by any of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure to which the alkenyl group is bonded.)

Preferably when it is desired A ^K1 and A ^K2 is to increase the Δn each independently is an aromatic, preferably to improve the response speed is an aliphatic, 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, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably 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-, -CH ₂ CH _2- or single bond is more preferred, and -CF ₂ O- or single bond is particularly preferred.

n ^K1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, 0 or 1 is preferable in the case of focusing on improvement of [Delta] _[epsilon], in the case of emphasizing _{T NI} 1 or 2 preferable.

The types of compounds that can be combined are not particularly limited, but they are used in combination according to desired performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, one type, two types, and three types as 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) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, seizure, and the like. It is necessary to make appropriate adjustments 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, and 30. It is mass%, it is 40 mass%, it is 50 mass%, it is 55 mass%, it is 60 mass%, it is 65 mass%, it is 70 mass%, it is 75 mass%, it is 80 mass%. Is. The upper limit 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 in one embodiment of the present invention. , 55% by mass, 45% by mass, 35% by mass, and 25% by mass.

When a composition having a low viscosity and a high response speed is required, it is preferable to lower the lower limit value and lower the upper limit value. Moreover, maintaining high T _{N I} of the liquid crystal composition of the present invention, when temperature stability good composition is required for lowering the lower limit of the above, it is preferable to set the upper limit to lower. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the above lower limit value and raise the upper limit value.

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

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

Represents a hydrogen atom on the 1,4-phenylene group may be substituted by a fluorine ^atom, W ^{M101 to W-M172} are each independently, -CH ₂ - represents a or -O-. )

Examples of the compound represented by the general formula (N-1) according to the present invention include a group of 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 ^Represents 0 or 1, n ^Nd11 represents 1 or 2, n ^Ne11 represents 1 or 2, n ^{Nf1 2} represents 1 or 2, n ^{Ng 11} represents 1 or 2, A ^{Ne 11} represents trans-1, It represents a 4-cyclohexylene group or a 1,4-phenylene group, and A ^Ng11 represents a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group, but n If ^NG11 is ^{1, a NG11} represents cyclohexenylene ^group, when ^{n NG11} is 2, represents at least one ^{a NG11} 1,4-cyclohexenylene ^{group, Z n e11} represents a single bond Alternatively, it represents an ethylene group, but when n ^Ne11 is 1, Z ^Ne11 represents an ethylene group. When n ^Ne11 is 2, at least one Z ^Ne11 represents an ethylene group.)
The compound represented by the general formula (N-2) according to the present invention is a compound selected from the compound group represented by the following general formulas (N2-1) to (N-2-3). Is preferable.

^{(Wherein, R N211} and ^{R N212} are each independently of the general formula (N-2) represent the same meaning as ^{R N 21} and ^{R N22.)}

^{(Wherein, R N221} and ^{R N222} are each independently of the general formula (N-2) represent the same meaning as ^{R N 21} and ^{R N22.)}

^{(Wherein, R N231} and ^{R N232} are each independently of the general formula (N-2) represent the same meaning as ^{R N 21} and ^{R N22.)}
The compound represented by the general formula (N-3) is preferably a compound selected from the compound group represented by the general formula (N-3-2).

^{(Wherein, R N321} and ^{R N322} are each independently the same meaning as ^{R N 31} and ^{R N32} in the general formula (N-3).)
When the entire 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 kind or two or more kinds of compounds selected from the above, and a compound represented by the general formula (L).

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

Further, the lower limit of the proportion of the component composed only of the compounds represented by the general formula (I), the general formula (J) and the 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 mass, 94% by mass, 95% by mass, 96% by mass, 97% by mass, 98% by mass, and 99% by mass.

When the entire 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 kind or two or more kinds of compounds selected from the above, and a compound represented by the general formula (L).

The proportion of the component composed only of the compounds represented by the general formula (I), the general formula (N-1), and the general formula (L) in the entire polymerizable monomer-containing liquid crystal composition according to the present invention. The upper limit values are 100% by mass, 99% by mass, 98% by mass, 97% by mass, 96% by mass, 95% by mass, 94% by mass, 93% by mass, 92% by mass, 91% by mass, 90% by mass, 89% by mass. %, 88% by mass, 87% by mass, 86% by mass, 85% by mass, and 84% by mass are preferable.

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

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, but 1.5 to 18.0 is preferable. 5 to 15.0 is more preferred, 1.5 to 11 is even more preferred, and 1.5 to 8 is particularly preferred.

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

The liquid crystal composition according to the present invention has a viscosity (η) at 20 ° C. of 10 to 50 mPa · s, preferably 10 to 45 mPa · s, preferably 10 to 40 mPa · s, and 10 to 40 mPa · s. It is preferably 35 mPa · s, preferably 10 to 30 mPa · s, 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 20 ° C. of 50 to 160 mPa · s, preferably 55 to 160 mPa · s, and preferably 60 to 160 mPa · s. It is preferably 60 to 150 mPa · s, preferably 60 to 140 mPa · s, preferably 60 to 130 mPa · s, and 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, more preferably 70 ° C to 100 ° C, and 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 a remarkable feature of high-speed response, and in addition, a sufficient tilt angle can be obtained, and there is an unreacted polymerizable monomer. Since the number is so small that it does not cause a problem and the voltage retention rate (VHR) is high, there are no problems such as poor orientation and poor display, or they are sufficiently suppressed. Further, 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 most suitable for improving production efficiency and stable mass production.

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

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples. In addition, "%" in the compositions of the following Examples and Comparative Examples means "mass%". The following abbreviations are used for the description of 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. η: Viscosity at 20 ° C. (mPa · s)
γ ₁ : Rotational viscosity at 20 ° C (mPa · s)
Δε: Dielectric modulus anisotropy at 20 ° C K ₃₃ : Elastic constant at 20 ° C K ₃₃ (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 evaluation of "low temperature storage", "vertical orientation", "pre-tilt angle formation" and "response characteristics" in this example and comparative example was carried out by the following methods.

(Evaluation test for low temperature storage)
The liquid crystal composition was filtered through a membrane filter (PTFE 13m-0.2μm 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, weighed 0.5 g in a sufficiently dried vial, and allowed to stand in an environment of -25 ° C. for 10 days. Then, the presence or absence of precipitation was visually observed and judged in the following two stages.

A: Precipitation cannot be confirmed.

B: Precipitates after 1 week.

C: Precipitation can be confirmed.

(Vertical orientation evaluation test)
It is driven by a first substrate (common electrode substrate) having a transparent electrode layer composed of transparent common electrodes patterned on an insulating layer and having no alignment film provided with a color filter layer, and an active element. A second substrate (pixel electrode substrate) having no alignment film having a pixel electrode layer having a transparent pixel electrode was prepared. The liquid crystal composition was dropped onto the first substrate, sandwiched on the second substrate, and the sealing material was cured at normal pressure at 110 ° C. for 2 hours to obtain a liquid crystal cell having a cell gap of 3.2 μm. At this time, the vertical orientation and the uneven orientation such as dripping marks were observed using a polarizing microscope and evaluated in the following five stages.
S: Especially excellent and uniformly vertical alignment A: Uniform vertical alignment over the entire surface B: Level that is acceptable even if there is a slight alignment defect C: Level that is unacceptable due to alignment defect D: Orientation defect is considerably poor (liquid crystal) Burn-in evaluation method (change in pre-tilt angle over time))
First, a polyimide alignment film that induces vertical alignment was applied to a substrate with ITO, and then the polyimide alignment film was injected by a vacuum injection method between liquid crystal cells (cell gap 3.5 μm) containing the substrate with ITO that had been rubbed. .. Then, a high-pressure mercury lamp was used in a state where a voltage of 10 V was applied to the liquid crystal cell into which the liquid crystal composition was injected at a frequency of 100 Hz, and ultraviolet rays were irradiated through a filter that cuts ultraviolet rays of 325 nm or less. At this time, the illuminance measured under the condition of a central wavelength of 365 nm was adjusted to be 100 mW / cm ² , and ultraviolet rays having an integrated light intensity of 10 J / cm ² were irradiated. The ultraviolet irradiation condition was defined as irradiation condition 1. The irradiation condition 1 imparts a pretilt angle to the liquid crystal molecules in the liquid crystal cell. Here, in order to evaluate the pretilt formation regardless of the presence or absence of vertical orientation, the evaluation is performed using a cell with a polyimide alignment film, but when a monomer having sufficiently high vertical orientation is used, the cell without the polyimide alignment film is used. It has been confirmed that the same result can be obtained even if the same evaluation is performed in.

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 ultraviolet irradiation condition was defined as irradiation condition 2. Irradiation condition 2 reduces the residual amount of the polymerizable monomer in the unreacted liquid crystal cell under irradiation condition 1.

After irradiation with ultraviolet rays, display defects (burn-in) due to changes in the pretilt angle were evaluated. First, the pre-tilt angle of the liquid crystal display element was measured and used as the pre-tilt angle (initial). The liquid crystal display element was irradiated with a backlight for 10 hours while applying a voltage of 30 V rectangular wave at a frequency of 100 Hz. Then, the pre-tilt angle was measured and used as the pre-tilt angle (after the test). The value obtained by subtracting the pretilt angle (after the test) from the measured pretilt angle (initial) was defined as the amount of change in the pretilt angle (= absolute value of the change in the pretilt angle) [°]. The pre-tilt angle was measured using OPTIPRO manufactured by Shintec. The magnitude of the voltage of 30V is several times larger than the normal drive voltage, and it is an acceleration test.

The closer the amount of change in the pretilt angle is to 0 [°], the lower the possibility that display defects will occur due to the change in the pretilt angle.

The amount of change in the pretilt angle measured above was divided into the following four stages.
S: Within 0.1 ° (almost no display defects occur)
A: 0.1 ° or more and 0.3 or less (display defects are unlikely to occur)
B: 0.3 ° or more and 0.5 ° or less (significant display defects occur)
C: 0.5 ° or more (unacceptable level due to display failure)
(Evaluation test of response characteristics)
The cell with a cell gap of 3.2 μm used in the above (evaluation test for pretilt angle formation) was further irradiated with a UV fluorescent lamp manufactured by Toshiba Lighting & Technology Corporation for 60 minutes (illuminance at 313 nm: 1.7 mW / cm ² ). The response speed was measured for the cells thus obtained. The response speed was measured by measuring Voff at 6 V under a temperature condition of 25 ° C. using DMS703 of AUTRONIC-MELCHERS.

(Preparation and evaluation results of liquid crystal composition)
A liquid crystal composition was prepared with the compound as shown below in a mixing ratio, and the composition was designated as LC-1. The composition of the liquid crystal composition and the results of its physical property values are shown below.

LC-1 has a nematic phase-isotropic liquid phase transition temperature (T _NI ) of 75 ° C., a solid phase-nematic phase transition temperature ( _TCN ) of -33 ° C., and a refractive index anisotropy (Δn) of 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. (hereinafter, the same applies).

(Comparative Examples 1 to 8)
When LC-1 is 100 parts by mass, 1.0 part by mass of the following spontaneously oriented monomer (P-1) and 0.3 parts by mass of the compound represented by the formula (RM-1) are added. A liquid crystal composition containing a sex monomer was designated as Comparative Example 1.

Polymerization of the liquid crystal composition LC-1 by adding 1.0 part by mass of the spontaneously oriented monomer (P-1) and 0.3 parts by mass of the compound represented by the formula (RM-2) to 100 parts by mass. A liquid crystal composition containing a sex monomer was designated as Comparative Example 2.

Polymerization of the liquid crystal composition LC-1 by adding 1.0 part by mass of the spontaneously oriented monomer (P-1) and 0.3 parts by mass of the compound represented by the formula (RM-3) to 100 parts by mass. A liquid crystal composition containing a sex monomer was designated as Comparative Example 3.

Polymerization of the liquid crystal composition LC-1 by adding 1.0 part by mass of the spontaneously oriented monomer (P-1) and 0.3 parts by mass of the compound represented by the formula (RM-4) to 100 parts by mass. A liquid crystal composition containing a sex monomer was designated as Comparative Example 4.

Polymerization of the liquid crystal composition LC-1 by adding 0.5 parts by mass of the spontaneously oriented monomer (P-1) and 0.3 parts by mass of the compound represented by the formula (RM-2) to 100 parts by mass. A liquid crystal composition containing a sex monomer was designated as Comparative Example 5.

Polymerization of the liquid crystal composition LC-1 by adding 0.5 parts by mass of the spontaneously oriented monomer (P-1) and 0.6 parts by mass of the compound represented by the formula (RM-1) to 100 parts by mass. A liquid crystal composition containing a sex monomer was designated as Comparative Example 6.

Polymerization of the liquid crystal composition LC-1 by adding 1.0 part by mass of the spontaneously oriented monomer (P-1) and 0.6 parts by mass of the compound represented by the formula (RM-1) to 100 parts by mass. A liquid crystal composition containing a sex monomer was designated as Comparative Example 7.

Polymerization of the liquid crystal composition LC-1 by adding 1.0 part by mass of the spontaneously oriented monomer (P-1) and 0.6 parts by mass of the compound represented by the formula (RM-3) to 100 parts by mass. A liquid crystal composition containing a sex monomer was designated as Comparative Example 8.

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

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

Regarding the low-temperature storage stability of Examples 1 to 95, precipitation begins to occur in the polymerizable monomer having a long-chain alkyl group as a substituent (for example, RM-9 to RM-11) after about 1 week. In addition, 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 good low-temperature storage stability. With respect to cryopreservation, the polymerizable monomer has relatively good solubility, and therefore largely depends on the solubility of the spontaneously oriented monomer.

Further, when a liquid crystal cell containing a liquid crystal composition containing two kinds of polymerizable monomers is set in a polarizing microscope in which a polarizer and an analyzer are arranged at right angles and the transmitted light is observed, the liquid crystal molecules are vertically aligned. For example, the cells are displayed in black because light cannot be transmitted due to the action of the polarizing plate. When the samples of the liquid crystal compositions of Examples 1 to 95 were evaluated by such a test method, when two kinds of polymerizable monomers were appropriately selected and added to the liquid crystal composition, the uneven orientation was remarkably reduced. It was confirmed that the vertical orientation was similar. One suitable 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 an absorption of 300 nm or more, and each monomer has an appropriate concentration. Good vertical orientation was confirmed by adding in.

On the other hand, in Comparative Examples 1, 2, 4, 5 to 7, it was confirmed that the amount of change in pretilt was relatively good by adding the polymerizable monomer, but the vertical orientation was low. In Comparative Example 3, the vertical orientation was high, but the amount of change in pretilt was large. In Comparative Examples 6 to 7, the vertical orientation was not improved even though the amount of one type of polymerizable monomer added was increased. From these results, it was confirmed that one kind of polymerizable monomer is not a monomer capable of achieving both vertical orientation and pre-tilt change amount.

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

Since Examples 1, 12, 26, 42, and 50 use two types of polymerizable monomers without introducing a hydrophobic group, it is considered that the vertical orientation is inferior to that of the other Examples. Be done. On the other hand, in Examples 5, 6, 24, 27, 28, 38, 39, and 46, the polymerization did not proceed easily because the polymerizable monomer whose light absorption region was not shifted to the relatively long wavelength side was used. In the initial stage of polymerization, the formation of the polymer network was insufficient, and as a result, the amount of change in pretilt was inferior to that of the other examples. From the above experimental results, high vertical orientation and a small amount of pre-tilt change can be achieved by appropriately selecting two types of monomers whose functions are separated from the polymerizable monomer involved in the polymerization and the polymerizable monomer contributing to the vertical orientation. It is thought that it can be done. In the other examples, it was confirmed that in addition to high vertical orientation, a sufficiently small amount of change in pretilt angle was exhibited, and display unevenness and seizure were small. In particular, the polymerizable monomer having a hydrophobic group introduced acts as an intermediary between the spontaneously oriented monomer and another type of polymerizable monomer, and the strength of the polymer is improved by improving the crosslink density of the polymerized layer while maintaining high vertical orientation. As a result of the increase in stability, it is considered that the stability is excellent.

Moreover, when the pretilt angle generated by the polymerization by ultraviolet light irradiation was evaluated, bifunctional monomers having a hydrophobic group introduced into the mesogen side chain (for example, RM-3, RM-5, RM-6, RM-8) were found. It was confirmed that an appropriate tilt angle was imparted to the sample to which the polymerizable monomer (for example, RM-4, RM-12 to RM-14) having absorption at a long wavelength was added. It was suggested that the liquid crystal display element using these has a sufficiently high-speed response because a sufficient pretilt angle is given.

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

Further, even when the amount of the spontaneously oriented monomer added in Examples 1 to 95 is replaced from 1.0 part by mass to 0.5 part by mass, the vertical orientation and the amount of change in pretilt are small, and display unevenness and seizure occur. I confirmed that it could be suppressed.

Instead of the composition LC-1, a composition composed of the compounds and a mixing ratio as shown below was prepared, and the liquid crystal composition was changed from LC-2 to LC-8.

(Examples 96 to 103)
It was confirmed that even if the base composition of Example 3 was replaced from LC1 to LC2, the vertical orientation and the amount of change in pre-tilt were small, and display unevenness and seizure were suppressed (Example 96).
It was confirmed that even if the base composition of Example 30 was replaced with LC1 to LC3, the vertical orientation and the amount of change in pre-tilt were small, and display unevenness and seizure were suppressed (Example 97).

It was confirmed that even if the base composition of Example 35 was replaced with LC1 to LC4, the vertical orientation and the amount of change in pre-tilt were small, and display unevenness and seizure were suppressed (Example 98).

It was confirmed that even if the base composition of Example 36 was replaced from LC1 to LC5 and the polymerizable compound was replaced from P-6 to P-11, the vertical orientation and the amount of change in pretilt were small, and display unevenness and seizure were suppressed ( Example 99).

It was confirmed that even if the base composition of Example 41 was replaced from LC1 to LC6 and the polymerizable compound was replaced from P-6 to P-18, the vertical orientation and the amount of change in pretilt were small, and display unevenness and seizure were suppressed ( Example 100).

It was confirmed that even if the base composition of Example 44 was replaced from LC1 to LC7 and the polymerizable compound was replaced from P-7 to P-23, the vertical orientation and the amount of change in pretilt were small, and display unevenness and seizure were suppressed ( Example 101).

It was confirmed that even if the base composition of Example 47 was replaced from LC1 to LC8 and the polymerizable compound was replaced from P-8 to P-30, the vertical orientation and the amount of change in pretilt were small, and display unevenness and seizure were suppressed ( Implementation 102).

It was confirmed that even if the base composition of Example 56 was replaced from LC1 to LC8 and the polymerizable compound was replaced from P-10 to P-34, the vertical orientation and the amount of change in pretilt were small, and display unevenness and seizure were suppressed ( Example 103).

Further, even when the amount of the spontaneously oriented monomer added in Examples 96 to 103 is replaced from 1.0 part by mass to 0.5 part by mass, the vertical orientation and the amount of change in pretilt are small, and display unevenness and seizure occur. I confirmed that it could be suppressed.

(Examples 104 to 123)
0.2 parts by mass of the spontaneously oriented monomer (1) shown in the table below, 0.4 parts by mass of the spontaneously oriented monomer (2), and the amounts of the polymerizable monomers (1) and (2) shown in the table below. ) Was added to any of the compositions LC-1 to LC-8, respectively, and a liquid crystal composition was prepared in the same manner as in Comparative Example 1.

The low-temperature storage stability, vertical orientation, and pre-tilt stability of the combination of two spontaneously oriented monomers and two polymerizable monomers were evaluated. By mixing two types of spontaneously oriented monomers with low solubility at a low concentration, it was confirmed that the vertical orientation was improved while maintaining low temperature storage. In addition, by using a mixture of several types of polymerizable monomers, the concentration of the polymerizable monomer component could be increased and the pretilt stability could be improved.

From the above-mentioned evaluation results of each example, the liquid crystal composition in the examples showed overall excellent performance as a liquid crystal display element.

(Examples 124 to 149)
Liquid crystal compositions were prepared in the same manner as in Example 1 except that the spontaneously oriented monomers of Example 1 were replaced with 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 even when various spontaneously oriented monomers were used, the vertical orientation and the amount of change in pretilt were small, and display unevenness and seizure were suppressed.

Claims (5)

Mesogen groups with two or more cyclic groups and
The general formula (PG1) is linked to the cyclic group located at one end of the mesogen group directly or via a spacer group.

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

(In the formulas (RI) to (R-IX),
R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are independent of each other and are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms.
W ¹ is a single bond, —O— or methylene group
T ¹ is a single bond or COO-
p ¹ , t ¹ and q ¹ are independently 0, 1 or 2, respectively.
Wherein one or more hydrogen atoms of the polymerizable group P ¹¹ may be substituted by a suction group or adsorptive group may have a polymerizable group as a substituent represented by the general formula (PG1),
In the above formula * binds to S ¹¹ represents a bond. )
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 -, as the oxygen atoms are not directly adjacent, the adsorptive group, -O -, - OCO- or -COO- May be replaced with
* In the above chemical formula represents a bond and binds to a cyclic group located at one end of the mesogen group directly or via a spacer group. )
With at least one polymerizable group represented by
The following general formula is linked to the cyclic group to which the polymerizable group is linked.

(In these formulas,
R ^ct is represented by a hydrogen atom, an alkyl group having 1 to 7 carbon atoms, or a polymerizable group P ¹¹ −S ¹¹ −.
The hydrogen atom in the molecule may be substituted with the above-mentioned polymerizable group P ¹¹ −S ¹¹ −.
* Represents a bond and is linked to the cyclic group to which the polymerizable group represented by the general formula (PG1) of the mesogen group is bonded. )
Containing at least one spontaneously oriented monomer having at least one adsorbent group represented by
The following general formula (I) having a chemical structure different from that of the spontaneously oriented monomer

(In the above general formula (I),
R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are independently alkyl groups having 1 to 18 carbon atoms and alkoxy groups having 1 to 18 carbon atoms, respectively. Represents either a halogen atom or a hydrogen atom
R ¹⁰¹ and ^{R 110} are each ^{independently,} P 21 ^{-S 21} - represents,
P ²¹ represents any of the following equations (RI) to (R-IX).

(In the above formulas (RI) to (R-IX),
R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are independent of each other and are alkyl groups having a hydrogen atom and 1 to 5 carbon atoms.
W is a single bond, —O— or methylene group,
T is a single bond or -COO-
p, t and q are 0, 1 or 2 independently of each other. )
S ²¹ represents a single bond or an alkylene group having 1 to 15 carbon atoms.
One or more -CH _2- in the alkylene group may be substituted with -O-, -OCO- or -COO- so that oxygen atoms are not directly adjacent to each other.
n ¹¹ represents 0, 1 or 2,
A ¹¹ is the following group (a), group (b) and group (c):
(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 = existing in this group or two or more -CH = not adjacent to each other may be replaced with -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) , 3,4-Tetrahydronaphthalene-2,6-Diyl group One -CH = or two or more non-adjacent -CH = may be replaced with -N =).
Represents a group selected from the group consisting of
The groups (a), groups (b) and groups (c) are independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen, a cyano group and a nitro group. Alternatively, it may be replaced with P ¹¹ − S ¹¹ −.
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 -, - 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- (in the formula) , R ^a each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, in the formula, z each independently represent a.) 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 from each other. )
A liquid crystal composition containing two or more kinds of polymerizable monomers selected from the group consisting of the polymerizable monomers represented by. The first aspect of the present invention, 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). Liquid crystal composition. General formulas (N-1), (N-2) and (N-3)

(During the ceremony,
^RN11 , ^RN12 , ^RN21 , ^RN22 , ^RN31 and ^RN32 each independently represent an alkyl group having 1 to 8 carbon atoms.
One or two or more non-adjacent −CH ₂ −s in the alkyl group are independently −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO. May be replaced by −
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 and A ^N32 are independently (a) 1,4-cyclohexylene groups (one -CH _2- or adjacent to each other in this group). Two or more -CH ₂ − that are not present may be replaced with -O-.)
(B) 1,4-Phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -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 = existing in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. ) And (d) represent a group selected from the group consisting of 1,4-cyclohexenylene groups.
The above group (a), group (b), group (c) and group (d) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, respectively.
^{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 = NN = CH-, -CH = CH-, -CF = CF- or -C≡C- Represent,
X ^N21 represents a hydrogen atom or a fluorine atom.
^TN31 represents −CH _2- or oxygen atom,
Although n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 and n ^N32 each independently represent an integer of 0 to 3,
n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are independently 1, 2 or 3, respectively.
When a plurality of A ^{N11 to} A ^N32 and Z ^{N11 to} Z ^N32 exist, they may be the same or different. )
The liquid crystal composition according to claim 1 or 2, which contains one or more compounds selected from the compounds represented by. General formula (L)

(During the ceremony,
^RL1 and ^RL2 each independently represent an alkyl group having 1 to 8 carbon atoms.
One or two or more non-adjacent −CH ₂ −s in the alkyl group are independently −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO. May be replaced by −
n ^L1 represents 0, 1, 2 or 3
A ^L1 , A ^L2, and A ^L3 are independently (a) 1,4-cyclohexylene groups (one -CH _2- existing in this group or two or more -CH ₂ not adjacent to each other. -May be replaced with -O-.)
(B) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -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) , 3,4-Tetrahydronaphthalene-2,6-Diyl group One -CH = or two or more non-adjacent -CH = may be replaced with -N =).
Represents a group selected from the group consisting of
The above group (a), group (b) and group (c) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, respectively.
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 -, - It represents OCF _2- , -CF ₂ O-, -CH = N-N = CH-, -CH = CH-, -CF = CF- or -C≡C-.
If n ^L1 is 2 or 3 and there are a plurality of A ^L2s , they may be the same or different, and if n ^L1 is 2 or 3 and there are a plurality of Z ^L2s , they may be the same or different. May be the same or different, except for compounds represented by the general formula (N-1), the general formula (N-2) and the general formula (N-3). )
The liquid crystal composition according to any one of claims 1 to 3, which contains one kind or two or more kinds of compounds selected from the compounds represented by. One of the polymerizable monomers represented by the general formula (I) has n ¹¹ of 0 and is any 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} - is a liquid crystal according to any one of claims 1-4 Composition.