JP2021001973A - Polymerizable liquid crystal composition, optical anisotropic substance, and manufacturing method therefor - Google Patents

Abstract

To provide a polymerizable liquid crystal composition that contains a polymerizable liquid crystal compound having reverse wavelength dispersibility or low wavelength dispersibility, which can be vertically orientated without a vertical orientation film, an optical anisotropic substance and a phase difference film obtained by curing the composition, and an elliptic polarization plate and a display device using the phase difference film.SOLUTION: The present invention is a polymerizable liquid crystal composition containing: a) a polymerizable compound having two or more polymerizable groups and satisfying formula (I): Re(450nm)/Re(550nm)<1.0 (where Re (450nm) represents an in-plane phase difference at a wavelength of 450 nm when the polymerizable compound having two or more polymerizable groups is horizontally oriented on a substrate in such a way that the long-axis direction of molecules is substantially parallel to the substrate, and Re (550nm) represents an in-plane phase difference at a wavelength of 550 nm when the polymerizable compound having one polymerizable group or the polymerizable compound having two or more polymerizable groups is horizontally oriented on the substrate in such a way that the long-axis direction of molecules is substantially parallel to the substrate; and b) an autonomously-orienting compound.SELECTED DRAWING: None

Description

The present invention is a polymerizable composition useful as a constituent member of a film or the like, and an optically anisotropic substance, a retardation film, or an optical body obtained from the polymerizable composition and having optical anisotropy requiring various optical characteristics. The present invention relates to a compensating film, an antireflection film, a liquid crystal display element using the polymerizable composition, an organic light emitting display element, a polarizing film, and the like.

Compounds having a polymerizable group (polymerizable compounds) are used in various optical materials. For example, a polymer having a uniform orientation can be produced by arranging a polymerizable composition containing a polymerizable compound in a liquid crystal state and then polymerizing the composition. Such a polymer can be used for a polarizing plate, a retardation plate, etc. required for a display. In many cases, two or more types of polymerization are performed to satisfy the required optical properties, polymerization rate, solubility, melting point, glass transition temperature, polymer transparency, mechanical strength, surface hardness, heat resistance and light resistance. A polymerizable composition containing a sex compound is used. At that time, the polymerizable compound used is required to bring good physical properties to the polymerizable composition without adversely affecting other properties.

In order to improve the visibility of liquid crystal displays and organic EL displays, it is required to reduce or reverse the wavelength dispersion of the birefringence of the retardation film. As a material for that purpose, various polymerizable liquid crystal compounds having reverse wavelength dispersibility or low wavelength dispersibility have been developed.

At present, as a λ / 4 film (positive A plate retardation film) used for a circular polarizing plate for an antireflection film of an OLED, a polymerizable liquid crystal compound having reverse wavelength dispersibility or low wavelength dispersibility has begun to be used. Patent Document 1 discloses a type of retardation film having a reverse wavelength dispersibility in an A plate to which a liquid crystal composition having a reverse wavelength dispersibility or a low wavelength dispersibility is applied. On the other hand, as the positive C plate retardation film for correcting the viewing angle, a film coated with a polymerizable composition mainly containing a polymerizable liquid crystal compound having positive wavelength dispersibility is used, and reverse wavelength dispersion is used. Alternatively, a coating type retardation film having low wavelength dispersibility is desired (see Patent Document 2). However, the polymerizable compound used in the above-mentioned inverse wavelength dispersible λ / 4 retardation film has a special T-shaped mesogen skeleton and has polymerizable groups at both ends in the long axis direction, so that it is a substrate. It is difficult to orient the film vertically, and a vertically oriented film is absolutely necessary. Therefore, a liquid crystal composition having a reverse wavelength dispersion or a low wavelength dispersion capable of vertically aligning a polymerizable liquid crystal composition having a reverse wavelength dispersibility or a low wavelength dispersibility without using a vertical alignment film, and a liquid crystal composition having a low wavelength dispersibility. The coating type retardation film is required.

JP-A-2002-267838 Japanese Unexamined Patent Publication No. 2008-273925

The problem to be solved by the present invention is the polymerization of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having inverse wavelength dispersibility or low wavelength dispersibility, which can be vertically oriented without providing a vertically oriented film. An object of the present invention is to provide a liquid crystal composition, an optically anisotropic substance obtained by curing the liquid crystal composition, a retardation film, an elliptical polarizing plate using these retardation films, and a display device.

The present invention has been provided as a result of intensive studies on the composition for obtaining vertical orientation in order to solve the above problems.
That is, the present invention a) has two or more polymerizable groups and has the formula (I).
: Re (450 nm) / Re (550 nm) <1.0 (I)
(In the formula, Re (450 nm) is the wavelength of 450 nm when the polymerizable compound having two or more polymerizable groups is oriented on the substrate in the major axis direction substantially horizontally with respect to the substrate. The in-plane retardation, Re (550 nm), is such that the polymerizable compound having one polymerizable group or the polymerizable compound having two or more polymerizable groups is substantially placed on the substrate in the major axis direction of the molecule. Represents the in-plane phase difference at a wavelength of 550 nm when oriented horizontally with respect to the substrate.)
Polymerizable compounds that satisfy
And b) relating to a polymerizable liquid crystal composition, which comprises a spontaneously oriented compound.

The present invention further relates to an optically anisotropic substance composed of a polymer of the polymerizable liquid crystal composition, which has a homeotropic orientation and satisfies the formula (D).
Rth (450) / Rth (550) <1.08 equation (D)
(In the formula, Rth (450) represents the out-of-plane phase difference at a wavelength of 450 nm, and in the formula, Rth (550) represents the out-of-plane phase difference at a wavelength of 550 nm.)
In the present invention, the polymerizable liquid crystal composition is further applied, dried if necessary, and then the composition formed on the substrate is 5 ° C. or more lower than the phase transition temperature of the nematic liquid crystal phase and the isotropic phase. The present invention relates to a method for producing an optically anisotropic substance, which comprises a step of heating at a temperature and then performing a condensation.

The present invention further relates to a polarizing film containing the retardation film (I) made of the optically anisotropic substance and a linear polarizing plate.

The present invention further relates to a display element containing the polarizing film.

The present invention further relates to a light emitting device containing the polarizing film.

According to the present invention, in a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having reverse wavelength dispersibility or low wavelength dispersibility, a polymerizable liquid crystal composition capable of vertical alignment without providing a vertical alignment film. , And an optical variant obtained by curing the same, a retardation film, an elliptical polarizing plate using these retardation films, and a display device.

By using the polymerizable liquid crystal composition of the present invention, it is not necessary to provide a vertically oriented film, so that a vertically oriented optical anisotropic substance can be obtained in fewer steps. In particular, the polymerizable liquid crystal composition of the present invention can impart vertical orientation in a polymerizable liquid crystal composition having reverse wavelength dispersibility or low wavelength dispersibility that is difficult to vertically orient. Therefore, a polymerizable liquid crystal composition suitable for a retardation film of a positive C plate having an inverse wavelength dispersion characteristic, a retardation film having excellent heat resistance obtained by curing the polymerizable liquid crystal composition, and an elliptical particle using these retardation films. A polarizing plate and a display device can be provided.

The best form of the polymerizable composition according to the present invention will be described below. In the present invention, the "liquid crystal compound" is intended to indicate a compound having a mesogenic skeleton, and the compound alone is not used. It does not have to show liquid crystallinity. The polymerizable composition can be polymerized (filmed) by subjecting it to a polymerization treatment by irradiation with light such as ultraviolet rays or heating.
<Spontaneous orientation compound>
First, b) a spontaneously oriented compound contained in the polymerizable liquid crystal composition of the present invention will be described. The spontaneously oriented compound of the present invention has the formula (I).
: Re (450 nm) / Re (550 nm) <1.0 (I)
(In the formula, Re (450 nm) is the wavelength of 450 nm when the polymerizable compound having two or more polymerizable groups is oriented on the substrate in the major axis direction substantially horizontally with respect to the substrate. The in-plane retardation, Re (550 nm), is such that the polymerizable compound having one polymerizable group or the polymerizable compound having two or more polymerizable groups is substantially placed on the substrate in the major axis direction of the molecule. Represents the in-plane phase difference at a wavelength of 550 nm when oriented horizontally with respect to the substrate.)
When a polymerizable liquid crystal composition containing a polymerizable compound satisfying the above conditions is applied to a substrate or the like, the spontaneously oriented compound is oriented perpendicularly to the substrate, thereby inducing vertical orientation of the polymerizable compound. Therefore, the coating film of the polymerizable liquid crystal composition containing the spontaneously oriented compound can realize the vertical orientation without providing the vertical alignment film.

Such a spontaneously oriented compound is preferably a compound having a partial structure represented by the following general formula (K-1), (K-2) or (K-3).

(In the formula, the black dots represent the bonds,
T ^k1 are independently from the general formulas (T-1) to (T-7).

(In the formula, the black dot represents the bond.) Represents the group represented by
^ST1 independently represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms, and the alkylene The −CH ₂₋ of the group or the alkenylene group may be replaced with −O−, −COO−, −C (= O) − or −OCO− so that the oxygen atom is not directly adjacent to the group.
R ^T1 represents an alkyl group having 1 to 5 carbon atoms independently, -CH ₂ of the alkyl groups - as is not adjacent the oxygen atom directly -O -, - COO -, - C (= O) May be replaced with − or −OCO−
^RT2 and ^RT3 independently represent hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, respectively.
R ^k1 independently represents a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group is −O−. May be replaced with
T ^k2 are independently from the general formulas (T-8) to (T-17).

(In the formula, the black dot represents the bond), X ^K1 and Y ^K1 independently represent −CH ₂ −, oxygen atom or sulfur atom, and Z ^K1 is independent of each other. W ^K1 , ^UK1 , V ^K1 and ^SK1 each independently represent a methine group or a nitrogen atom, and here, from the general formula (T-8) to (T-17). The hydrogen atom in the group represented by) may be substituted with −Sp ⁱ⁵ −P ⁱ³ .
Sp ⁱ³ , Sp ⁱ⁴ and Sp ⁱ⁵ each independently represent a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms or a linear or branched halogenated alkylene group having 1 to 20 carbon atoms. -CH _2- in the alkylene group or halogenated alkylene group may be substituted with -CH = CH-, -C≡C- or -O- without the two -O- adjacent to each other.
P ⁱ² and P ⁱ³ are independently from the general formulas (P-1) to (P-16).

(In the formula, the black dot represents the bond.)
When a plurality of P ⁱ² , P ⁱ³ , Sp ⁱ³ , Sp ⁱ⁴ , Sp ⁱ⁵ , T ^k1 , and R ^k1 exist, they may be the same or different.
ki1 represents an integer of 1 to 3, ki2 and ki3 each independently represent an integer of 0 to 3, but the sum of ki1, ki2 and ki3 is 3. )
Since the partial structure represented by the general formula (K-1), (K-2) or (K-3) has polarity, when the polymerizable liquid crystal composition is applied to a substrate, it is adsorbed on the substrate and polymerized. It is considered that it contributes to the vertical orientation of the polymerizable compound in the polar liquid crystal composition. Therefore, the spontaneously oriented compound has a partial structure represented by the general formula (K-1), (K-2) or (K-3) at the end of the molecule, and the end portion is adsorbed on the substrate. , In order to hold the polymerizable compound in a vertically oriented state, the bonding portion of the partial structure represented by the general formula (K-1), (K-2) or (K-3) is substantially vertical. It is preferable to have an elongated molecular structure. Further, the spontaneously oriented compound preferably has a polymerizable group from the viewpoint of maintaining the orientation.

Each of T ^k1 in the general formula (K-1) independently represents a group represented by the above-mentioned general formulas (T-1) to (T-7), and among them, the general formula (T-1). , (T-3), (T-4) or (T-7) is preferable.

Formula (T-3) and (T-7) ^{S T1} in each independently a single bond, the number alkylene or carbon atom of from one to ten carbon atoms, straight-chain or branched 2-10 It is preferable to represent an individual linear or branched alkenylene group, which is a linear or branched alkylene group having 1 to 7 carbon atoms or a linear or branched alkenylene group having 2 to 7 carbon atoms. Is preferable, and a linear alkylene group having 1 to 3 carbon atoms is preferable. Further, -CH _2- in the alkylene group or alkenylene group may be substituted with -O-, -COO-, -C (= O)-or -OCO- so that oxygen atoms are not directly adjacent to each other.

^{R T1} in formula (T-3) each independently represent an alkyl group having 1 to 5 carbon atoms. The alkyl group is linear or branched. The alkyl groups -CH ₂ - such that oxygen atoms are not directly adjacent are -O -, - COO -, - C (= O) - or optionally substituted in -OCO-. Of these, ^RT1 is preferably a linear alkyl group having 1 to 3 carbon atoms. Further, in the general formula (T-3), it is preferable that at least two or more secondary carbon atoms contain −C (= O).

^RT2 and ^RT3 in the general formula (T-6) each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and among them, it is preferable to represent a hydrogen atom.

In the general formula (K-1), R ^k1 independently represents a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms, and one or two or more non-adjacent alkyl groups in the alkyl group. -CH ₂ − may be substituted with −O −, and more preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms.

In the general formula (K-1), ki1, ki2, and ki3 each independently represent an integer of 0 to 3, but the sum of ki1, ki2, and ki3 is 3. ki1 preferably represents an integer of 1 or 2 from the viewpoint of improving the orientation of the liquid crystal and the solubility in the liquid crystal compound. ki2 preferably represents an integer of 1 or 2, and more preferably represents an integer of 1 from the viewpoint of improving orientation. ki3 preferably represents an integer of 0 or 1.

Such a combination of ki1, ki2 and ki3 can be appropriately selected, but as a preferable combination, for example, ki1 represents an integer of 1, ki2 represents an integer of 2, and ki3 represents an integer of 0. Combination A, ki1 represents an integer of 2, ki2 represents an integer of 1, ki3 represents an integer of 0 Combination B, ki1 represents an integer of 2, ki2 represents an integer of 0, ki3 represents an integer of 1. Examples include a combination C representing the above, a combination D in which ki1 represents an integer of 1, ki2 represents an integer of 1, and ki3 represents an integer of 1.

Here, in the partial structure represented by the general formula (K-1), better orientation can be obtained by adjoining the polar group T ^k1 and the polymerizable group ^{Pi 2.} Also, it can show good solubility in the liquid crystal composition. Therefore, the combination of ki1, ki2, and ki3 is preferably the above combination A when the orientation of the liquid crystal is important, while the above combination C is preferable when the solubility in the liquid crystal composition is important.

Preferred examples of the general formula (K-1) include the following general formulas (K-1-1) to (K-1-5). Of these, the general formulas (K-1-1), (K-1-3) or (K-1--4) are more preferable.

(In the above general formulas (K-1-1) to (K-1-5), a plurality of ^TK1s may be the same or different.)

More specifically, the general formula (K-1) includes the following general formulas (K-1-1A) to (K-1-5D).

(An alkyl group in the general formula (K-1-1A) from among ^{(K-1-5D), R T4} , R T5 and ^{R T6} 1 to 3 carbon atoms ^{independently, n T1} and n ^T2 independently represents 0 or 1, n ^T2 independently represents an integer of 1 to 3, and a plurality of ^RT4 , ^RT5 , ^RT6 , ^nT1 , ^nT2 and ^nT3 , respectively. It may be the same or different.)

Each of T ^k2 in the general formula (K-2) independently represents a group represented by the above-mentioned general formulas (T-8) to (T-17). Preferred examples of the general formulas (T-8) to (T-17) include the following formulas (T-8-1) to (T-17-1). Among them, from the viewpoint of orientation and reactivity, the formulas (T-8-1), (T-8-3), (T-8-5), (T-10-1), (T-13-1) ), (T-15-1) and (T-17-1) are preferable, and formulas (T-8-1), (T-10-1), and (T-13-1) are particularly preferable. Be done.

(In the formula, the black dots represent the bonds.)
Sp ⁱ³ , Sp ⁱ⁴ and Sp ⁱ⁵ each independently represent a single-bonded, linear or branched alkylene group having 1 to 20 carbon atoms or a linear or branched halogenated alkylene group having 1 to 20 carbon atoms. -CH _2- in the alkylene group or halogenated alkylene group may be substituted with -CH = CH-, -C≡C- or -O- without the two -O- adjacent to each other, but is preferable. Represents a linear or branched alkylene group having 1 to 20 carbon atoms or a linear or branched halogenated alkylene group having 1 to 20 carbon atoms, and −CH ₂ − in the alkylene group or halogenated alkylene group. May be replaced by -CH = CH-, -C≡C- or -O- without the two -O- adjacent to each other. Of these, at least one of Sp ⁱ¹ , Sp ⁱ² , Sp ⁱ³ , Sp ⁱ⁴ and Sp ⁱ⁵ represents an alkylene group having 1 to 18 carbon atoms, and more preferably an alkylene group having 2 to 15 carbon atoms. More preferably, it represents an alkylene group having 2 to 8 carbon atoms.

P ⁱ² and P ⁱ³ each independently represent a group selected from the group represented by the general formula (P-1) to the general formula (P-16) described above, and among them, the points of ease of handling and reactivity. Therefore, it is preferable that they are each independently a methacrylate group or an acrylate group, and specifically, a group represented by the general formula (P-1) or (P-2) is particularly preferable.

R ^k1 in the general formula (K-3) independently represents a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms, and one or two or more non-adjacent alkyl groups in the alkyl group. -CH ₂ − may be substituted with −O −, and more preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, but a linear alkyl group having 1 to 3 carbon atoms. It is preferable to represent. Examples of the spontaneously oriented compound having a one-group type (K-3) partial structure include a silane coupling agent. The silane coupling agent is not particularly limited, and a known silane coupling agent can be used.

The spontaneous orientation agent having a partial structure represented by the general formula (K-1), (K-2) or (K-3) is preferably a compound represented by the following general formula (i). ..

(In the formula, ^Ki1 has the same meaning as the general formula (K-1), (K-2) or (K-3) according to claim 2.
R ^{i1 is, K i1} represents general formula (K-1) or a linear or branched alkyl group or halogenated alkyl group having carbon atoms 1 to 40 when (K-2) represent the, in these groups secondary carbon atom, as the oxygen atoms are not directly adjacent -O of -, - CH = CH- or -C≡C- may be substituted ^{with, when K i1} represents the general formula (K-3) Represents a linear or branched alkyl group or halogenated alkyl group having 1 to 40 carbon atoms, and the secondary carbon atoms in these groups are -O-, -CH = CH so that oxygen atoms are not directly adjacent to each other. It may be substituted with −, −C≡C−, −NH−, or represents any group represented by the general formulas (P-101) to (P-121).

A ⁱ¹ represents a divalent aromatic group, a divalent cyclic aliphatic group, or a divalent heterocyclic compound group, and the hydrogen atom in A ⁱ¹ may be substituted with ^{Li 1} , and A ^{when i1} there are multiple, the ^{a i1} closest to Sp ^i1, hydrogen atoms in the structure ^is, L ^i1, P i1 ^{-Sp i1} - or ^{-K i1} may be substituted with,
^Li1 represents a halogen atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 40 carbon atoms, and an alkyl halide group, and the secondary carbon atom in the alkyl group is directly adjacent to an oxygen atom. It may be replaced with -CH = CH-, -C≡C-, -O-, -NH-, -COO- or -OCO- so as not to be.
^{Pi 1} represents a polymerizable group
Sp ⁱ¹ represents a spacer group or a single bond,
Z ⁱ¹ is a single bond, -CH = CH -, - CF = CF -, - C≡C -, - COO -, - OCO -, - OCOO -, - CF 2 O -, - OCF 2 -, - CH = CHCOO-, -OCOCH = CH-, -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 2 to 20 carbon atoms, and one or two or more non-adjacent -CH _2- in this alkylene group is -O-, -COO- or May be replaced with −OCO−
^mi1 represents an integer of 0 to 5, and when there are a plurality of A ⁱ¹ , Z ⁱ¹ , ^{Li 1} , ^{Ki 1} , ^{Pi 1,} and Sp ^{i 1 in} the general formula (i), they are different even if they are the same. You may be. )
The compound represented by the general formula (i) has −K ⁱ¹ on one side in the major axis direction in its molecular structure. As described above, by having a characteristic structure in which polar groups are unevenly distributed on one side in the major axis direction, the effect of the polymerizable liquid crystal composition containing the compound represented by the above-mentioned general formula (i) is further exhibited. It will be easier.

Hereinafter, a case where ^{Ki 1} in the general formula (i) represents the general formula (K-1) or (K-2) will be described first. When K ⁱ¹ in the general formula (i) represents the general formula (K-1) or (K-2), R ⁱ¹ is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. , More preferably a linear or branched alkyl group having 3 to 18 carbon atoms. -CH ₂₋ in the alkyl group may be substituted with −CH = CH−, −C≡C− or −O−. However, two or more -O-s are not adjacent to each other. From the viewpoint of improving the orientation of the liquid crystal compound, the number of carbon atoms in ^Ri1 is preferably 3 or more, preferably 4 or more, and preferably 5 or more. When K ⁱ¹ in the general formula (i) represents the general formula (K-1) or (K-2), it is assumed that R ⁱ¹ does not contain a polymerizable group.

Specifically, ^Ai1 is a 1,4-phenylene group, a 1,4-cyclohexylene group, an anthracene-2,6-diyl group, a phenanthrene-2,7-diyl group, a pyridine-2,5-diyl group. , Pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, chromane-3,7-diyl, 1,2,3,4-tetrahydronaphthalene-2,6 The −diyl group or 1,3-dioxane-2,5-diyl group is preferable, and the ring structure in these groups is preferably unsubstituted or the hydrogen atom is preferably substituted with ^Li1 .

Further, the ring structure in these ^groups, P i1 ^{-Sp i1} - it is also preferably substituted with. Having at least one In the general formula (i), from the viewpoint of improving the orientation property, the polymerizable group having a group ^{(P i1 -Sp i1 -, P} i2 -Sp i3 - - or ^P i3 ^{-Sp i5)} it is ^preferred, P i1 ^{-Sp i1} - and ^P i2 ^{-Sp i3} -, or ^P i1 ^{-Sp i1} - and ^P i3 ^{-Sp i5} - as in the group in the general formula (i) having a polymerizable group It is preferable to have two or more.

^Li1 is an alkyl group having 1 to 12 carbon atoms, an alkyl halide group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, or a halogen. Atoms are preferable, and alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, or halogen atoms are more preferable. Examples of the halogen atom include a fluorine atom and a chlorine atom, and among them, a fluorine atom is preferable. The alkyl group, the halogenated alkyl group, and the alkoxy group may be linear or branched.

Preferably, ^Ai1 is a divalent unsubstituted 6-membered ring aromatic group, or a divalent unsubstituted 6-membered ring aliphatic group, or hydrogen atoms in these ring structures having 1 to 12 carbon atoms. It represents an alkyl group, an alkyl halide group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, or a group substituted with a halogen atom. More preferably, in ^Ai1 , the hydrogen atom in the ring structure is an alkyl group having 1 to 6 carbon atoms, an alkyl halide group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom. Represents a 1,4-phenylene group, a 2,6-naphthalene group or a 1,4-cyclohexyl group which may be substituted with. The halogen atom is preferably a fluorine atom.

Z ⁱ in the general formula (i) is a single bond, -CH = CH-, -CF = CF-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH = CHCOO-, -OCOCH = CH-, -OCH ₂ CH ₂ O-, or an alkylene group having 1 to 10 carbon atoms, or one or two or more non-adjacent -CH _{2- in the} alkylene group. Preferably represents a group substituted with -O-, -COO- or -OCO-. More preferably, Z ⁱ¹ is a single bond, -COO-, -OCO-, -CH = CHCOO-, -OCOCH = CH-, -OCH ₂ CH ₂ O-, linear or branched with 1 to 6 carbon atoms. Represents a alkylene group, or a group in which one or two or more -CH ₂ − not adjacent to each other are substituted with an -O-, -COO- or -OCO-. More preferably, Z ⁱ¹ is in a single bond, -COO-, -OCO-, -OCH ₂ CH ₂ O-, or an alkylene group having 2 carbon atoms (ethylene group (-CH ₂ CH _2- )) or an ethylene group. One of -CH _2- is substituted with -O- (-CH ₂ O-, -OCH _2- ), or one of -CH _2- in the ethylene group is -COO-, -OCO- Represents a group substituted with (-CH _2- CH ₂ COO-, -OCOCH _2- CH _2- ).

Sp ⁱ¹ represents a single-bonded, linear or branched alkylene group having 1 to 20 carbon atoms or a linear or branched halogenated alkylene group having 1 to 20 carbon atoms, and is contained in the alkylene group or halogenated alkylene group. -CH ₂ − may be substituted with −CH = CH −, −C≡C− or −O− without the two −O−s adjacent to each other, but preferably directly having 1 to 20 carbon atoms. Represents a chain or branched alkylene group or a linear or branched halogenated alkylene group having 1 to 20 carbon atoms, and -CH _2- in the alkylene group or halogenated alkylene group has two -O- adjacent to each other. It may be replaced with −CH = CH−, −C≡C− or −O− without the exception. Of these, at least one of Sp ⁱ¹ , Sp ⁱ² , Sp ⁱ³ , Sp ⁱ⁴ and Sp ⁱ⁵ represents an alkylene group having 1 to 18 carbon atoms, and more preferably an alkylene group having 2 to 15 carbon atoms. More preferably, it represents an alkylene group having 2 to 8 carbon atoms.

^{Pi 1} represents a polymerizable group, preferably a group selected from the group represented by the general formula (P-1) to the general formula (P-16) described above, and among them, convenience of handling and reactivity. From this point of view, it is preferable that they are each independently a methacrylate group or an acrylate group, and specifically, a group represented by the general formula (P-1) or (P-2) is particularly preferable.

^mi1 represents an integer from 0 to 5. When ^Ki1 in the general formula (i) represents (K-1-1) to (K-1-4) and (K-2), ^mi1 preferably represents 2-4, or 3 or. It is more preferable to represent 4. In this case, the general formula (i) preferably represents the following general formulas (R-1) to (R-6).

^{(Wherein, R i1, K i1, Sp} i1 and ^{L i1} represents ^R i1 in the general formula ^(i), K i1, and ^{Sp i1} and ^{L i1} the same meanings, respectively.)
More specific examples of such a general formula (i) are represented by the following formulas (R-1-1) to (R-8-1), but are not limited thereto.

^{(Wherein, R i1, P i1, P} i2, P i3, Sp i1, Sp i3, Sp i5, X K1, T k1 and ^{R k1} are each independently formula (i), the general formula (K1 ), the general formula (K-3) and ^R i1 in the general formula ^{(T-8), P i1} , P i2, P i3, Sp i1, Sp i3, same as ^{Sp i5,} X ^{K1, T k1} and ^{R k1} Represents the meaning.)
When ^Ki1 in the general formula (i) represents (K-1-5), ^mi1 preferably represents 0. When K ⁱ¹ represents (K-1-5), R ^k1 preferably represents a hydrogen atom, more preferably (K-1-5A). In this case, it represents the m ⁱ¹ in the general formula (i) is 0, Ri1 is preferably represents a straight-chain or branched alkyl group having 3 to 40 carbon atoms, of the general formula 6 to 40 linear or branched It preferably represents an alkyl group, preferably a so-called higher alcohol.

Next, a case where ^{Ki 1} in the general formula (i) represents the general formula (K-3) will be described. When K ⁱ¹ represents the general formula (K-3), the general formula (i) has a function of a silane coupling agent.

Specifically, when K ⁱ¹ in the general formula (i) represents the general formula (K-3), R ⁱ¹ is preferably a linear or branched alkyl group having 1 to 18 carbon atoms. More preferably, it is a linear or branched alkyl group having 3 to 18 carbon atoms, and −CH ₂ − in the alkyl group is preferably substituted with −CH = CH − or −NH−. Specifically, it preferably has a vinyl group or amino group structure. Further, R ⁱ¹ represents any group represented by the general formulas (P-101) to (P-121), but (P-101), (P-102), (P-107) to ( It is preferable to represent P-110), (P-115) or (P-121).

When ^Ki1 in the general formula (i) represents the general formula (K-3), ^mi1 preferably represents 0 or 1, and more preferably 0.

When K ⁱ¹ in the general formula (i) represents the general formula (K-3), Sp ⁱ¹ is a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms, or a direct chain having 1 to 20 carbon atoms. Represents a chain or branched halogenated alkylene group, where -CH ₂ − in the alkylene group or halogenated alkylene group is −CH = CH−, −C≡C− or − without two −O−s adjacent to each other. Although it may be substituted with O−, it preferably represents a linear or branched alkylene group having 1 to 20 carbon atoms or a linear or branched halogenated alkylene group having 1 to 20 carbon atoms, and the alkylene group. Alternatively, −CH ₂₋ in the halogenated alkylene group may be substituted with −CH = CH−, −C≡C− or −O− without the two −O−s adjacent to each other. Of these, at least one of Sp ⁱ¹ , Sp ⁱ² , Sp ⁱ³ , Sp ⁱ⁴ and Sp ⁱ⁵ represents an alkylene group having 1 to 18 carbon atoms, and more preferably an alkylene group having 2 to 15 carbon atoms. More preferably, it represents an alkylene group having 2 to 8 carbon atoms.

The content of the spontaneously oriented compound of the present invention in the total amount of the polymerizable liquid crystal compound is preferably 0.01 to 30% by mass, but the lower limit thereof is the liquid crystal composition from the viewpoint of preferably orienting the liquid crystal molecules. Based on the total amount of the substance, it is preferably 1% by mass or more, 3% by mass or more, 5% by mass or more, 10% by mass or more, or 5% by mass or more. The upper limit of the content of the spontaneous alignment agent of the present invention is preferably 30% by mass or less, 20% by mass or less, and 15% by mass with respect to the entire polymerizable liquid crystal composition from the viewpoint of preferably orienting the liquid crystal molecules. % Or less.
<Polymerizable compound>
The polymerizable liquid crystal composition of the present invention contains a) has two or more polymerizable groups and has the formula (I).
: Re (450 nm) / Re (550 nm) <1.0 (I)
(In the formula, Re (450 nm) is the wavelength of 450 nm when the polymerizable compound having two or more polymerizable groups is oriented substantially horizontally with respect to the substrate in the long axis direction of the molecule. The in-plane retardation, Re (550 nm), is 550 nm when the polymerizable compound having two or more polymerizable groups is oriented on the substrate in the major axis direction of the molecule substantially horizontally with respect to the substrate. Represents the in-plane phase difference at the wavelength of.)
A polymerizable compound satisfying the above conditions will be described.

The polymerizable compound of the present invention is not particularly limited as long as it is a polymerizable compound satisfying the above a), but preferred compounds will be specifically described below.
(Horizontal and vertical bifunctional polymerizable compound)
The preferred polymerizable liquid crystal compound of the present invention has two polymerizable groups and satisfies the above formula (I).
Re (450 nm) / Re (550 nm) <1.0 (I)
(In the formula, Re (450 nm) is a plane at a wavelength of 450 nm when the polymerizable compound having two polymerizable groups is oriented on the substrate in the major axis direction substantially horizontally with respect to the substrate. The internal phase difference, Re (550 nm), is the plane at a wavelength of 550 nm when the polymerizable compound having two polymerizable groups is oriented on the substrate in the major axis direction substantially horizontally with respect to the substrate. It represents an internal phase difference) and has a molecular structure represented by the general formula (1), and the two polymerizable groups are polymerized on the major axis of the molecule represented by the following general formula (1). A horizontally-vertical bifunctional polymerizable compound having one sex group and having one polymerizable group in G which is a vertical component of the following general formula (1) (hereinafter, this compound is referred to as "horizontal-vertical bifunctional". It may be abbreviated as "polymerizable compound").

Here, in the formula (I), when Re (450 nm) / Re (550 nm) represented by is less than 1, it means that the polymerizable liquid crystal compound exhibits so-called inverse wavelength dispersibility. In particular, 0.80 <Re (450 nm) / Re (550 nm) <0.95, and further 0.80 <Re (450 nm) / Re (550 nm) <0.90 is the color as an optical anisotropic substance. Is preferable from the viewpoint that

(In the formula, P ¹¹ represents a polymerizable group, R ¹² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, Alternatively, it represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom. well, one -CH ₂ in the alkyl group - or nonadjacent two or more -CH ₂ - each independently -O is -, - S -, - CO -, - COO -, - OCO -, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- may be substituted.
S ¹¹ and S ¹² represent a spacer group or a single bond, but if there are multiple S ¹¹ and S ^12, they may be the same or different, respectively.
X ¹¹ and X ¹² are -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-,- O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF ₂ -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -, -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH _2- OCO-, -CH = CH-, -N = N-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, but if there are multiple X ^{11 to} X ^12, they They may be the same or different (however, each P- (SX) -bond does not include -O-O-) from the viewpoint of availability of raw materials and ease of synthesis. , If there are multiple, they may be the same or different, and they are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -COO-, -OCO-,-. CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -,- CH ₂ CH ₂ -COO-, -CH ₂ CH _2- OCO- or a single bond is preferred, and each independently -O-, -OCH _2- , -CH ₂ O-, -COO-, -OCO _{-, - COO-CH 2 CH} 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - it is more preferable that represent _CH 2 CH 2 -OCO- or a single ^{bond, X 21} ~ When a plurality of X ^22s are present, they may be the same or different, and it is particularly preferable that they independently represent -O-, -COO-, -OCO- or a single bond.
A ¹¹ and A ¹² are independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl, respectively. Represents a group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group. groups may be substituted by unsubstituted or one or more L ^2, but when a ¹¹ and / or a ¹² appears more may each have identical or different,
Z ¹¹ and Z ¹² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, -OCO-, -CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO -, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = N-N = CH-, -CF = CF-,- It represents C≡C− or a single bond, but when multiple Z ¹¹ and / or Z ¹² appear, they may be the same or different.
M is from the following formula (M-1) to formula (M-9)

It represents a group selected from these groups may be substituted by unsubstituted or one or more L ^2,
G is from the following formula (G-1) to formula (G-5)

(In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, and may be arbitrary in the alkyl group. the hydrogen atoms may be substituted by a fluorine atom, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S- , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- May be replaced by
W ⁸¹ has at least one aromatic group, an aromatic represents a 30 group from 5 carbon atoms, said group may be substituted by unsubstituted or one or more L ^2, contained in W ⁸¹ The group may be an aromatic hydrocarbon group or an aromatic complex group, and may contain both. These aromatic groups may be bonded via a single bond or a linking group (-OCO-, -COO-, -CO-, -O-), or may form a fused ring. Further, W ⁸¹ may contain an acyclic structure and / or a cyclic structure other than the aromatic group in addition to the aromatic group. Aromatic group contained in W ⁸¹ from the standpoint of ease of raw material availability and synthesis, the following may be substituted by unsubstituted or substituted with one or more L ² from the formula (W-1) Equation (W-19)

(In the formula, these groups may have a bond at an arbitrary position, and may form a group in which two or more aromatic groups selected from these groups are linked by a single bond, Q ¹ Represents -O-, -S-, -NR ^5- (in the formula, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) or -CO-. Among these aromatic groups. -CH = may be replaced each independently -N =, -CH ₂ - are each independently -O -, - S -, - NR 4 - ( wherein, ^{R 4} is hydrogen or C It represents an alkyl group having 1 to 8 atoms.) Or may be replaced with −CO−, but a group represented by —O—O− bond is preferred. Formula (W-1) the group represented by the formula from Equation good following substituted (W-1-1) by unsubstituted or substituted with one or more ^{L 2} (W-1-8 )

(In the formula, these groups may have a bond at an arbitrary position.) It is preferable to represent a group selected from, and the group represented by the formula (W-7) is unsubstituted. expression from equation may following be substituted (W-7-1) or by one or more ^{L 2} (W-7-7)

(In the formula, these groups may have a bond at an arbitrary position.) It is preferable to represent a group selected from, and the group represented by the formula (W-10) is unsubstituted. expression from equation may following be substituted (W-10-1) or by one or more ^{L 2} (W-10-8)

(In the formula, these groups may have a bond at an arbitrary position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group selected from. formula (W-11) the group represented by the formula from equation good following substituted (W-11-1) by unsubstituted or substituted with one or more ^{L 2} (W-11-13 )

(In the formula, these groups may have a bond at an arbitrary position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group selected from. wherein the group represented by (W-12), formula from equation good following substituted (W-12-1) by unsubstituted or substituted with one or more ^{L 2} (W-12-19 )

(In the formula, these groups may have a bond at any position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but they are the same when there are a plurality of R ⁶ atoms. even, it is preferable to represent a group selected from different may.), the group represented by the formula (W-13), is substituted by unsubstituted or substituted with one or more L ² The following formulas (W-13-1) to formulas (W-13-10) may be used.

(In the formula, these groups may have a bond at any position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but they are the same when there are a plurality of R ⁶ atoms. even, it is preferable to represent a group selected from different may.), the group represented by the formula (W-14), is substituted by unsubstituted or substituted with one or more L ² The following equations (W-14-1) to equations (W-14-4) may be used.

(In the formula, these groups may have a bond at an arbitrary position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group selected from. wherein the group represented by (W-15), formula from equation good following substituted (W-15-1) by unsubstituted or substituted with one or more ^{L 2} (W-15-18 )

(In the formula, these groups may have a bond at any position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but they are the same when there are a plurality of R ⁶ atoms. even, it is preferable to represent a group selected from different may.), the group represented by the formula (W-16), is substituted by unsubstituted or substituted with one or more L ² The following equations (W-16-1) to equations (W-16-4) may be used.

(In the formula, these groups may have a bond at an arbitrary position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group selected from. wherein the group represented by (W-17), formula from equation good following substituted (W-17-1) by unsubstituted or substituted with one or more ^{L 2} (W-17-6 )

(In the formula, these groups may have a bond at an arbitrary position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It is preferable to represent a group selected from. wherein the group represented by (W-18), wherein the unsubstituted or one or more equations may following be replaced by ^{L 2 (W-18-1) (} W-18-6)

(In the formula, these groups may have a bond at any position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but they are the same when there are a plurality of R ⁶ atoms. even, it is preferable to represent a group selected from different may.), the group represented by the formula (W-19), is substituted by unsubstituted or substituted with one or more L ² The following equations (W-19-1) to equations (W-19-9) may be used.

(In the formula, these groups may have a bond at an arbitrary position, and R ⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, but is the same when there are a plurality of R ⁶ atoms. It may be present or different.) It is preferable to represent a group selected from. The aromatic group contained in W ⁸¹ is an optionally substituted by unsubstituted or substituted with one or more ^{L 2} formula (W-1-1), the formula (W-7-1), formula (W- 7-2), formula (W-7-7), formula (W-8), formula (W-10-6), formula (W-10-7), formula (W-10-8), formula ( W-11-8), formula (W-11-9), formula (W-11-10), formula (W-11-11), formula (W-11-12) or formula (W-11-13) ), It is more preferable to represent a group selected from the formulas (W-1-1), formulas (W-7-1), and formulas (W) which are unsubstituted or may be substituted by one or more Ls. In particular, it represents a group selected from -7-2), formula (W-7-7), formula (W-10-6), formula (W-10-7) or formula (W-10-8). preferable. Further, W ⁸¹ is expressed by the following equations (W-a-1) to (W-a-6).

(In the formula, r represents an integer from 0 to 5, s represents an integer from 0 to 4, and t represents an integer from 0 to 3.) It is particularly preferable to represent a group selected from.

W ⁸² is a group represented by the following formula (82).

^{(Wherein, P W82} has the same meaning as ^{P 11, S W82} has the same meaning as ^{S 11, X W82} has the same meaning as ^{X 11, m W82} represent. The same meanings as m11) represents ,
The total number of π electrons contained in W ⁸¹ and W ⁸² is preferably 4 to 24 from the viewpoint of wavelength dispersion characteristics, storage stability, liquid crystallinity and ease of synthesis.

W ⁸³ and W ⁸⁴ each have a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, and at least one aromatic group and have 5 to 30 carbon atoms. Group, alkyl group with 1 to 20 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, alkenyl group with 2 to 20 carbon atoms, cycloalkenyl group with 3 to 20 carbon atoms, 1 to 20 carbon atoms Aalkoxy group, an acyloxy group having 2 to 20 carbon atoms, an alkylcarbonyloxy group having 2 to 20 carbon atoms, or a group represented by the following formula (84).

^{(Wherein, P W84} has the same meaning as ^{P 11, S W84} has the same meaning as ^{S 11, X W84} has the same meaning as ^{X 11, m W84} represent. The same meanings as m11) represents the But,
W ⁸³ and W ⁸⁴ have at least one group represented by the above formula (84), and among the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, acyloxy group and alkylcarbonyloxy group. One -CH _2- or two or more non-adjacent -CH ₂ -s are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S- , -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-, where the above M is in equation (M-1). ~ When selected from the formula (M-8) G is selected from the formulas (G-1) to (G-4), and when M is the formula (M-9), G is the formula (G-5). L ² represents fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group, dimethylamino group, diethylamino group. , Diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or alkyl group having 1 to 20 carbon atoms. The alkyl group may be linear or branched, and is optional. the hydrogen atoms may be substituted by a fluorine atom, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S- , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH- Depending on the group selected from COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- It may be substituted, but if a plurality of L ^2s are present in the compound, they may be the same or different. ), N11 and n12 independently represent integers 1 to 4, n11 + n12 represent integers 1 to 5, m11 and m12 each independently represent integers 1 to 4, but m11 + m12 Represents an integer from 1 to 5.

In the general formula (1), the above P ¹¹ represents a polymerizable group, but each of them independently has the following formulas (P-1) to (P-20).

It is preferable to represent a group selected from the above, and these polymerizable groups are polymerized by radical polymerization, radical addition polymerization, cationic polymerization and anionic polymerization. In particular, when ultraviolet polymerization is carried out as a polymerization method, the formula (P-1), the formula (P-2), the formula (P-3), the formula (P-4), the formula (P-6), and the formula (P) -10), formula (P-12), formula (P-14) or formula (P-17) is preferable, and formula (P-1), formula (P-2), formula (P-6), formula (P-6) P-10) or formula (P-12) is more preferable, formula (P-1), formula (P-2) or formula (P-3) is more preferable, and formula (P-1) or formula (P-). 2) is particularly preferable.

In the general formula (1), the S ¹¹ and S ¹² each independently represent a spacer group, but when a plurality of S ¹¹ and S ¹² are present, they may be the same or different. From the viewpoint of liquidity, availability of raw materials, and ease of synthesis, when there are a plurality of them, they may be the same or different, and each of them is independently one −CH ₂ − or not adjacent to each other. Two or more -CH ₂ -are independent of -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO-, -CH ₂ -OCO-, -CH = CH-, -N = N-, -CH = N-N = CH-, -CF = CF- or -C≡C- may be replaced with 1 to 20 carbon atoms. It is preferable to represent the alkylene group of, and if there are a plurality of them, they may be the same or different from each other, and each of them independently has one -CH _2- or two or more -CH _2- that are not adjacent to each other. More preferably represent a linear or branched alkylene group having 1 to 20 carbon atoms, each of which may be independently replaced by -O-, -COO-, -OCO-, -OCO-O-. , If there are a plurality of them, they may be the same or different, and one −CH ₂ − or two or more non-adjacent −CH ₂ −s are independently −O−. It is more preferable to represent a linear or branched alkylene group having 1 to 12 carbon atoms which may be replaced with. From the viewpoint of liquid crystallinity and solubility in a solvent, it is particularly preferable that S ¹¹ and S ¹² each independently represent a linear or branched alkylene group having 1 to 12 carbon atoms.

In the general formula (1), the above X ¹¹ and X ¹² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, respectively. -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-,- OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO- CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _{2 -COO -, - CH 2 -OCO -} , - CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single bond , X ¹¹ and X ¹² may be the same or different if there are more than one. From the viewpoint of availability of raw materials and ease of synthesis, when a plurality of X ¹¹ and X ¹² exist, they may be the same or different, and they are independently -O-, -S-, and-. OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -COO-CH ₂ CH _2- , -OCO- _{CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - it is preferable to represent a _CH 2 CH 2 -OCO- or a single bond, each independently -O -, - COO -, - OCO- or a single bond It is more preferable to represent. From the viewpoint of ease of synthesis, it is particularly preferable that X ¹¹ represents −O− and X ¹² represents a single bond.

In the general formula (1), A ¹¹ and A ¹² are independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidin-2,5-diyl group, respectively. Naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl Representing groups, these groups may be unsubstituted or substituted with one or more substituents L. From the viewpoint of ease of synthesis, availability of raw materials, and liquid crystallinity, A ¹¹ and A ¹² may be independently unsubstituted or substituted with one or more substituents L 1,4. It is more preferable to represent a −phenylene group, a 1,4-cyclohexylene group, and a naphthalene-2,6-diyl group, and each of them independently represents the following formulas (A-1) to (A-11).

It is more preferable to represent the groups selected from the formulas (A-1), and it is even more preferable to represent the groups selected from the formulas (A-1) to (A-8) independently of the formulas (A-1). It is particularly preferable to represent a group selected from the formula (A-4).

In the general formula (1), L is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, A dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyanogroup, or one -CH _2- or two or more non-adjacent -CH ₂ --independently -O. -, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, By -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- It represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom. From the viewpoint of liquidity and ease of synthesis, L may be the same or different when a plurality of L are present, and a fluorine atom, a chlorine atom, or any hydrogen atom may be replaced with a fluorine atom. One -CH _2- or two or more non-adjacent -CH _2- may be independently substituted with a group selected from -O-, -COO- or -OCO-. It preferably represents 1 to 12 linear or branched alkyl groups, where L may be the same or different when a plurality of L atoms are present, and a fluorine atom, a chlorine atom, or any hydrogen atom may be a fluorine atom. It is more preferable to represent a linear or branched alkyl group or an alkoxy group having 1 to 12 carbon atoms which may be substituted with, and when a plurality of L are present, they may be the same or different, and a fluorine atom may be used. , A chlorine atom, or a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms, and when a plurality of L's are present, they may be the same or different, and the fluorine atom and chlorine may be different. It is particularly preferred to represent an atom, methyl group or methoxy group.
In the general formula (1), Z ¹¹ and Z ¹² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, respectively. , -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-,- NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF ₂ -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -, -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH _2- OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, If Z ¹¹ there are a plurality thereof may be the same or different and they may be the same or different if Z ¹² there are a plurality. From the viewpoint of liquidity, availability of raw materials, and ease of synthesis, Z ¹¹ and Z ¹² may be the same or different when a plurality of them exist, and they are independently -OCH _2- and -CH, respectively. ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -COO-CH ₂ CH _2- , -OCO-CH _{2 CH 2 -, - CH 2} CH 2 -COO -, - it is preferable to represent a _CH 2 CH 2 -OCO- or a single bond, may be different even if the same case there are a plurality, each independently It is more preferable to represent -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- or a single bond, and if there are a plurality of them, they are different even if they are the same. It may be preferable that each of them independently represents -OCH _2- , -CH ₂ O-, -COO- or -OCO-. In particular, Z ¹¹ and Z ¹² bound to M are preferably −OCH _2- or −CH ₂ O− from the viewpoint of excellent solvent solubility.
In the general formula (1), n11 and n12 independently represent integers from 1 to 4, while n11 + n12 represent integers from 1 to 5. From the viewpoint of solubility in a solvent, liquid crystallinity, phase difference, and stability over time of inverse wavelength dispersibility, n11 and n12 preferably each independently represent an integer of 1 to 3, and each independently represents 1 or 2. Is more preferable, and 2 is particularly preferable.
In the general formula (1), m11 and m12 independently represent integers from 0 to 4, while m11 + m12 represent integers from 0 to 4. From the viewpoint of solubility in a solvent, liquidity, and orientation, m11 and m12 preferably each independently represent an integer of 0 to 3, and more preferably each independently represent an integer of 0 to 2. It is particularly preferable that each independently represents 0 or 1.

The compound represented by the general formula (1) is preferably represented by the following general formula (1-i) from the viewpoint of orientation, phase difference and anti-wavelength dispersibility over time.

(In the formula, P ¹¹ , R ¹² , S ¹¹ , S ¹² , X ¹¹ , X ¹² , A ¹¹ , Z ¹¹ , m11, m12, n11 have the same meanings as in the general formula (1), and preferred groups are also general. It represents the same as the formula (1). A ¹²¹ represents a 1,4-phenylene group, a 1,4-cyclohexylene group or a naphthalene-2,6-diyl group, and Z ¹²¹ represents -OCH _2- , -CH. ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ −COO−, −CH ₂ CH ₂ −OCO−, −CH = CH-COO−, −OCO-CH = CH− or a single bond)
Further, it is particularly preferable that it is represented by the following general formula (1-i-i).

(In the formula, P ¹¹ , R ¹² , S ¹¹ , S ¹² , X ¹¹ , X ¹² , A ¹¹ , Z ¹¹ , m11, m12, n11 have the same meanings as in the general formula (1), and preferred groups are also general. It represents the same as the formula (1). A ¹²¹ represents a 1,4-phenylene group and a 1,4-cyclohexylene group, and Z ¹²¹ represents -OCH _2- , -CH ₂ O-, -CH ₂ CH _2. -, -COO-, -OCO- or single bond.)
Specifically, as the polymerizable liquid crystal compound represented by the general formula (1), compounds represented by the following formulas (1-1-1) to (1-1-61) are preferable.

Next, in the polymerizable liquid crystal composition of the present invention, it is preferable to use the horizontally and vertically bifunctional polymerizable compounds described in detail above as a) the polymerizable compound, but the total content of the horizontally and vertically bifunctional polymerizable compounds is contained. The amount is preferably 30 to 100% by mass, more preferably 35 to 100% by mass, and particularly preferably 40 to 100% by mass, based on the total amount of the polymerizable compound used in the polymerizable composition. preferable.

Further, when the orientation of the polymerizable composition is emphasized, the lower limit value is preferably 40% by mass or more, and more preferably 50% by mass or more.
Further, when the storage stability of the polymerizable composition is important, the upper limit value is preferably 95% by mass or less, and more preferably 90% by mass or less.
(Reverse wavelength dispersible polyfunctional polymerizable compound)
The polymerizable liquid crystal composition of the present invention has two or more polymerizable groups in addition to the above horizontal and vertical bifunctional polymerizable compounds, and satisfies the following formula (I).
Re (450 nm) / Re (550 nm) <1.0 (I)
(In the formula, Re (450 nm) is the wavelength of 450 nm when the polymerizable compound having two or more polymerizable groups is oriented substantially horizontally with respect to the substrate in the long axis direction of the molecule. The in-plane retardation, Re (550 nm), is 550 nm when the polymerizable compound having two or more polymerizable groups is oriented on the substrate in the major axis direction of the molecule substantially horizontally with respect to the substrate. It represents the in-horizontal phase difference at the wavelength of (2), and preferably contains a compound represented by the general formula (2).

Here, the formula (I) means that the compound exhibits inverse wavelength dispersibility as described above, and in particular 0.8 <Re (450 nm) / Re (550 nm) <0.95, further. , 0.8 <Re (450 nm) / Re (550 nm) <0.90 is preferable from the viewpoint that the color is good as an optically anisotropic substance.

The compound represented by the general formula (2) is specifically a polymerizable compound having two polymerizable groups in the molecular major axis direction, or in addition to the molecular major axis direction with respect to the molecular major axis direction. It means a polymerizable compound having three or more polymerizable groups having a polymerizable group in the vertical direction (reverse wavelength dispersible polyfunctional polymerizable compound).

In the general formula (2), P ¹¹ and P ¹² represent a polymerizable group and have the same meaning as in the general formula (1). Further, S ¹¹ , S ¹² , X ¹¹ , X ¹² , A ¹¹ , A ¹² , Z ¹¹ , Z ¹² , m11, m12, n11, n12 have the same meanings as in the general formula (1).

In the general formula (2), M ² is expressed by the following formula (M-21) to formula (M-213).

It represents a group selected from these groups may be substituted by or one or more L ² or unsubstituted. M ² is a raw material of the easy availability and the synthesis of a ease aspect each independently unsubstituted from or one or more which may be the formula substituted by L ² (M-21) or Formula (M-22 ) or preferably represents a group selected from the formulas (M-26) from the unsubstituted formula (M-23), unsubstituted or 1 or more which may be the formula substituted by L ² (M-21) or It is more preferable to represent a group selected from the formula (M-22), and it is particularly preferable to represent a group selected from the unsubstituted formula (M-21) or the formula (M-22).

In the general formula (2), G ² represents a group selected from the formula (G-21) to the formula (G-26).

In the general formula (2), R ³ , W ⁸¹ , W ⁸² , W ⁸³ and W ⁸⁴ have the same meanings as in the general formula (1).

The compound represented by the general formula (2) is preferably represented by the following general formula (2-i) from the viewpoint of orientation, phase difference and anti-wavelength dispersibility over time.

(In the formula, P ¹¹ , P ¹² , S ¹¹ , S ¹² , X ¹¹ , X ¹² , m11, m12 have the same meaning as the general formula (2), and the preferred group is also the same as the general formula (2). A ¹¹¹ , A ¹¹² , A ¹²¹ and A ¹²² represent a 1,4-phenylene group and a 1,4-cyclohexylene group, and Z ¹¹¹ , Z ¹¹² , Z ¹²¹ and Z ¹²² are -OCH ₂ -,-. CH ₂ O-, -CH ₂ CH _2- , -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -,- CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -CH = CH-COO-, -OCO-CH = CH- or single bond.
In the formula, P ¹¹ , P ¹² , S ¹¹ , S ¹² , X ¹¹ , X ¹² , m11, and m12 have the same meanings as those in the general formula (2), and the preferred groups are also the same as those in the general formula (2). Represent. A ¹¹¹ and A ¹²² represent a 1,4-phenylene group and a 1,4-cyclohexylene group, A ¹¹² and A ¹²¹ represent a 1,4-cyclohexylene group, and Z ¹¹¹ and Z ¹²² represent -COO-,-. _{OCO -, - COO-CH 2} CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- or a single ^{bond, Z 112} and ^{Z 121} are Represents -OCH _2- , -CH ₂ O-, -COO-, -OCO- or a single bond. )
Further, it is particularly preferable that it is represented by the following general formula (2-i-i).

Specifically, as the compound represented by the general formula (2-i-i), a compound represented by the following formulas (2-1-1) to (2-1-74) is preferable.

(In the formula, n represents an integer of 1 to 10.)
The total content of the inverse wavelength dispersible polyfunctional polymerizable compound is preferably 10 to 90% by mass, preferably 10 to 80% by mass, based on the total amount of the polymerizable compound used in the polymerizable composition. Is more preferable, and 10 to 70% by mass is particularly preferable.

Further, when the orientation of the polymerizable composition is emphasized, the upper limit value is preferably 60% by mass or less, and more preferably 50% by mass or less.
Further, when the storage stability of the polymerizable composition is important, the upper limit value is preferably 95% by mass or less, and more preferably 90% by mass or less.
(Positive wavelength dispersible bifunctional polymerizable compound)
In addition to the above-mentioned inverse wavelength-dispersible polymerizable compound, the polymerizable liquid crystal composition of the present invention has a positive wavelength-dispersible polymerizable group having two polymerizable groups represented by the following general formula (3) as long as the performance is not impaired. The compound can be further contained.

In the above general formula (3), the polymerizable groups P ³¹ and P ³² are independently expressed by the following formulas (P-1) to (P-20).

It is preferable to represent a group selected from the above, and among these polymerizable groups, from the viewpoint of enhancing the polymerizable property and storage stability, the formula (P-1), the formula (P-2), the formula (P-7), The formula (P-12) or the formula (P-13) is preferable, and the formula (P-1), the formula (P-7), and the formula (P-12) are more preferable.

In the general formula (3), S ³¹ and S ³² independently represent a spacer group or a single bond, but when a plurality of S ³¹ and S ³² are present, they may be the same or different. The spacer group represents an alkylene group having 1 to 18 carbon atoms, and the alkylene group has one or more halogen atoms, a CN group, an alkyl group having 1 to 8 carbon atoms, or a polymerizable functional group. It may be substituted with an alkyl group having 1 to 8 carbon atoms, and one CH ₂ group existing in this group or two or more CH ₂ groups not adjacent to each other are independent of each other and have an oxygen atom. -O-, -S-, -NH-, -N (CH ₃ )-, -CO-, -CH (OH)-, CH (COOH), -COO-,-in a form in which are not directly bonded to each other. It may be replaced by OCO-, -OCOO-, -SCO-, -COS- or -C≡C-. Among these spacer groups, from the viewpoint of orientation, a linear alkylene group having 2 to 8 carbon atoms, an alkylene group having 2 to 6 carbon atoms substituted with a fluorine atom, and a part of the alkylene group are −O−. Substituted alkylene groups having 5 to 14 carbon atoms are preferred.

In the general formula (3), X ³¹ and X ³² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO. -S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO Represents −, −CH ₂ −OCO−, −CH = CH−, −N = N−, −CH = N−N = CH−, −CF = CF−, −C≡C− or a single bond, but with X ^{When a} plurality of ³¹ and X ³² are present, they may be the same or different (however, each P- (SX)-does not include an -O-O- bond). Further, from the viewpoint of easy availability of raw materials and ease of synthesis, when a plurality of raw materials exist, they may be the same or different from each other, and they are independently -O-, -S-, -OCH _2- ,. -CH ₂ O-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -COO-CH _{2 CH 2 -, - OCO-} CH 2 CH 2 -, - CH 2 CH 2 -COO -, - it is preferable to represent a _CH 2 CH 2 -OCO- or a single bond, each independently -O -, - OCH _2- , -CH ₂ O-, -COO-, -OCO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _2- It is more preferable to represent OCO- or a single bond, and when a plurality of X ³¹ and X ³² are present, they may be the same or different, and they are independently -O-, -COO-, and -OCO. -Or it is particularly preferable to represent a single bond.

In the general formula (3), A ³¹ and A ³² are independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidin-2,5-diyl group, respectively. Naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl represents a group, these groups may be substituted by or one or more L ² or is unsubstituted, but each may be the same or different if a ³¹ and a ³² appears more .. A ³¹ and A ³² which may be substituted by each independently unsubstituted or 1 or more L ² from the standpoint of ease of raw material availability and the synthesis of 1,4-phenylene, 1,4-cyclohexylene It is preferable to represent a hexylene group or naphthalene-2,6-diyl, and each of them independently has the following formulas (A-1) to (A-11).

It is more preferable to represent the groups selected from the formulas (A-1), and it is further preferable to represent the groups selected from the formulas (A-1) to (A-8) independently of the formulas (A-1). It is particularly preferable to represent a group selected from the formula (A-4).

In the general formula (3), Z ³¹ and Z ³² are independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, respectively. , -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-,- NH-CO-NH-, -NH-O-, -O-NH-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF ₂ -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -, -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH ₂ -COO-, -CH _2- OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, When a plurality of Z ³¹ and Z ³² appear, they may be the same or different. Z ³¹ and Z ³² are independently single-bonded, -OCH _2- , -CH ₂ O-, -COO-, and -OCO-, respectively, from the viewpoint of the liquidity of the compound, the availability of raw materials, and the ease of synthesis. _{, -CF 2 O -, - OCF} 2 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -CH = CH-, It preferably represents −CF = CF−, −C≡C− or a single bond, where Z ³¹ and Z ³² are independently −OCH ₂ −, −CH ₂ O−, −CH ₂ CH ₂ −, −COO, respectively. -, -OCO-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH ₂ -OCO-, -CH = CH-, -C More preferably, it represents ≡ C− or a single bond, where Z ³¹ and Z ³² are independently −CH ₂ CH ₂ −, −COO−, −OCO−, −COO−CH ₂ CH ₂₋ , −OCO−. _{CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO- or more preferably represents a single bond, _-CH 2 each independently _{CH 2 -, - COO -,} - OCO -Or it is particularly preferable to represent a single bond.

In the general formula (3), M ³¹ is a 1,4-phenylene group, a 1,4-cyclohexylene group, a 1,4-cyclohexenyl group, a tetrahydropyran-2,5-diyl group, a 1,3-dioxane-2. , 5-Diyl group, tetrahydrothiopyran-2,5-Diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl Group, pyrimidin-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, naphthylene- 1,4-Diyl group, naphthylene-1,5-diyl group, naphthylene-1,6-diyl group, naphthylene-2,6-diyl 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, 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] Benzoselenopheno [3,2-b] Represents a group selected from a serenophen-2,7-diyl group or a fluorene-2,7-diyl group, wherein these groups are unsubstituted or one or more. It may be substituted with L ² , and M ²¹² may be independently unsubstituted or substituted with one or more L ² from the viewpoint of availability of raw materials and ease of synthesis 1,4. - phenylene group, a naphthylene-1,4-diyl group, or a naphthylene-2,6-diyl group is preferred, unsubstituted or one or more groups selected from a good 1,4-phenylene group optionally substituted by ^{L 2} It is more preferable to represent.

In the general formula (3), L ² is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group and a dimethylamino group. , Diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or one -CH _2- or two or more non-adjacent -CH ₂ --independently -O-,-, respectively. S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = Replaced by CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- Although it represents a linear or branched alkyl group having 1 to 20 carbon atoms, any hydrogen atom in the alkyl group may be substituted with a fluorine atom. From the viewpoint of liquidity and ease of synthesis, L ² is a fluorine atom, chlorine atom, pentafluorosulfuranyl group, nitro group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, or any hydrogen. Atoms may be replaced by fluorine atoms, with one -CH _2- or two or more non-adjacent -CH ₂ --independently -O-, -S-, -CO-, -COO. Directly 1 to 20 carbon atoms which may be substituted by a group selected from −, −OCO−, −O−CO−O−, −CH = CH−, −CF = CF− or −C≡C− It preferably represents a chain or branched alkyl group, and a fluorine atom, a chlorine atom, or any hydrogen atom may be replaced with a fluorine atom, and one −CH ₂ − or two or more not adjacent to each other. -CH _2- represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be independently substituted with a group selected from -O-, -COO- or -OCO-. It is more preferable that the fluorine atom, the chlorine atom, or any hydrogen atom represents a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms which may be substituted with the fluorine atom. It is particularly preferable to represent a fluorine atom, a chlorine atom, or a linear alkyl group or a linear alkoxy group having 1 to 8 carbon atoms.

In the general formula (3), m31 and m32 each independently represent an integer of 0 to 5, but it is preferable to represent an integer of 0 to 4 from the viewpoint of liquid crystallinity, availability of raw materials, and ease of synthesis. , 0 to 2 is more preferred, and 0 or 1 is even more preferred.

In the general formula (3), j31 and j32 independently represent integers from 0 to 5, while j31 + j32 represent integers from 1 to 5. From the viewpoint of liquid crystallinity, ease of synthesis, and storage stability, j31 and j32 preferably each independently represent an integer of 1 to 4, more preferably an integer of 1 to 3, and 1 or 2. It is particularly preferable to represent. j31 + j32 preferably represent an integer from 1 to 4, and particularly preferably 2 or 3.

Specifically, as the compound represented by the general formula (3), the compounds represented by the following formulas (3-1) to (3-33) are preferable.

(In the formula, m and n each independently represent an integer of 1 to 18, and R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cyano group. If these groups are alkyl groups with 1 to 6 carbon atoms or alkoxy groups with 1 to 6 carbon atoms, they may all be unsubstituted or substituted with one or more halogen atoms. Good.) These liquid crystal compounds may be used alone or in combination of two or more.

The total content of the positive wavelength dispersible bifunctional polymerizable compound is preferably 0 to 30% by mass, preferably 0 to 20% by mass, based on the total amount of the polymerizable compound used in the polymerizable composition. Is more preferable, and it is particularly preferable that the content is 0 to 15% by mass.

Further, when the orientation of the polymerizable composition is emphasized, the upper limit value is preferably 10% by mass or less, and more preferably 5% by mass or less.

Further, when the storage stability of the polymerizable composition is important, the lower limit value is preferably 5% by mass or more, and more preferably 10% by mass or more.
(Fluorine-based surfactant)
The polymerizable liquid crystal composition of the present invention may contain a fluorine-based surfactant, if necessary. By using the fluorine-based surfactant, the polymerizable liquid crystal composition of the present invention has good compatibility between the polymerizable compound and the fluorine-based surfactant, so that it has excellent solution stability, and when it is made into an optically isomer. Has excellent surface smoothness (repellency resistance).

The fluorine-based surfactant is preferably composed of only carbon atoms, hydrogen atoms, oxygen atoms, fluorine atoms, and nitrogen atoms. The surfactant composed of these atoms is the same as the atom constituting the structure (spacer (Sp) portion and mesogen (MG) portion) other than the terminal portion (terminal group) of the polymerizable compound used in the present invention. Therefore, it is considered that the compatibility with the polymerizable compound is increased.

Further, the fluorine-based surfactant has a group represented by − (XO) _S − (X is an alkylene group having 1 to 10 carbon atoms, and S is an integer of 1 or more). It is preferable because it has excellent surface smoothness (repellency resistance) when it is made into an optically heterogeneous body. Although X represents an alkylene group, an ethylene group, a propylene group, a butylene group and a tetramethylene group are preferable, and an ethylene group, a propylene group and a butylene group are more preferable. In the present invention, "butylene" refers to a branched alkylene having four carbon atoms, and "tetramethylene" refers to a linear alkylene having four carbon atoms.

As the fluorine-based surfactant used in the present invention, it is preferable to use one having a weight average molecular weight (Mw) of 2000 to 30,000. When a fluorine-based surfactant having a weight average molecular weight of less than 2000 is used, surface smoothness (repellency) is improved when a polymerizable liquid crystal composition containing the compound is applied to a substrate to form an optically isomer. If a fluorine-based surfactant having a weight average molecular weight of more than 30,000 is used, the compatibility with the polymerizable liquid crystal composition is lowered, which may adversely affect the orientation of the liquid crystal compound. .. Further, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 1.05 to 5.00. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values converted into polystyrene based on GPC (gel permeation chromatography) measurement. The measurement conditions of GPC are as follows.
[GPC measurement conditions]
Measuring device: "HLC-8220 GPC" manufactured by Tosoh Corporation, Column: Guard column "HHR-H" (6.0 mm ID x 4 cm) manufactured by Tosoh Corporation + "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8 mm ID x 30 cm) + "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8 mm ID x 30 cm) + "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8 mm I) .D. x 30 cm) + "TSK-GEL GMHHR-N" manufactured by Tosoh Corporation (7.8 mm ID x 30 cm)
Measurement conditions: Column temperature 40 ° C., developing solvent: tetrahydrofuran (THF), flow velocity 1.0 ml / min Sample: Tetrahydrofuran solution of 1.0% by mass in terms of resin solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of "GPC-8020 Model II Data Analysis Version 4.30".
[Dispersed polystyrene]
"A-500" manufactured by Tosoh Corporation, "A-1000" manufactured by Tosoh Corporation, "A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation, "F-1" manufactured by Tosoh Corporation, "F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation, "F-10" manufactured by Tosoh Corporation, "F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation, "F-80" manufactured by Tosoh Corporation, "F-128" manufactured by Tosoh Corporation
"F-288" manufactured by Tosoh Corporation, "F-550" manufactured by Tosoh Corporation
The amount of the fluorine-based surfactant added is preferably 0.005 to 5% by mass, more preferably 0.007 to 3% by mass, and 0, based on the total amount of the polymerizable compound and the chiral compound. More preferably, it is 0.01 to 2.0% by mass. The amount of the fluorine-based surfactant added is preferably adjusted appropriately in consideration of the molecular weight of the fluorine-based surfactant to be blended. Generally, when a fluorine-based surfactant having a low molecular weight is used, the molecular weight is high. It is desirable to add more than when a high fluorine-based surfactant is used, but when using a fluorine-based surfactant having a weight average molecular weight (Mw) of about 2000 to 30,000, it should be in the above range. Is preferable.

The fluorine-based surfactant has an oxyalkylene group represented by − (XO) _s- (X is an alkylene group having 1 to 10 carbon atoms, and s is an integer of 1 or more). Is preferable. As the oxyalkylene group, an oxyethylene group, an oxypropylene group, an oxybutylene group and an oxytetramethylene group are preferable.

Further, the fluorine-based surfactant may have a fluoroalkyl group, a fluoroalkenyl group and / or a fluoroalkylene ether group. The fluoroalkyl group, fluoroalkyl group and / or fluoroalkylene ether group are partially fluorinated or wholly fluorinated, and are linear or branched fluoroalkyl groups having about 3 to 12 carbon atoms, fluoro. Examples thereof include an alkenyl group and / or a fluoroalkylene ether group.

As a specific example of the fluorine-based surfactant used in the invention, a polymerizable single amount having a fluoroalkyl group having 4 to 6 carbon atoms (however, the alkyl group also includes one having an ether bond by an oxygen atom). A copolymer (III-) obtained by copolymerizing the body (A) and a polymerizable monomer having an oxyalkylene group and a polymerizable unsaturated group represented by the following general formula (B) as an essential monomer. 1) can be mentioned.

Examples of the polymerizable monomer (A) include those represented by the following general formula (A1).

(In the above general formula (A1), R ⁴ represents a hydrogen atom, a fluorine atom, a methyl group, a cyano group, a phenyl group, a benzyl group or −C _n H _2n −Rf'(n represents an integer of 1 to 8 and Rf. 'Represents any one group of the following formulas (Rf-1) to (Rf-7)), and L represents any one group of the following formulas (L-1) to (L-10). Rf represents any one group of the following formulas (Rf-1) to (Rf-7).)

(N in the above formulas (L-1), (L-3), (L-5), (L-6) and (L-7) represents an integer of 1 to 8. The above formula (L-8). ), (L-9) and (L-10), m represents an integer of 1 to 8, and n represents an integer of 0 to 8. In the above formulas (L-6) and (L-7). Rf'' represents any one group of the following formulas (Rf-1) to (Rf-7).)

(N in the above formulas (Rf-1) to (Rf-4) represents an integer of 4 to 6. In the above formula (Rf-5), m is an integer of 1 to 5, and n is 0 to 4. And the sum of m and n is 4 to 5. In the above equation (Rf-6), m is an integer of 0 to 4, n is an integer of 1 to 4, and p is 0. It is an integer of ~ 4, and the sum of m, n, and p is 4 to 5.)
Moreover, the following monomers (A-1) to (A-15) and the like are mentioned as a more preferable specific example of the said polymerizable monomer (A). It should be noted that these monomers (A) can be used alone or in combination of two or more.

The polymerizable monomer (B) is a monomer having an oxyalkylene chain. Examples of the monomer include those represented by the general formula (B).

(In the formula, R is a hydrogen atom or a methyl group, X, Y, and Z are independent alkylene groups, s is an integer of 1 or more, and t and u are 0 or 1 or more, respectively. It is an integer, and W is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Although X, Y, and Z in the general formula (B) are alkylene groups, the alkylene group may have a substituent. As a specific example of the −O− (XO) s− (YO) t− (ZO) u− portion, a poly in which the number of repetition units s is an integer of 3 or more, t and u are 0, and X is propylene. Oxypropylene, polyoxybutylene in which the number of repetition units s is an integer of 3 or more and t and u are 0 and X is butylene, and the number of repetition units s is an integer of 3 or more and t and u are 0 and Polyoxytetramethylene in which X is tetramethylene, the common weight of ethylene oxide and propylene oxide in which the number of repetition units s and t are both integers of 1 or more, u is 0, and X or Y is ethylene and the other is propylene. It is a copolymer of propylene oxide and butylene oxide, which are coalesced polyoxyalkylenes, the number of repetition units s and t are both integers of 1 or more, u is 0, and X or Y is propylene and the other is butylene. Polyoxyalkylene, which is a copolymer of ethylene oxide and tetrahydrofuran, in which both the number of repetition units s and t are integers of 1 or more, u is 0, and X or Y is ethylene and the other is tetramethylene. Polyoxyalkylene, which is a copolymer of propylene oxide and tetrahydrofuran, in which the number of repetition units s and t are both integers of 1 or more, u is 0, and X or Y is propylene and the other is tetramethylene. Examples thereof include polyoxyalkylene, which is a copolymer of ethylene oxide, propylene oxide, and ethylene oxide, in which the numbers s, t, and u are all integers of 1 or more, X and Z are ethylene, and Y is propylene. ..

It is preferable that the degree of polymerization of these polyoxyalkylenes, that is, the total of s, t and u in the general formula (B) is 3 to 50. The repeating unit including X, the repeating unit including Y, and the repeating unit including Z may be arranged randomly or in a block shape.

Among the polyoxyalkylene chains contained in the monomer (B), those having at least a polyoxypropylene chain, a polyoxybutylene chain or a polyoxytetramethylene chain are added to the polymerizable liquid crystal composition of the present invention. , It is preferable because it exhibits more excellent repellency resistance. Those having at least a polyoxypropylene chain, a polyoxybutylene chain or a polyoxytetramethylene chain may be those having these polyoxyalkylene chains alone or copolymers with other polyoxyalkylene chains. I do not care.

When the number of repeating units s is an integer of 3 or more and t and u are 0, the monomer (B) is a mono (polyalkylene glycol mono (polyalkylene glycol) such as polypropylene glycol, polybutylene glycol, and polytetramethylene glycol. Examples thereof include a meta) acrylic acid ester and a mono (meth) acrylic acid ester of this polyalkylene glycol having a non-(meth) acrylic acid ester terminal sealed with an alkyl group having 1 to 6 carbon atoms.

More specific examples of the monomer (B) include polypropylene glycol mono (meth) acrylate, polytetramethylene glycol (meth) acrylate, poly (ethylene glycol / propylene glycol) mono (meth) acrylate, and polyethylene glycol. Polypropylene glycol mono (meth) acrylate, poly (ethylene glycol / tetramethylene glycol) mono (meth) acrylate, polyethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol / tetramethylene glycol) mono (meth) acrylate , Polypropylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (propylene glycol / butylene glycol) mono (meth) acrylate, polypropylene glycol / polybutylene glycol mono (meth) acrylate, poly (ethylene glycol / butylene glycol) mono ( Meta) acrylate, polyethylene glycol / polybutylene glycol mono (meth) acrylate, poly (tetraethylene glycol / butylene glycol) mono (meth) acrylate, polytetraethylene glycol / polybutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) Meta) acrylate, poly (ethylene glycol / trimethylene glycol) mono (meth) acrylate, polyethylene glycol / polytrimethylethylene glycol mono (meth) acrylate, poly (propylene glycol / trimethylene glycol) mono (meth) acrylate, polypropylene glycol / Polytrimethylethylene glycol mono (meth) acrylate, poly (trimethylethylene glycol / tetramethylene glycol) mono (meth) acrylate, polytrimethylethylene glycol / polytetramethylene glycol mono (meth) acrylate, poly (butylene glycol / trimethylene glycol) Examples thereof include mono (meth) acrylate, polybutylene glycol and polytrimethylene glycol mono (meth) acrylate. These monomers (B) can be used alone or in combination of two or more. In addition, "poly (ethylene glycol / propylene glycol)" means a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol / polypropylene glycol" is a block copolymer of ethylene glycol and propylene glycol. Means, and so on.

The copolymer (III-1) contains the above-mentioned monomer (A) and monomer (B) as essential components as raw materials, but as other monomers, the monomer (C) having an alkyl group. May be used together. Examples of the monomer (C) include those represented by the following general formula (C-1).

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ² is an alkyl group having a linear, branched or ring structure having 1 to 18 carbon atoms.)
Incidentally, formula (C-1) in R ² is a straight-chain having 1 to 18 carbon atoms, is an alkyl group having a branched or cyclic structure, the alkyl group may be aliphatic or aromatic It may have a substituent such as a hydrocarbon group or a hydroxyl group. Specific examples of the ethylenically unsaturated monomer having an alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic. Alkyl having 1 to 18 carbon atoms of (meth) acrylic acid such as octyl acid, -2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, and stearyl (meth) acrylate. Esters: Dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate , A bridging cyclic alkyl ester having 1 to 18 carbon atoms of (meth) acrylic acid such as dicyclopentenyl (meth) acrylate. These monomers (C) can be used alone or in combination of two or more.

Further, as a raw material of the fluorine-based surfactant of the present invention, as monomers other than the above-mentioned monomer (A), monomer (B) and monomer (C), styrene, α-methylstyrene, p. Aromatic vinyls such as -methylstyrene and p-methoxystyrene; maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide and cyclohexylmaleimide. Etc. can also be used.

In order to improve the leveling performance of the fluorine-based surfactant of the present invention, the mass ratio of the monomer (A) and the monomer (B), which are the raw materials of the fluorine-based surfactant, [(A). / (B)] is preferably in the range of 5/95 to 70/30, more preferably in the range of 7.5 / 92.5 to 60/40, and even more preferably in the range of 10/90 to 50/50. When a monomer other than the monomer (A) and the monomer (B) is used, it is preferably 50% by mass or less of all the monomers.
(Initiator)
The polymerizable liquid crystal composition of the present invention may contain an initiator, if necessary. The polymerization initiator used in the polymerizable liquid crystal composition of the present invention is used to polymerize the polymerizable liquid crystal composition of the present invention. The photopolymerization initiator used when the polymerization is carried out by light irradiation is not particularly limited, but known and commonly used ones can be used to the extent that the orientation state of the polymerizable compound is not impaired.

For example, 1-hydroxycyclohexylphenyl ketone "Irgacure 184", 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one "Darocure 1116", 2-methyl-1-[(methylthio) phenyl] -2-Molihorinopropan-1 "Irgacure 907", 2,2-dimethoxy-1,2-diphenylethane-1-one "Irgacure 651", 2-benzyl-2-dimethylamino-1- (4-morpho) Renophenyl) -butanone "Irgacure 369"), 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholino-phenyl) butane-1-one "Irgacure 379", 2,2-dimethoxy- 1,2-Diphenylethane-1-one, bis (2,4,6-trimethylbenzoyl) -diphenylphosphine oxide "Lucillin TPO", 2,4,6-trimethylbenzoyl-phenyl-phosphine oxide "Irgacure 819" , 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone "Irgacure OXE01"), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) "Irgacure OXE02", "Irgacure OXE04" (above, manufactured by BASF Co., Ltd. 2,4-diethylthioxanthone ("Kayacure" manufactured by Nippon Kayakusha EDTA ") and ethyl p-dimethylaminobenzoate (" Kayacure EPA "manufactured by Nippon Kayaku Co., Ltd.), isopropylthioxanthone (" CantaCure-ITX "manufactured by Ward Prekinsop) and ethyl p-dimethylaminobenzoate. Mixtures, "Esacure ONE", "Esacure KIP150", "Esacure KIP160", "Esacure 1001M", "Esacure A198", "Esacure KIP IT", "Esacure KTO46", "Esacure TZT" (manufactured by Benzyl Group),
Examples thereof include "Speed Cure BMS", "Speed Cure PBZ", and "Benzophenone" manufactured by LAMBSON. Further, as the photocation initiator, a photoacid generator can be used. Examples of the photoacid generator include diazodisulfone compounds, triphenylsulfonium compounds, phenylsulfone compounds, sulfonylpyridine compounds, triazine compounds and diphenyliodonium compounds.

The content of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, particularly preferably 1 to 8 parts by mass, based on 100 parts by mass of the total content of the polymerizable compounds contained in the polymerizable composition. These can be used alone or in combination of two or more.

Further, as the thermal polymerization initiator used in the thermal polymerization, known and commonly used agents can be used, for example, methylacetate acetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl). Peroxydicarbonate, t-butylperoxybenzoate, methylethylketone peroxide, 1,1-bis (t-hexylpaoxy) 3,3,5-trimethylcyclohexane, p-pentahydroperoxide, t-butylhydro Organic peroxides such as peroxide, dicumyl peroxide, isobutyl peroxide, di (3-methyl-3-methoxybutyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, 2, 2'-Azobisisobutyronitrile, azonitrile compounds such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methyl-N-phenylpropion-amidin) dihydro Azoamidin compounds such as chloride, azoamide compounds such as 2,2'azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2' azobis (2, An alkylazo compound such as 4,4-trimethylpentane) can be used. The content of the thermal polymerization initiator is preferably 0.1 to 10 parts by mass, particularly preferably 1 to 6 parts by mass, based on 100 parts by mass of the total content of the polymerizable compounds contained in the polymerizable composition. These can be used alone or in combination of two or more.
(Organic solvent)
The polymerizable liquid crystal composition of the present invention can contain an organic solvent, if necessary. The organic solvent used is not particularly limited, but an organic solvent in which the polymerizable compound exhibits good solubility is preferable, and an organic solvent that can be dried at a temperature of 100 ° C. or lower is preferable. Examples of such a solvent include aromatic hydrocarbons such as toluene, xylene, cumene, mesityrene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexyl acetate, 3-butoxymethyl acetate, ethyl lactate and the like. Ester solvent, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone and other ketone solvents, tetrahydrofuran, 1,2-dimethoxyethane, anisole and other ether solvents, N, N-dimethylformamide, N-methyl-2- Examples thereof include amide solvents such as pyrrolidone, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol monomethyl propyl ether, diethylene glycol monomethyl ether acetate, γ-butyrolactone and chlorobenzene. .. These can be used alone or in combination of two or more, but any one of a ketone solvent, an ether solvent, an ester solvent and an aromatic hydrocarbon solvent. It is preferable to use the above from the viewpoint of solution stability.

Since the polymerizable composition used in the present invention is usually applied, the ratio of the organic solvent used is not particularly limited as long as the applied state is not significantly impaired, but the polymerizable composition contained in the polymerizable composition. The total content of the compound is preferably 50 to 700 parts by mass, more preferably 100 to 650 parts by mass, and particularly preferably 150 to 600 parts by mass with respect to 100 parts by mass.

Further, when the polymerizable liquid crystal compound is dissolved in an organic solvent, it is preferable to heat and stir in order to dissolve the polymerizable liquid crystal compound uniformly. The heating temperature during heating and stirring may be appropriately adjusted in consideration of the solubility of the polymerizable liquid crystal compound to be used in an organic solvent, but from the viewpoint of productivity, it is preferably 15 ° C to 130 ° C, and more preferably 30 ° C to 110 ° C. Preferably, 50 ° C to 100 ° C is particularly preferable.
(Additive)
The polymerizable liquid crystal composition of the present invention can be uniformly applied, or general-purpose additives can be used depending on the respective purposes. For example, polymerization inhibitors, antioxidants, UV absorbers, orientation control agents, chain transfer agents, infrared absorbers, thixo agents, antioxidants, dyes, fillers, chiral compounds, non-liquid crystal compounds having polymerizable groups, Other additives such as liquid crystal compounds and alignment materials can be added to the extent that the orientation of the liquid crystal is not significantly reduced.
(Polymerization inhibitor)
The polymerizable liquid crystal composition of the present invention may contain a polymerization inhibitor, if necessary. The polymerization inhibitor to be used is not particularly limited, and known and customary ones can be used.

For example, p-methoxyphenol, cresol, t-butylcatechol, 3.5-di-t-butyl-4-hydroxytoluene, 2.2'-methylenebis (4-methyl-6-t-butylphenol), 2.2 '-Methylenebis (4-ethyl-6-t-butylphenol), 4.4'-thiobis (3-methyl-6-t-butylphenol), 4-methoxy-1-naphthol, 4,4'-dialkoxy-2 , 2'-bi-1-naphthol, and other phenolic compounds, hydroquinones, methylhydroquinones, tert-butylhydroquinones, p-benzoquinones, methyl-p-benzoquinones, tert-butyl-p-benzoquinones, 2,5-diphenylbenzoquinones. , 2-Hydroxy-1,4-naphthoquinone, 1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, anthraquinone, diphenoquinone, and other quinone compounds, p-phenylenediamine, 4-aminodiphenylamine, N .. N'-diphenyl-p-phenylenediamine, N-i-propyl-N'-phenyl-p-phenylenediamine, N- (1.3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N. Amin-based compounds such as N'-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4.4'-dicumyl-diphenylamine, 4.4'-dioctyl-diphenylamine, phenothiazine, Thioether compounds such as distearylthiodipropionate, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaftylamine, p-nitrosophenol, nitrosobenzene, p-nitrosodiphenylamine, α-nitroso-β-naphthol Etc., N, N-dimethyl p-nitrosoaniline, p-nitrosodiphenylamine, p-nitrosodimethylamine, p-nitroso-N, N-diethylamine, N-nitrosoethanolamine, N-nitrosodi-n-butylamine, N-nitroso -N-n-butyl-4-butanolamine, N-nitroso-diisopropanolamine, N-nitroso-N-ethyl-4-butanolamine, 5-nitroso-8-hydroxyquinoline, N-nitrosomorpholin, N-2 Troso N-phenylhydroxylamine ammonium salt, ditrosobenzene, 2,4.6-tree tert-butylnitronbenzene, N-nitroso-N-methyl-p-toluenesulfonamide, N-nitroso-N-ethylurethane, N -Nitroso-N-n-propyl urethane, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 1-nitroso-2-naphthol-3,6-sodium sulfonate, 2-nitroso-1-naphthol- Examples thereof include nitroso compounds such as sodium 4-sulfonate, 2-nitroso-5-methylaminophenol hydrochloride, 2-nitroso-5-methylaminophenol hydrochloride, and the like.

The amount of the polymerization inhibitor added is preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the total content of the polymerizable compounds contained in the polymerizable composition, and 0.05 to 1. More preferably, it is 0 parts by mass.
(Antioxidant)
The polymerizable liquid crystal composition of the present invention may contain an antioxidant or the like, if necessary. Examples of such a compound include a hydroquinone derivative, a nitrosoamine-based polymerization inhibitor, a hindered phenol-based antioxidant, and more specifically, tert-butylhydroquinone, "Q-1300" manufactured by Wako Pure Chemical Industries, Ltd., "Q-1301", pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate "IRGANOX1010", thiodiethylenebis [3- (3,5-di-tert-butyl-) 4-Hydroxyphenyl) propionate "IRGANOX1035", octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate "IRGANOX1076", "IRGANOX1135", "IRGANOX1330", 4,6-bis (octyl) Thiomethyl) -o-cresol "IRGANOX1520L", "IRGANOX1726", "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", "IRGANOX565" (manufactured by BASF Corporation), ADEKA Co., Ltd. Adecastab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80 manufactured by Sumitomo Chemical Co., Ltd., Sumilyzer BHT, Sumilyzer BBM-S, Sumilyzer GA-80, and the like.

The amount of the antioxidant added is preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the total content of the polymerizable compound contained in the polymerizable composition, and 0.05 to 1. More preferably, it is 0 parts by mass.
(UV absorber)
The polymerizable liquid crystal composition of the present invention may contain an ultraviolet absorber and a light stabilizer, if necessary. The ultraviolet absorber and light stabilizer used are not particularly limited, but those that improve the light resistance of an optically anisotropic substance, an optical film, or the like are preferable.

Examples of the ultraviolet absorber include 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole "Tinubin PS", "Tinubin 99-2", "Tinubin 109", "TINUVIN 213", and the like. "TINUVIN 234", "TINUVIN 326", "TINUVIN 328", "TINUVIN 329", "TINUVIN 384-2", "TINUVIN 571", 2- (2H-benzotriazol-2-yl) -4,6-bis (1-Methyl-1-phenylethyl) Phenol "TINUVIN 900", 2- (2H-benzotriazole-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3) , 3-Tetramethylbutyl) Phenol "TINUVIN 928", "TINUVIN 1130", "TINUVIN 400", "TINUVIN 405", 2,4-Bis [2-Hydroxy-4-butoxyphenyl] -6- (2,4) -Dibutoxyphenyl) -1,3,5-triazine "TINUVIN 460", "Tinubin 479", "TINUVIN 5236" (above, manufactured by BASF Co., Ltd.), "Adecastab LA-32", "Adecastab LA-34", Examples thereof include "Adekastab LA-36", "Adekastab LA-31", "Adekastab 1413", and "Adekastab LA-51" (all manufactured by ADEKA Co., Ltd.).

Examples of the light stabilizer include "TINUVIN 111FDL", "TINUVIN 123", "TINUVIN 144", "TINUVIN 152", "TINUVIN 292", "TINUVIN 622", "TINUVIN 770", "TINUVIN 765", "TINUVIN 780". , "TINUVIN 905", "TINUVIN 5100", "TINUVIN 5050", "TINUVIN 5060", "TINUVIN 5151", "CHIMASSORB 119FL", "CHIMASORB 944FL", "CHIMASORB 944LD" (above, BASF) "ADEKA STAB LA-52", "ADEKA STAB LA-57", "ADEKA STAB LA-62", "ADEKA STAB LA-67", "ADEKA STAB LA-63P", "ADEKA STAB LA-68LD", "ADEKA STAB LA-77", " Examples thereof include "ADEKA STAB LA-82" and "ADEKA STAB LA-87" (all manufactured by ADEKA CORPORATION).
(Chain transfer agent)
The polymerizable liquid crystal composition of the present invention may contain a chain transfer agent in order to further improve the adhesion between the polymer or the optically anisotropic substance and the base material. Chain transfer agents include aromatic hydrocarbons, chloroform, carbon tetrachloride, carbon tetrabromide, halogenated hydrocarbons such as bromotrichloromethane, and the like.
Mercaptan compounds such as octyl mercaptan, n-butyl mercaptan, n-pentyl mercaptan, n-hexadecyl mercaptan, n-tetradecylmel, n-dodecyl mercaptan, t-tetradecyl mercaptan, t-dodecyl mercaptan, hexanedithiol, decandthiol. , 1,4-Butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane triththioglycolate, trimethylolpropane Tristhiopropionate, Trimethylol Propanetris (3-mercaptobutyrate), Pentaerythritol tetraxthioglycolate, Pentaerythritol tetraxthiopropionate, Trimercaptopropionate (2-hydroxyethyl) isocyanurate, 1,4 Thiol compounds such as −dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, dimethylxanthogen disulfide, diethylxantogen disulfide , Diisopropylxanthogen disulfide, tetramethylthiolam disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide and other sulfide compounds, N, N-dimethylaniline, N, N-divinylaniline, pentaphenylethane, α-methylstyrene dimer, achlorine, allyl Alcohol, turpinolene, α-terpinene, γ-terbinene, dipentene, etc. can be mentioned, but 2,4-diphenyl-4-methyl-1-pentene and thiol compounds are more preferable.

Specifically, compounds represented by the following general formulas (9-1) to (9-12) are preferable.

In the formula, R ⁹⁵ represents an alkyl group having 2 to 18 carbon atoms, the alkyl group may be a straight chain or a branched chain, and one or more methylene groups in the alkyl group are oxygen atoms. , And sulfur atoms may be substituted with oxygen atoms, sulfur atoms, -CO-, -OCO-, -COO-, or -CH = CH-, assuming that they do not bond directly to each other, where R ⁹⁶ is a carbon atom. Representing the number 2 to 18 alkylene groups, one or more methylene groups in the alkylene group assume that the oxygen atom and the sulfur atom do not directly bond with each other, and the oxygen atom, the sulfur atom, -CO-, and -OCO- , -COO-, or -CH = CH- may be substituted.

The chain transfer agent is preferably added in the step of mixing the polymerizable liquid crystal compound with the organic solvent and heating and stirring to prepare the polymerizable solution, but is added in the subsequent step of mixing the polymerization initiator with the polymerizable solution. It may be added in both steps.

The amount of the chain transfer agent added is preferably 0.5 to 10 parts by mass, preferably 1.0 to 5.0 parts by mass, based on 100 parts by mass of the total content of the polymerizable compound contained in the polymerizable composition. It is more preferable that it is a part.

Further, in order to adjust the physical properties, it is possible to add a non-polymerizable liquid crystal compound or the like as needed. Non-polymerizable polymerizable compounds are preferably added in the step of mixing the polymerizable compound with an organic solvent and heating and stirring to prepare a polymerizable solution, but non-polymerizable liquid crystal compounds and the like are subsequently polymerizable. It may be added in the step of mixing the polymerization initiator with the solution, or it may be added in both steps. The amount of these compounds added is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less, based on 100 parts by mass of the total content of the polymerizable compounds contained in the polymerizable composition. More preferred.
(Infrared absorber)
The polymerizable liquid crystal composition of the present invention may contain an infrared absorber, if necessary. The infrared absorber to be used is not particularly limited, and known and commonly used ones can be contained as long as the orientation is not disturbed.

Examples of the infrared absorber include cyanine compounds, phthalocyanine compounds, naphthoquinone compounds, dithiol compounds, diimmonium compounds, azo compounds, aluminum salts and the like.

Specifically, diimmonium salt type "NIR-IM1", aluminum salt type "NIR-AM1" (above, manufactured by Nagase Chemtech Co., Ltd.), "Karenzu IR-T", "Karenzu IR-13F" (above) , Showa Denko Co., Ltd.), "YKR-2200", "YKR-2100" (above, manufactured by Yamamoto Chemicals, Inc.), "IRA908", "IRA931", "IRA955", "IRA1034" (above, INDEC O Co., Ltd.) ) Etc. can be mentioned.
(Antistatic agent)
The polymerizable liquid crystal composition of the present invention may contain an antistatic agent, if necessary. The antistatic agent used is not particularly limited and may contain known and commonly used antistatic agents as long as the orientation is not disturbed.

Examples of such an antistatic agent include a polymer compound having at least one kind of sulfonic acid base or phosphate base in the molecule, a compound having a quaternary ammonium salt, a surfactant having a polymerizable group, and the like.

Of these, surfactants having a polymerizable group are preferable. For example, among the surfactants having a polymerizable group, "Antox SAD" and "Antox MS-2N" (above, Japan Emulsifier Co., Ltd.) are preferred as anionic ones. (Manufactured by the company), "Aqualon KH-05", "Aqualon KH-10", "Aqualon KH-20", "Aqualon KH-0530", "Aqualon KH-1025" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Alkyl ethers such as "Adecaria Soap SR-10N", "Adecaria Soap SR-20N" (manufactured by ADEKA Corporation), "Latemuru PD-104" (manufactured by Kao Corporation), "Latemuru S-120" , "Latemuru S-120A", "Latemuru S-180P", "Latemuru S-180A" (manufactured by Kao Corporation), "Ereminol JS-2" (manufactured by Sanyo Kasei Co., Ltd.), etc. , "Aqualon H-2855A", "Aqualon H-3855B", "Aqualon H-3855C", "Aqualon H-3856", "Aqualon HS-05", "Aqualon HS-10", "Aqualon HS-20", "Aqualon HS-30", "Aqualon HS-1025", "Aqualon BC-05", "Aqualon BC-10", "Aqualon BC-20", "Aqualon BC-1025", "Aqualon BC-1020" (and above) , Made by Daiichi Kogyo Seiyaku Co., Ltd.), "Adecaria Soap SDX-222", "Adecaria Soap SDX-223", "Adecaria Soap SDX-232", "Adecaria Soap SDX-233", "Adecaria Soap" Alkylphenyl ether or alkylphenyl ester type such as "SDX-259", "Adecaria Soap SE-10N", "Adecaria Soap SE-20N" (all manufactured by ADEKA Corporation), "Antox MS-60", (Meta) acrylate sulfate ester type such as "Antox MS-2N" (manufactured by Nippon Emulsifier Co., Ltd.), "Eleminor RS-30" (manufactured by Sanyo Kasei Co., Ltd.), "H-3330P" (Daiichi Kogyo Phosphate esters such as "Adecaria Soap PP-70" (manufactured by ADEKA Corporation), etc. (manufactured by Pharmaceutical Co., Ltd.) can be mentioned.

On the other hand, among the surfactants having a polymerizable group, nonionic ones include, for example, "Antox LMA-20", "Antox LMA-27", "Antox EMH-20", and "Antox LMH-". 20, "Antox SMH-20" (manufactured by Nippon Emulsorium Co., Ltd.), "ADEKA RIA SOLP ER-10", "ADEKA RIA SOLP ER-20", "ADEKA RIA SOLP ER-30", "ADEKA CORPORATION" Alkyl ethers such as "ER-40" (manufactured by ADEKA Corporation), "Latemuru PD-420", "Latemuru PD-430", "Latemuru PD-450" (manufactured by Kao Corporation), "Aqualon" RN-10, "Aqualon RN-20", "Aqualon RN-30", "Aqualon RN-50", "Aqualon RN-2025" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), "Adecaria Soap NE-" 10 ”,“ Adecaria Soap NE-20 ”,“ Adecaria Soap NE-30 ”,“ Adecaria Soap NE-40 ”(above, manufactured by ADEKA Corporation), etc., alkylphenyl ether type or alkylphenyl ester type, Examples thereof include (meth) acrylate sulfate esters such as "RMA-564", "RMA-568", and "RMA-1114" (all manufactured by Nippon Emulsifier Co., Ltd.).

Examples of other antistatic agents include polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, propoxypolyethylene glycol (meth) acrylate, and n-butoxypolyethylene glycol (meth) acrylate. , N-pentoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, propoxypolypropylene glycol (meth) acrylate , N-Butoxy polypropylene glycol (meth) acrylate, n-pentoxy polypropylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, polytetramethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, phenoxy Examples thereof include tetraethylene glycol (meth) acrylate, hexaethylene glycol (meth) acrylate, and methoxyhexaethylene glycol (meth) acrylate.

The antistatic agent may be used alone or in combination of two or more. The amount of the antistatic agent added is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, based on 100 parts by mass of the total content of the polymerizable compound contained in the polymerizable composition. ..
(Non-liquid crystal compound having a polymerizable group)
In the polymerizable liquid crystal composition of the present invention, a compound having a polymerizable group but not a liquid crystal compound can be added. As such a compound, usually, any compound recognized as a polymerizable monomer or a polymerizable oligomer in the art can be used without particular limitation. When added, the total content of the polymerizable compound contained in the polymerizable composition is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, based on 100 parts by mass.

Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl acrylate, propyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 4-Hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, Dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyl (meth) acrylate Cyclopentenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethylcarbitol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxydiethylene glycol (meth) Acrylate, 2-hydroxy-3-phenoxyethyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, (3-ethyloxetane-3-yl) Methyl (meth) acrylate, o-phenylphenol ethoxy (meth) acrylate, dimethylamino (meth) acrylate, diethylamino (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2,2 , 3,4,4,4-hexafluorobutyl (meth) acrylate, 2,2,3,3,4,5,4-heptafluorobutyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) Acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) acrylate, 1H, 1H, 7H-dodeca Fluoroheptyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 1,2,2,2-te Trafluoro-1- (trifluoromethyl) ethyl (meth) acrylate, 1H, 1H-pentadecafluorooctyl (meth) acrylate, 1H, 1H, 2H, 2H-tridecafluorooctyl (meth) acrylate, 2- (meth) ) Acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, acryloylmorpholine, dimethylacrylamide, dimethylaminopropylacrylamide, iropropyl Mono (meth) acrylates such as acrylamide, diethyl acrylamide, hydroxyethyl acrylamide, N-acryloyloxyethyl hexahydrophthalimide, 1,4-butanediol di (meth) acrylates, 1,6-hexanediol di (meth) acrylates, 1 , 9-Nonandiol di (meth) acrylate, neopentyldiol di (meth) acrylate, tripropylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) ) Acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, glycerin di (meth) acrylate , 2-Hydroxy-3-acroyloxypropyl methacrylate, acrylic acid adduct of 1,6-hexanediol diglycidyl ether, acrylic acid adduct of 1,4-butanediol diglycidyl ether, etc. Diacrylate, trimethylol Tri (meth) acrylates such as propanetri (meth) acrylate, ethoxylated isocyanuric acid triacrylate, pentaerythritol tri (meth) acrylate, ε-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, pentaerythritol tetra ( Tetra (meth) acrylates such as meta) acrylates and ditrimethylolpropane tetra (meth) acrylates, dipentaerythritol hexa (meth) acrylates, oligomer-type (meth) acrylates, various urethane acrylates, various macromonomers, ethylene glycol diglycidyl Acrylate, diethylene glycol diglycy Examples thereof include epoxy compounds such as diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether and bisphenol A diglycidyl ether, and maleimide. These can be used alone or in combination of two or more.
(Polymer)
A polymer can be obtained by polymerizing the polymerizable liquid crystal composition of the present invention in a state of containing an initiator. The polymer thus obtained is useful as an optically anisotropic substance, a retardation film, or the like.
(Optical anisotropic body)
The polymerizable liquid crystal composition of the present invention can be shaped into a film as described above to obtain the optically anisotropic substance of the present invention. The optically anisotropic substance of the present invention improves visibility over a wide wavelength range by achromaticizing a slight amount of reflected light generated when observed from an angle, especially by satisfying the condition of the following formula (D). it can.
Rth (450) / Rth (550) <1.08 equation (D)
(In the formula, Rth (450) represents the out-of-plane phase difference at a wavelength of 450 nm, and in the formula, Rth (550) represents the out-of-plane phase difference at a wavelength of 550 nm.)
Here, the thickness direction retardation value Rth is an in-plane retardation value R ₀ , a retardation value R ₅₀ measured at an inclination of 50 ° with the slow axis as an inclination axis, a film thickness d, and an average refractive index n of the film. _{Using 0} , nx, ny, and nz can be obtained by numerical calculation from the equation (1) and the following equations (4) to (7), and these can be substituted into the equation (2) for calculation. Further, the Nz coefficient = can be calculated from the equation (3). Hereinafter, the same applies to other descriptions in the present specification.

R ₀ = (nx-ny) x d (1)
Rth = [(nx + ny) /2-nz] × d (2)
Nz coefficient = (nx-nz) / (nx-ny) (3)
R ₅₀ = (nx-ny') × d / cos (φ) (4)
(Nx + ny + nz) / 3 = n0 (5)
here,
φ = sin ^-1 [sin (50 °) / n ₀ ] (6)
ny'= ny x nz / [ny ² x sin ² (φ) + nz ² x cos ² (φ)] ^1/2 (7)
In a commercially available phase difference measuring device, the numerical calculation shown here is automatically performed in the device, and the in-plane phase difference value R ₀ , the thickness direction phase difference value Rth, etc. are automatically displayed. There are many. Examples of such a measuring device include RETS-100 (manufactured by Otsuka Chemical Co., Ltd.).
The values of Rth (450) / Rth (550) are, in particular, 0.7 <Rth (450) / Rth (550) <1.05, 0.7 <Rth (450) / Rth (550) <1. The range of 02, 0.7 <Rth (450) / Rth (550) <1.00 is preferable from the viewpoint of color.
Such an optical variant is applied onto a base material or a base material having an orientation function, and the liquid crystal molecules in the polymerizable liquid crystal composition of the present invention are uniformly coated while maintaining a nematic phase or a smectic phase. It can be produced by orienting and polymerizing.
(Ratio of polymerizable liquid crystal compounds present in the optically anisotropic substance)
The optically anisotropic substance of the present invention contains a polymerizable compound that has not been polymerized after the polymerization reaction, that is, a residual monomer. The residual monomer ratio in the present invention was determined as the ratio of the unpolymerized polymerizable liquid crystal compound to the coating amount of the optically anisotropic substance. The residual monomer ratio can be determined by extracting a polymerizable liquid crystal compound from an optically anisotropic substance with a solvent and quantifying it by a chromatographic method. The residual monomer may be extracted by any method. For example, the optical variant may be extracted by immersing the optical variant in the solvent together with the substrate, or the optical variant may be scraped from the substrate and immersed in the solvent. It may be extracted by. In order to improve the heat resistance of the optical anisotropic substance of the present invention, the ratio of the residual monomer in the optical anisotropic substance of the present invention is 20% by weight or less, preferably 15% by weight or less. It is more preferably 10% by weight or less, and particularly preferably 5% by weight or less.
(Solid surface free energy)
The wettability with respect to the coating film can be evaluated by the surface free energy γ of the film represented by the formula (9). The surface free energy γ is a numerical value of the surface state of a solid substance, and is a value that serves as an index when knowing the order of wettability between solid substances. In addition, surface free energy is the force that molecules on the solid surface pull each other, and this force is called intermolecular force (Van der Waals force), such as ionic bonds and covalent bonds in which electrons move between atoms. It is not a chemical bond, but a force that pulls molecules together.

γ = γd + γp + γh (9)
(In formula (9), γ represents the surface free energy of the substance, γd represents the dispersion component, γp represents the polar component, and γh represents the hydrogen bond component).
The analysis of the surface free energy on the solid surface uses a method of calculating from the measurement result of the contact angle of the solid surface, and there are several theories in this calculation method. A method of calculating from the Owns-Wendt theory using two kinds of solvents having a known surface free energy, a method of calculating from the Kitazaki-Hata theory using three kinds of solvents having a known surface free energy, and the like are used. .. The contact angle of the solid surface is the angle formed by the solid and the droplet in the wetted portion when the droplet is present on the solid surface.

In the optical variant of the present invention, the surface free energy of the film surface on which the liquid crystal composition is polymerized does not reduce the tilt angle of the liquid crystal molecules with respect to the gas-liquid interface, and the adhesive layer on the film surface. for ^lamination, preferably ^{40mJ / m 2 ~70mJ / m 2} , more preferably ^{45mJ / m 2 ~70mJ / m 2} , 50mJ / m 2 ~70mJ / m 2 is particularly preferred.
(Base material)
The base material used for the optically anisotropic substance of the present invention is a base material usually used for liquid crystal display elements, organic light emitting display elements, other display elements, optical parts, colorants, markings, printed matter and optical films. It is a material having heat resistance that can withstand heating during drying after application of the polymerizable liquid crystal composition solution of the present invention, and is not particularly limited. Examples of such a base material include a glass base material, a metal base material, a ceramic base material, a plastic base material, and an organic material such as paper. In particular, when the base material is an organic material, examples thereof include cellulose derivatives, polyolefins, polyesters, polyolefins, polycarbonates, polyacrylates, polyarylates, polyether sulfone, polyimides, polyphenylene sulfides, polyphenylene ethers, nylons and polystyrenes. Of these, plastic substrates such as polyester, polystyrene, polyolefin, cellulose derivatives, polyarylate, and polycarbonate are preferable. The shape of the base material may be a flat surface or a curved surface. These base materials may have an electrode layer, an antireflection function, and a reflection function, if necessary.

Since the optically anisotropic substance of the present invention uses a polymerizable liquid crystal composition containing a spontaneously oriented compound represented by the general formulas (K-1), (K-2), and (K-3). , It is not necessary that the base material is provided with a vertical alignment film such as a polyimide alignment film. That is, the optically anisotropic substance of the present embodiment can have a configuration in which the substrate does not have a vertical alignment film such as a polyimide alignment film.

In order to improve the coatability of the polymerizable liquid crystal composition of the present invention and the adhesiveness with the polymer, the surface treatment of these substrates may be performed. Examples of the surface treatment include ozone treatment, plasma treatment, corona treatment, and silane coupling treatment. In addition, in order to adjust the light transmittance and reflectance, an organic thin film, an inorganic oxide thin film, a metal thin film, etc. are provided on the surface of the base material by a method such as thin film deposition, or in order to add optical value. The material may be a pickup lens, a rod lens, an optical disk, a retardation film, a light diffusing film, a color filter, or the like. Of these, pickup lenses, retardation films, light diffusing films, and color filters, which have higher added value, are preferable.
(Painting)
The coating method for obtaining the optically anisotropic substance of the present invention includes an applicator method, a bar coating method, a spin coating method, a roll coating method, a direct gravure coating method, a reverse gravure coating method, a flexographic coating method, an inkjet method, and a die coating method. Known and commonly used methods such as a method, a cap coating method, a dip coating method, a slit coating method, and a spray coating method can be performed.

After the polymerizable liquid crystal composition of the present invention is applied to a base material, heat treatment is required for uniform vertical orientation. By this step, the vertical alignment agent can be arranged (oriented) on the substrate side. In order to obtain good vertical orientation of the polymerizable liquid crystal composition, an appropriate temperature and time are desirable. The specific temperature is about 80 to 140 ° C., and the time is preferably 5 to 60 minutes. From there, the nematic phase is expressed by slow cooling as needed. At this time, it is desirable to temporarily maintain the temperature at which the liquid crystal phase is exhibited and sufficiently grow the liquid crystal phase domain to form a monodomain. Alternatively, after applying the polymerizable liquid crystal composition of the present invention on a substrate, heat treatment may be performed so as to maintain the temperature for a certain period of time within the temperature range in which the nematic phase of the polymerizable liquid crystal composition of the present invention appears.

If the heating temperature is too high, the polymerizable liquid crystal compound may undergo an unfavorable polymerization reaction and deteriorate, and if the base material is plastic, the substrate will be deformed. On the other hand, if it is cooled too much, the polymerizable composition may undergo phase separation, and a higher-order liquid crystal phase such as crystal precipitation or smectic phase may be expressed, which may make the orientation treatment impossible. Temperature and time are desirable.

By performing such a heat treatment, it is possible to produce a homogeneous optical anisotropic body having few orientation defects as compared with a coating method in which only coating is performed.

Further, after performing the uniform orientation treatment in this way, the liquid crystal phase is cooled to the lowest temperature at which phase separation does not occur, that is, a supercooled state, and the liquid crystal phase is polymerized in the oriented state at that temperature. , It is possible to obtain an optical variant having a higher orientation order and excellent transparency.
(Polymerization process)
The polymerization treatment of the dried polymerizable composition is generally carried out by irradiation with light such as visible ultraviolet light or heating in a uniformly oriented state. When the polymerization is carried out by light irradiation, specifically, it is preferable to irradiate visible ultraviolet light of 420 nm or less, and most preferably to irradiate ultraviolet light having a wavelength of 250 to 370 nm. However, when the polymerizable composition is decomposed by visible ultraviolet light of 420 nm or less, it may be preferable to carry out the polymerization treatment with visible ultraviolet light of 420 nm or more.
(Polymerization method)
Examples of the method for polymerizing the polymerizable liquid crystal composition of the present invention include a method of irradiating an active energy ray and a thermal polymerization method. However, since the reaction proceeds at room temperature without requiring heating, the active energy ray is used. The method of irradiating is preferable, and above all, the method of irradiating light such as ultraviolet rays is preferable because the operation is simple. The temperature at the time of irradiation is a temperature at which the polymerizable liquid crystal composition of the present invention can hold the liquid crystal phase, and in order to avoid inducing thermal polymerization of the polymerizable composition, a temperature at which a liquid crystal phase of 100 ° C. or lower is expressed as much as possible. It is preferable to do so. The polymerizable liquid crystal composition usually has a temperature within the range of the C (solid phase) -N (nematic) transition temperature (hereinafter abbreviated as CN transition temperature) to the NI transition temperature during the temperature rise process. Shows the liquid crystal phase. On the other hand, in the temperature lowering process, since a non-equilibrium state is thermodynamically taken, the liquid crystal state may be maintained without solidification even below the CN transition temperature. This state is called a supercooled state. In the present invention, the liquid crystal composition in the supercooled state is also included in the state of holding the liquid crystal phase. Specifically, it is preferable to irradiate ultraviolet light of 390 nm or less, and most preferably light having a wavelength of 250 to 370 nm. However, when the polymerizable composition is decomposed by ultraviolet light of 390 nm or less, it may be preferable to carry out the polymerization treatment with ultraviolet light of 390 nm or more. This light is preferably diffused light and is not polarized light. The ultraviolet irradiation intensity is preferably in the range of 0.05 mW / cm ^{2 to} 10 W / cm ² . In particular, a range of 0.2 mW / cm ^{2 to 2} W / cm ² is preferable. When the ultraviolet intensity is less than 0.05 mW / cm ² , it takes a long time to complete the polymerization. On the other hand, when the intensity exceeds ² W / cm ² , the liquid crystal molecules in the polymerizable composition tend to be photodecomposed, and a large amount of heat of polymerization is generated to raise the temperature during polymerization, which is an order parameter of the polymerizable liquid crystal. May change and the retardation of the film after polymerization may be out of order.

The ultraviolet irradiation amount is ^preferably in the range of ^{10mJ / cm 2 ~20J / cm 2} , more preferably ^{50mJ / cm 2 ~10J / cm 2} , 100mJ / cm 2 ~5J / cm 2 is particularly preferred.

It is different when only a specific part is polymerized by ultraviolet irradiation using a mask, the orientation state of the unpolymerized part is changed by applying an electric field, a magnetic field, a temperature, or the like, and then the unpolymerized part is polymerized. It is also possible to obtain an optical variant having a plurality of regions having orientation directions.

Further, when only a specific part is polymerized by ultraviolet irradiation using a mask, the orientation of the unpolymerized polymerizable liquid crystal composition is regulated by applying an electric field, a magnetic field, or a temperature in advance, and the state is maintained. By irradiating light from the mask as it is and polymerizing it, an optically anisotropic substance having a plurality of regions having different orientation directions can be obtained.

The optically anisotropic substance obtained by polymerizing the polymerizable liquid crystal composition of the present invention can be peeled off from the substrate and used alone as an optical anisotropic substance, or can be used as it is as an optical anisotropic substance without peeling from the substrate. You can also do it. In particular, since it is difficult to contaminate other members, it is useful when it is used as a substrate to be laminated or when it is used by being bonded to another substrate.

The optical anisotropic substance can also be heat-aged in order to stabilize the solvent resistance and heat resistance of the obtained optical anisotropic substance. In this case, it is preferable to heat at the glass transition point or higher of the polymerized film. Usually, 50 to 300 ° C. is preferable, 60 to 200 ° C. is more preferable, and 80 to 150 ° C. is particularly preferable.
(Phase difference film)
The optically anisotropic substance of the present invention is particularly useful as a retardation film. In the retardation film of the present invention, the liquid crystal compound forms a uniformly continuous orientation state with respect to the base material, and is in-plane, out-of-plane, both in-plane and out-of-plane, or with respect to the base material. It suffices to have biaxiality in the plane. Further, an adhesive or an adhesive layer, an adhesive or an adhesive layer, a protective film, a polarizing film or the like may be laminated. Since the retardation film of the present invention can be produced without providing an alignment film, for example, when the retardation film (I) and the retardation film (II) are laminated, the retardation film does not have a layer of the alignment film. A laminate can be formed.

Examples of such a retardation film include a positive C plate in which a rod-shaped liquid crystal compound is substantially vertically oriented with respect to a base material, and a positive O plate in which a rod-shaped liquid crystal compound is hybrid-oriented with respect to a base material. However, in the present invention, it is preferable to use it as a positive C plate because it has a feature of exhibiting excellent heat resistance as a positive C plate.

When the optical variant of the present invention is used as a positive C plate, the positive A plate in which the rod-shaped liquid crystal compound is substantially horizontally oriented with respect to the base material and the disc-shaped liquid crystal compound are perpendicular to the base material. Various retardation films such as a uniaxially oriented negative A plate, a rod-shaped liquid crystal compound oriented cholesterically with respect to the substrate, or a disc-shaped liquid crystal compound horizontally oriented uniaxially can be further laminated. In particular, the retardation film (II) satisfying the following formula (E)
nx> ny ≒ nz equation (E)
(Nz represents the refractive index in the thickness direction, nx represents the refractive index in the direction that produces the maximum refractive index in the plane, and ny represents the refractive index in the direction orthogonal to the direction of nx in the plane. Represents)
The so-called positive A plates represented by are laminated to compensate for the viewing angle dependence of the polarization axis orthogonality when used in a liquid crystal cell and widen the viewing angle, and for liquid crystal cells or OLEDs. As a reflector for use, it is preferable because it can improve the color. In particular, it is preferable to use the positive A plate as the λ / 4 plate and stack it with the positive C plate of the present invention from the viewpoint that good viewing angle correction and color tint can be improved as the λ / 4 plate.
Here, the positive A plate preferably has an in-plane retardation value in the range of 30 to 500 nm at a wavelength of 550 nm. Further, the thickness direction retardation value is not particularly limited. The Nz coefficient is preferably in the range of 0.5 to 1.5.
(Liquid crystal display element)
The polymerizable liquid crystal composition of the present invention can be used for the liquid crystal display element of the present invention by applying it on a substrate not subjected to the alignment function, uniformly aligning the composition by heat treatment, and polymerizing the composition. Examples of the usage form include an optical compensation film, a patterned retardation film of a liquid crystal stereoscopic display element, a retardation correction layer of a color filter, an overcoat layer, an alignment film for a liquid crystal medium, and the like. The liquid crystal display element has at least two base materials having a liquid crystal medium layer, a TFT drive circuit, a black matrix layer, a color filter layer, a spacer, and an electrode circuit corresponding to the liquid crystal medium layer at a minimum, and is usually optically compensated. The layer, n layer, and touch panel layer are arranged outside the two base materials, but in some cases, the optical compensation layer, the overcoat layer, the polarizing plate layer, and the electrode layer for the touch panel are sandwiched between the two base materials. May be done.

The orientation mode of the liquid crystal display element includes TN mode, VA mode, IPS mode, FFS mode, OCB mode, etc., but when used in an optical compensation film or an optical compensation layer, a phase difference corresponding to the alignment mode is obtained. It is possible to make a film having. When used in an overcoat layer, a liquid crystal compound having more polymerizable groups in one molecule may be thermally polymerized. When used in an alignment film for a liquid crystal medium, it is preferable to use a polymerizable composition in which an alignment material and a liquid crystal compound having a polymerizable group are mixed. It can also be mixed in a liquid crystal medium, and has the effect of improving various characteristics such as response speed and contrast depending on the ratio of the liquid crystal medium and the liquid crystal compound.
(Organic light emitting display element)
The polymerizable liquid crystal composition of the present invention can be used for the organic light emitting display device of the present invention by applying it on a substrate not subjected to the alignment function, uniformly aligning it by heat treatment, and polymerizing it. As a form of use, by combining the positive C plate obtained by the polymerization with a circular polarizing plate, it can be used as a viewing angle compensating film for an organic light emitting display element. The circular polarizing plate and the retardation film may be bonded with an adhesive, an adhesive, or the like. .. The polarizing plate used for the circular polarizing plate used at this time may be a film having a polarizing function. For example, a polyvinyl alcohol-based film adsorbed with iodine or a dichroic dye and stretched, or a polyvinyl alcohol-based film. A film in which iodine or a dichroic dye or a dichroic dye is adsorbed by stretching, a film in which an aqueous solution containing the dichroic dye is applied onto a substrate to form a polarizing layer, a wire grid polarizing element, etc. Can be mentioned.

As the polyvinyl alcohol-based resin, a saponified polyvinyl acetate-based resin can be used, and as the polyvinyl acetate-based resin, in addition to polyvinyl acetate, which is a copolymer of vinyl acetate, vinyl acetate and this can be used. Examples thereof include copolymers with other copolymerizable monomers. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group. The method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The thickness of the polyvinyl alcohol-based raw film is not particularly limited, but is, for example, about 10 to 150 μm.

When iodine is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide for dyeing is usually adopted. When a dichroic dye is used as the dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye and dyeing is usually adopted.

In the case of a film in which an aqueous solution containing a bicolor dye is applied onto a substrate to form a polarizing layer, examples of the bicolor dye to be applied include direct dyes, acid dyes, etc., depending on the type of substrate used. Examples thereof include water-soluble dyes, acid dyes and disperse dyes thereof, and water-insoluble dyes such as oil-soluble dyes. These dyes are usually dissolved in water and an organic solvent, and in some cases, a surfactant is added and applied to a base material that has been subjected to rubbing and corona treatment. The organic solvent varies depending on the solvent resistance of the base material, but is generally alcohols such as methanol, ethanol and isoprovir alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, ketone cheeks such as acetone and methyl ethyl ketone, and dimethylformamide. , N-methylvirolidone and other amides, and benzene, toluene and other aromatic organic solvents. The amount of the dye applied varies depending on the polarization performance of the dye, but is generally 0.05 to 1.0 g / po, preferably 0.1 to 0.8 g / rrf. Examples of the method of applying the color liquid to the base material include various coating methods such as bar coder coating spray coating, roll coating, and gravure coating.

When a wire grid polarizer is used, it is preferable to use one formed of a conductive material such as Al, Cu, Ag, Cu, Ni, Cr, and Si.

The present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" are based on mass.
(Preparation of Polymerizable Liquid Crystal Composition (1))
50 parts of the compound represented by the formula (1-1-51), 50 parts of the compound represented by the formula (1-1-52), 1 part of the compound represented by the formula (B-1), p-methoxyphenol. (MEHQ: manufactured by Wako Pure Chemical Industries, Ltd.) After adding 0.1 part to 233 parts of toluene, heat to 60 ° C. and stir to dissolve, and after confirmation of dissolution, return to room temperature and Omnirad819 (O). −819: 6 parts (manufactured by IGM Resin VV) was added and further stirred to obtain a solution. The solution was clear and uniform. The obtained solution was filtered through a 0.20 μm membrane filter to obtain the polymerizable liquid crystal composition (1) used in Example 1.
(Preparation of Polymerizable Liquid Crystal Compositions (2) to (32), Comparative Polymerizable Liquid Crystal Compositions (C1) to (C3))
The polymerizable liquid crystal used in Examples 2 to 32 under the same conditions as the preparation of the polymerizable liquid crystal composition (1) in Example 1 except that each of the compounds shown below was changed to the ratio shown in Tables 1 to 5 below. The polymerizable liquid crystal compositions (C1) to (C3) used in the compositions (2) to (32) and Comparative Examples 1 to 3 were obtained.

The following table shows the specific compositions of the polymerizable liquid crystal compositions (1) to (32) of the present invention and the comparative polymerizable liquid crystal compositions (C1) to (C3).
In addition, each component in each composition is as follows.
(Polymerizable liquid crystal compound)

(Example 1)
(Solubility)
When the polymerizable liquid crystal composition (1) of the present invention was stored in a sealed state at each temperature of 25 ° C., 20 ° C., 15 ° C., and 10 ° C. for 1 week and then the solubility was confirmed, precipitation and the like were observed under any temperature condition. It remained transparent.

⊚: No precipitate was observed under the conditions of 25 ° C., 20 ° C., 15 ° C. and 10 ° C., and the transparent state was maintained.
◯: No precipitate was observed under the conditions of 25 ° C., 20 ° C., and 15 ° C., and the transparent state was maintained.
Δ: No precipitate was observed under the conditions of 25 ° C. and 20 ° C., and the transparent state was maintained.
X: Precipitates were observed under any temperature condition.

(Phase transition temperature)
A glass substrate (D263: manufactured by Matsunami Glass Industry Co., Ltd.) having no alignment layer was subjected to ozone treatment for 30 seconds. The polymerizable liquid crystal composition (1) of the present invention was applied to this substrate by a spin coating method, and dried at 80 ° C. for 5 minutes to volatilize the solvent. After cooling the obtained coating film at room temperature for 2 minutes, the phase transition temperature was measured by observation with a polarizing microscope while raising the temperature from room temperature at a rate of 2 ° C./min. As a result, the nematic phase to the isotropic phase was measured at around 43 ° C. The phase transition temperature Tni (° C.) was observed.

(Preparation of optical anisotropic body)
A glass substrate (D263: manufactured by Matsunami Glass Industry Co., Ltd.) having no alignment layer was subjected to ozone treatment for 30 seconds. The polymerizable liquid crystal composition (1) of the present invention was applied to this substrate by a spin coating method, and dried at a temperature of 110 ° C. for 30 minutes. The obtained coating film was cooled at room temperature for 2 minutes and then irradiated with ultraviolet rays at an intensity of 100 mW / cm ² for 2.5 seconds using a high-pressure mercury lamp to obtain an optical variant of Example 1. The orientation evaluation, phase difference evaluation, and adhesion evaluation of the obtained optical anisotropic body were performed according to the following methods.

(Orientation evaluation)
Visual observation: Two polarizing plates are arranged on the light box so as to have cross Nicol conditions, the obtained optical anisotropic body is placed between the two polarizing plates, and the optical anisotropic body is visually observed while rotating. did.
[Evaluation criteria]
⊚: No defects are visually observed and the orientation is vertical.
◯: There are no defects visually, but there are some parts that are not vertically oriented.
Δ: There are some defects visually, and there are many parts that are not vertically oriented.
X: Many defects are visually observed, and the orientation is not vertical as a whole.

(Phase difference evaluation)
The out-of-plane retardation (Rth) of the obtained optically anisotropic substance was measured for the angular dependence of the phase difference using a retardation film / optical material inspection device RETS-100 (manufactured by Otsuka Electronics Co., Ltd.), and out-of-plane. The phase difference Rth (wavelength: 550 nm) was determined.

(Evaluation of wavelength dispersibility value)
The out-of-plane retardation (Rth) of the obtained optically anisotropic substance was measured for the angular dependence of the phase difference using a retardation film / optical material inspection device RETS-100 (manufactured by Otsuka Electronics Co., Ltd.), and out-of-plane. The retardation Rth (wavelength: 450 nm) and Rth (wavelength: 550 nm) were determined, and Rth (450 nm) / Rth (550 nm) was calculated.

(Adhesion evaluation)
The cellophane tape was attached to the obtained optically anisotropic substance and quickly peeled off from the optically anisotropic substance in the 90-degree direction to evaluate the adhesion of the optically anisotropic substance to the substrate.
⊚: 90% or more of the area where the optically anisotropic substance and the substrate are not separated remains.
◯: The area where the optically anisotropic substance and the substrate are not separated remains 50% or more and less than 90%.
Δ: 20% or more and less than 50% of the area where the optically anisotropic substance and the substrate are not separated remains.
X: The area where the optically anisotropic substance and the substrate are not separated is less than 20%.

(Examples 2-32)
The orientation of the optically anisotropic substances of Examples 2 to 32 under the same conditions as in Example 1 except that the polymerizable liquid crystal composition used was changed to the polymerizable liquid crystal compositions (2) to (32) of the present invention. Sex evaluation, phase difference evaluation, and adhesion evaluation were performed.

(Comparative Examples 1 to 3)
Under the same conditions as in Example 1 except that the polymerizable liquid crystal composition used was changed to the comparative polymerizable liquid crystal compositions (C1) to (C3), the orientation evaluation and adhesion of the films of Comparative Examples 1 to 3 were performed. Sexual evaluation was performed.
The results are shown in the table below.

(Example 33)
(Preparation of Polymerizable Liquid Crystal Composition (a) for A Plate)
49 parts of the compound represented by the formula (2-1-65, n = 6), 49 parts of the compound represented by the formula (2-1-58, n = 6), formula (3-1; m = n = 3. Add 2 parts of the compound represented by R = CH ₃ ) and 0.1 part of p-methoxyphenol (MEHQ: manufactured by Wako Pure Chemical Industries, Ltd.) to 300 parts of toluene, and then heat and stir at 70 ° C. After the dissolution was confirmed, the temperature was returned to room temperature, and 3 parts of Omnirad 651 (O-651: manufactured by IGM Resin V.V.) and Omnirad 819 (O-819: manufactured by IGM Resin B.V.) were manufactured. ) 3 parts, 0.2 part of the compound represented by the formula (E-2) was added, and further stirring was performed to obtain a solution. The solution was clear and uniform. The obtained solution was filtered through a 0.20 μm membrane filter to obtain a polymerizable liquid crystal composition (a) for an A plate.

Compound (E-2) Number average molecular weight 4,500, weight average molecular weight 9,000

An N-methylpyrrolidone solution (concentration: 5 wt%) of the photo-aligned polymer represented by the formula (5) was applied on a PET film substrate having a thickness of 50 μm with a bar coater, dried at 100 ° C. for 2 minutes, and had a wavelength of 313 nm. The linear polarization of ultraviolet light was irradiated from the direction perpendicular to the substrate to obtain a PET substrate on which a photoalignment film was laminated. The polymerizable liquid crystal composition (a) for A plate is applied onto this PET substrate with a bar coater, dried at 80 ° C. for 2 minutes, left at room temperature for 1 minute, and then the integrated light amount is 300 mJ / using a high-pressure mercury lamp. Ultraviolet rays were irradiated so as to be cm ^2, and a retardation layer A33, which was a positive A plate, was obtained. After ozone-treating the surface of the obtained retardation layer A33, the polymerizable liquid crystal composition (5) of the present invention was applied with a bar coater and dried at a temperature of 110 ° C. for 30 minutes. After cooling the obtained coating film to room temperature for 2 minutes, a plurality of retardation layers C33, which are positive C plates, were laminated by irradiating ultraviolet rays at an intensity of 30 mW / cm ² for 30 seconds using a high-pressure mercury lamp. A retardation layer AC33 was obtained. The PET film is peeled off from the obtained optically anisotropic AC33, the pressure-sensitive adhesive layer "DAITAC ZB7010W-15 (manufactured by DIC Co., Ltd.)" is attached thereto, and a commercially available polarizing plate is used as a slow phase of the optically anisotropic AC33. An elliptical polarizing plate was prepared by laminating so that the direction of the axis and the angle (bonding angle) of the absorption axis of the polarizing plate were 45 °. Further, the adhesive layer "DAITAC ZB7010W-15" is attached to the retardation layer C33 surface of the optically anisotropic AC33, and instead of the circular polarizing plate used in the SAMSUNG GALAXY SII equipped with an organic EL panel, the above The circular polarizing plate of No. 1 was attached to evaluate the tint of black from the front or at an angle of 45 °.
(Example 34)
An N-methylpyrrolidone solution (concentration: 5 wt%) of the photo-aligned polymer represented by the formula (5) was applied on a PET film substrate having a thickness of 50 μm with a bar coater, dried at 100 ° C. for 2 minutes, and had a wavelength of 313 nm. The linear polarization of ultraviolet light was irradiated from the direction perpendicular to the substrate to obtain a PET substrate on which a photoalignment film was laminated. The polymerizable liquid crystal composition (a) for A plate is applied onto this PET substrate with a bar coater, dried at 80 ° C. for 2 minutes, left at room temperature for 1 minute, and then the integrated light amount is 300 mJ / using a high-pressure mercury lamp. Ultraviolet rays were irradiated so as to be cm ^2, and a retardation layer A34, which was a positive A plate, was obtained. The pressure-sensitive adhesive layer "DAITAC ZB7010W-15 (manufactured by DIC Corporation)" is attached onto the obtained retardation layer A34, and a commercially available polarizing plate is applied to the direction of the slow axis of the retardation layer A34 and the absorption axis of the polarizing plate. A circular polarizing plate CP34 was prepared by laminating so that the angle (bonding angle) was 45 °.
The polymerizable liquid crystal composition (5) of the present invention was applied on a PET having a thickness of 50 μm with a bar coater, and dried at a temperature of 110 ° C. for 30 minutes. The obtained coating film was cooled to room temperature for 2 minutes, and then irradiated with ultraviolet rays at an intensity of 30 mW / cm ² for 30 seconds using a high-pressure mercury lamp to obtain a retardation layer C34 which is a positive C plate. The pressure-sensitive adhesive layer "DAITAC ZB7010W-15 (manufactured by DIC Co., Ltd.)" is attached onto the obtained retardation layer C34, and is attached to the circular polarizing plate CP34 from which the PET film has been removed, and further on the optical variant C34 side. After removing a certain PET film, the above-mentioned circular polarizing plate is attached instead of the circular polarizing plate used in GALAXY SII manufactured by SAMSUNG, which is mounted on an organic EL panel, and a black color from the front or an angle of 45 ° is attached. The taste and appearance were evaluated.
The results are shown in the table below.

As shown in the above examples, a) the polymerizable compound of the present invention containing a polymerizable compound having two or more polymerizable groups and satisfying the formula (I) and the self-directing compound of the present invention. As for the liquid crystal composition, the optical variant of the present invention (Examples 1 to 32) formed from the polymerizable liquid crystal compositions (1) to (32) has good orientation evaluation results and is highly productive. It can be said that it is excellent. Among them, in particular, the polymerizable liquid crystal composition using the spontaneously oriented compound represented by the general formula (i) and having a specific structure having a polymerizable group has very high results of orientation evaluation and adhesion evaluation. The result was good. On the other hand, from the results of Comparative Example 1, in the case of the polymerizable liquid crystal composition containing no spontaneously oriented compound of the present invention, the orientation evaluation was poor, and the result was inferior to that of the polymerizable liquid crystal composition of the present invention. ..

The polymerizable liquid crystal composition of the present invention is useful for optically anisotropic substances such as retardation films, optical compensation films, and antireflection films, and these members can be used for liquid crystal display elements and organic light emission display elements.

Claims (21)

a) It has two or more polymerizable groups and has the formula (I).
: Re (450 nm) / Re (550 nm) <1.0 (I)
(In the formula, Re (450 nm) is the wavelength of 450 nm when the polymerizable compound having two or more polymerizable groups is oriented on the substrate in the major axis direction substantially horizontally with respect to the substrate. The in-plane retardation, Re (550 nm), is such that the polymerizable compound having one polymerizable group or the polymerizable compound having two or more polymerizable groups is substantially placed on the substrate in the major axis direction of the molecule. Represents the in-plane phase difference at a wavelength of 550 nm when oriented horizontally with respect to the substrate.)
Polymerizable compounds that satisfy
And b) A polymerizable liquid crystal composition containing a spontaneously oriented compound. The polymerizable liquid crystal composition according to claim 1, wherein the spontaneously oriented compound is a compound having a partial structure represented by the following general formula (K-1), (K-2) or (K-3). ..

(In the formula, the black dots represent the bonds,
T ^k1 are independently from the general formulas (T-1) to (T-7).

(In the formula, the black dot represents the bond.) Represents the group represented by
^ST1 independently represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms, and the alkylene The −CH ₂₋ of the group or the alkenylene group may be replaced with −O−, −COO−, −C (= O) − or −OCO− so that the oxygen atom is not directly adjacent to the group.
R ^T1 represents an alkyl group having 1 to 5 carbon atoms independently, -CH ₂ of the alkyl groups - as is not adjacent the oxygen atom directly -O -, - COO -, - C (= O) May be replaced with − or −OCO−
^RT2 and ^RT3 independently represent hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, respectively.
R ^k1 independently represents a hydrogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group is −O−. May be replaced with
T ^k2 are independently from the general formulas (T-8) to (T-17).

(In the formula, the black dot represents the bond), X ^K1 and Y ^K1 independently represent −CH ₂ −, oxygen atom or sulfur atom, and Z ^K1 is independent of each other. W ^K1 , ^UK1 , V ^K1 and ^SK1 each independently represent a methine group or a nitrogen atom, and here, from the general formula (T-8) to (T-17). The hydrogen atom in the group represented by) may be substituted with −Sp ⁱ⁵ −P ⁱ³ .
Sp ⁱ³ , Sp ⁱ⁴ and Sp ⁱ⁵ each independently represent a single bond, a linear or branched alkylene group having 1 to 20 carbon atoms or a linear or branched halogenated alkylene group having 1 to 20 carbon atoms. -CH _2- in the alkylene group or halogenated alkylene group may be substituted with -CH = CH-, -C≡C- or -O- without the two -O- adjacent to each other.
P ⁱ² and P ⁱ³ are independently from the general formulas (P-1) to (P-16).

(In the formula, the black dot represents the bond.)
When a plurality of P ⁱ² , P ⁱ³ , Sp ⁱ³ , Sp ⁱ⁴ , Sp ⁱ⁵ , T ^k1 , and R ^k1 exist, they may be the same or different.
ki1 represents an integer of 1 to 3, ki2 and ki3 each independently represent an integer of 0 to 3, but the sum of ki1, ki2 and ki3 is 3. ) The polymerizable liquid crystal composition according to claim 2, wherein the spontaneously oriented compound is represented by the general formula (i).

(In the formula, ^Ki1 has the same meaning as the general formula (K-1), (K-2) or (K-3) according to claim 2.
R ^{i1 is, K i1} represents general formula (K-1) or a linear or branched alkyl group or halogenated alkyl group having carbon atoms 1 to 40 when (K-2) represent the, in these groups secondary carbon atom, as the oxygen atoms are not directly adjacent -O of -, - CH = CH- or -C≡C- may be substituted ^{with, when K i1} represents the general formula (K-3) Represents a linear or branched alkyl group or halogenated alkyl group having 1 to 40 carbon atoms, and the secondary carbon atoms in these groups are -O-, -CH = CH so that oxygen atoms are not directly adjacent to each other. It may be substituted with −, −C≡C−, −NH−, or represents any group represented by the general formulas (P-101) to (P-121).

A ⁱ¹ represents a divalent aromatic group, a divalent cyclic aliphatic group, or a divalent heterocyclic compound group, and the hydrogen atom in A ⁱ¹ may be substituted with ^{Li 1} , and A ^{when i1} there are multiple, the ^{a i1} closest to Sp ^i1, hydrogen atoms in the structure ^is, L ^i1, P i1 ^{-Sp i1} - or ^{-K i1} may be substituted with,
^Li1 represents a halogen atom, a cyano group, a nitro group, a linear or branched alkyl group having 1 to 40 carbon atoms, and an alkyl halide group, and the secondary carbon atom in the alkyl group is directly adjacent to an oxygen atom. It may be replaced with -CH = CH-, -C≡C-, -O-, -NH-, -COO- or -OCO- so as not to be.
^{Pi 1} represents a polymerizable group
Sp ⁱ¹ represents a spacer group or a single bond,
Z ⁱ¹ is a single bond, -CH = CH -, - CF = CF -, - C≡C -, - COO -, - OCO -, - OCOO -, - CF 2 O -, - OCF 2 -, - CH = CHCOO-, -OCOCH = CH-, -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 2 to 20 carbon atoms, and one or two or more non-adjacent -CH _2- in this alkylene group is -O-, -COO- or May be replaced with −OCO−
^mi1 represents an integer of 0 to 5, and when there are a plurality of A ⁱ¹ , Z ⁱ¹ , ^{Li 1} , ^{Ki 1} , ^{Pi 1,} and Sp ^{i 1 in} the general formula (i), they are different even if they are the same. You may be. ) The polymerizable liquid crystal composition according to claim 3, which has at least one polymerizable group in the general formula (i). The polymerizable liquid crystal composition according to any one of claims 1 to 4, which contains 0.01 to 30% by mass of the spontaneously oriented compound in the total amount of the polymerizable liquid crystal compound. The polymerizable compound has the following general formula (1).

(In the formula, P ¹¹ represents a polymerizable group, and R ¹² is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, a nitro group, an isocyano group, a thioisocyano group, Alternatively, it represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom. well, one -CH ₂ in the alkyl group - or nonadjacent two or more -CH ₂ - each independently -O is -, - S -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O-CO-O -, - CO-NH -, - NH-CO- or may be substituted by ^{-C≡C-, S 11} and S ¹² represents a spacer group or a single bond, but when a plurality of S ¹¹ and S ¹² are present, they may be the same or different, and X ¹¹ and X ¹² are −O−, −S−, −. OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH -CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH- OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO-, -CH _2- OCO-, -CH = CH-, -N = N-, -CH = N- It represents N = CH-, -CF = CF-, -C≡C- or a single bond, but if there are multiple X ^{11 to} X ^12, they may be the same or different (however, each). The P- (SX) -bond does not contain -O-O-), A ¹¹ and A ¹² are independently 1,4-phenylene group, 1,4-cyclohexylene group and pyridine-2, respectively. , 5-diyl group, pyrimidin-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6 - represents a diyl group or 1,3-dioxane-2,5-diyl group, these groups may be substituted by unsubstituted or one or more L ² However, when a plurality of A ¹¹ and / or A ¹² appear, they may be the same or different, and Z ¹¹ and Z ¹² are independently -O-, -S-, -OCH ₂ -,-. CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH _2- , -CH ₂ CH _2- COO-, -CH ₂ CH ₂ -OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO-, -CH _2- OCO-, -CH = CH-, -N = N-, -CH = Represents N-, -N = CH-, -CH = N-N = CH-, -CF = CF-, -C≡C- or a single bond, but when multiple Z ¹¹ and / or Z ¹² appear, respectively It may be the same or different, and M is from the following equations (M-1) to (M-9).

Represents a group selected from these groups may be substituted by unsubstituted or one or more L ^2, G is the formula from the following formulas (G-1) (G- 5)

(In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, and may be arbitrary in the alkyl group. the hydrogen atoms may be substituted by a fluorine atom, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S- , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- Any hydrogen atom may be replaced with a fluorine atom from the viewpoint of liquidity and ease of synthesis, and one −CH ₂ − or two or more non-adjacent −CHs may be substituted with the fluorine atom. ₂ - -O independently each -, - COO- or preferably represents a linear or branched alkyl group having 12 good 1 -C be replaced by -OCO-, any hydrogen atom It is more preferable to represent a linear or branched alkyl group having 1 to 12 carbon atoms which may be substituted with a fluorine atom, and particularly preferably to represent a linear alkyl group having 1 to 12 carbon atoms. ⁸¹ has at least one aromatic group, represents a 30 group from 5 carbon atoms, said group may be substituted by unsubstituted or one or more L ^2, W ⁸² is the following formula (82) Group represented by

^{(Wherein, P W82} has the same meaning as ^{P 11, S W82} has the same meaning as ^{S 11, X W82} has the same meaning as ^{X 11, m W82} represent. The same meanings as m11) represents ,
W ⁸³ and W ⁸⁴ each have a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, and at least one aromatic group and have 5 to 30 carbon atoms. Group, alkyl group with 1 to 20 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, alkenyl group with 2 to 20 carbon atoms, cycloalkenyl group with 3 to 20 carbon atoms, 1 to 20 carbon atoms Aalkoxy group, an acyloxy group having 2 to 20 carbon atoms, an alkylcarbonyloxy group having 2 to 20 carbon atoms, or a group represented by the following formula (84).

^{(Wherein, P W84} has the same meaning as ^{P 11, S W84} has the same meaning as ^{S 11, X W84} has the same meaning as ^{X 11, m W84} represent. The same meanings as m11) represents the However, either W ⁸³ or W ⁸⁴ is a group represented by the above formula (84), and the alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, acyloxy group, alkylcarbonyloxy group. One -CH _2- or two or more non-adjacent -CH ₂ -in each of them are independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-. It may be replaced by S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C-, where M is the formula (M-). 1) When selected from the formula (M-8) G is selected from the formulas (G-1) to (G-4), and when M is the formula (M-9), G is the formula (G-). Representing 5), L ² represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, It represents a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched. , arbitrary hydrogen atom may be substituted by a fluorine atom, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = Selected from CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- it may be substituted by a group, if L ² is more present in the compounds they may be the same or different and represent an integer of n11 and n12 from 1 each independently is 4, n11 + n12 Represents an integer from 1 to 5. ), And m11 and m12 independently represent integers from 0 to 5. ). The polymerizable liquid crystal composition according to any one of claims 1 to 5. In addition to the polymerizable liquid crystal compound represented by the general formula (1), it has two or more polymerizable groups and satisfies the formula (I).
Re (450 nm) / Re (550 nm) <1.0 (I)
(In the formula, Re (450 nm) is the wavelength of 450 nm when the polymerizable compound having two or more polymerizable groups is oriented substantially horizontally with respect to the substrate in the long axis direction of the molecule. The in-plane retardation, Re (550 nm), is 550 nm when the polymerizable compound having two or more polymerizable groups is oriented on the substrate in the major axis direction of the molecule substantially horizontally with respect to the substrate. Represents the in-plane phase difference at the wavelength of (2) and the general formula (2).

(In the formula, P ¹¹ , S ¹¹ , S ¹² , X ¹¹ , X ¹² , A ¹¹ , A ¹² , Z ¹¹ , Z ¹² , m11, m12, n11, and n12 are the same as those in the general formula (1). P ¹² has the same meaning as P ^11, and M ² has the following equations (M-201) to (M-211).

Represents a group selected from these groups may be substituted by unsubstituted or one or more ^{L 1, G 2} of the formula from the following formula (G-201) (G- 206)

(In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, and may be arbitrary in the alkyl group. the hydrogen atoms may be substituted by a fluorine atom, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S- , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- May be replaced by
W ²¹ has at least one aromatic group, represents a 30 group from 5 carbon atoms, said group may be substituted by unsubstituted or one or more L ^1,
W ²² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and the alkyl group may be linear or branched, and any hydrogen atom in the alkyl group may be used. may be substituted by a fluorine atom and / or -OH, 1 single -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S -, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH Even if substituted by -COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- well, ^{or, W 22} may represent a similar meaning as ^{W 21, also, W 21} and ^{W 22} may form a connection to the same ring structure, or ^{W 22} is the following formula (22) Group represented by

^{(Wherein, P W22} has the same meaning as ^{P 11, S W22} has the same meaning as ^{S 11, X W22} has the same meaning as ^{X 11, m W22} represent. The same meanings as m11) represents ,
W ²³ and W ²⁴ each have a halogen atom, a cyano group, a hydroxy group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, and at least one aromatic group and have 5 to 30 carbon atoms. Group, alkyl group with 1 to 20 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, alkenyl group with 2 to 20 carbon atoms, cycloalkenyl group with 3 to 20 carbon atoms, 1 to 20 carbon atoms Represents an alkoxy group, an acyloxy group having 2 to 20 carbon atoms, or an alkylcarbonyloxy group having 2 to 20 carbon atoms, the above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkoxy group, acyloxy group. , one -CH ₂ in the alkyl carbonyl group - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or -C≡C- may be substituted, or the following formula ( Group represented by 24)

^{(Wherein, P W24} has the same meaning as ^{P 11, S W24} has the same meaning as ^{S 11, X W24} has the same meaning as ^{X 11, m W24} represent. The same meanings as m11) represents ,
However, when the above M ² is selected from the formulas (M-201) to (M-210), G ² is selected from the formulas (G-201) to (G-205), and M is selected from the formula (M-205). In the case of 211), G ² represents the equation (G-206). The polymerizable liquid crystal composition according to claim 6, further comprising the compound represented by). The polymerizable liquid crystal composition according to claim 6 or 7, further comprising a polymerizable compound represented by the following general formula (3) having two polymerizable groups.

(In the formula, P ³¹ and P ³² represent polymerizable groups.
S ³¹ and S ³² represent a spacer group or a single bond, but if there are multiple S ³¹ and S ^32, they may be the same or different, respectively.
X ³¹ and X ³² are -O-, -S-, -OCH _2- , -CH ₂ O-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-,- O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S-, -SCF ₂ -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO-CH ₂ CH ₂ -, -CH ₂ CH _2- COO-, -CH ₂ CH _2- OCO-, -COO-CH _2- , -OCO-CH _2- , -CH _2- COO-, -CH _2- OCO-, -CH = CH -, - N = N -, - CH = N-N = CH -, - CF = CF -, - C≡C- or represents a single ^bond, they ^{If X 31} and ^{X 32} there are a plurality They may be the same or different (although each P- (SX) -bond does not include -O-O-).
A ³¹ and A ³² are independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidin-2,5-diyl group, naphthalene-2,6-diyl, respectively. Represents a group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, but these. each group may be substituted by unsubstituted or one or more L ^2, but when a ³¹ and / or a ³² appears more often are each independently selected from a same, Z ³¹ and Z ³² is Independently -O-, -S-, -OCH _2- , -CH ₂ O-, -CH ₂ CH _2- , -CO-, -COO-, -OCO-, -CO-S-, -S- CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -SCH _2- , -CH ₂ S-, -CF ₂ O-, -OCF _2- , -CF ₂ S- , -SCF _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -COO-CH ₂ CH _2- , -OCO- _{CH 2 CH 2 -, - CH} 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH 2 -OCO −, −CH = CH−, −N = N−, −CH = N−, −N = CH−, −CH = N−N = CH−, −CF = CF−, −C≡C− or single bond However, when a plurality of Z ⁸³ and / or Z ⁸⁴ appear, they may be the same or different, and M ³¹ is a 1,4-phenylene group, a 1,4-cyclohexylene group, or 1,4-. Cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydrothiopyran-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-tetrahydronaphthalene-2,6-diyl group, naphthylene-1,4-diyl group, naphthylene-1,5-diyl group, naphthylene-1,6-diyl group, naphthylene-2, 6-diyl 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, 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] Benzoselenopheno [3,2-b] represents a group selected from a selenophen-2,7-diyl group or a fluorene-2,7-diyl group, wherein these groups are unsubstituted or one or more. L ² may be substituted with L ² of, where L ² is a fluorine atom, chlorine atom, bromine atom, iodine atom, pentafluorosulfuranyl group, nitro group, isocyano group, amino group, hydroxyl group, mercapto group, methylamino group. , Dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or alkyl group having 1 to 20 carbon atoms. The alkyl group is branched even if it is linear. may be in any of the hydrogen atoms may be substituted by a fluorine atom, one -CH 2 in the alkyl group _- or nonadjacent two or more -CH 2 _- are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C - may be substituted by a group selected from, but if L ² is more present in the compounds they may be different even in the same, J31 and j32 are each independently 1 to 4 integer , But j31 + j32 represent an integer from 1 to 5. ), And m31 and m32 independently represent integers from 0 to 5. ) Formula (1) polymerizable group ^{P 11} in the formula (82) in the polymerizable group ^{P W82,} the formula (84) in the polymerizable group ^{P W84,} polymerizable in the general formula (2) group ^{P 11, P 12,} the formula (22) the polymerizable group ^{P W22} in the formula (24) in the polymerizable group ^{P W24,} the polymerizable group ^{P 31, P 32} in the general formula (3) The polymerizable liquid crystal composition according to any one of claims 6 to 8, which is represented by any of the general formulas (P-1) to (P-20).

The polymerizable liquid crystal composition according to any one of claims 6 to 9, which contains 30 to 100% by mass of the polymerizable liquid crystal compound represented by the formula (1) in the total amount of the polymerizable compound of a). .. An optically anisotropic substance comprising a polymer of the polymerizable liquid crystal composition according to any one of claims 1 to 10, which has a homeotropic orientation and satisfies the formula (D).
Rth (450) / Rth (550) <1.08 equation (D)
(In the formula, Rth (450) represents the out-of-plane phase difference at a wavelength of 450 nm, and in the formula, Rth (550) represents the out-of-plane phase difference at a wavelength of 550 nm.) The optical anisotropic substance according to claim 11, wherein the proportion of the polymerizable liquid crystal compound present in the optical anisotropic substance is 20% by weight or less. A retardation film in which a retardation film (I) made of the optically anisotropic substance according to any one of claims 11 or 12 and a retardation film (II) satisfying the following formula (E) are laminated.
nx> ny ≒ nz equation (E)
(Nz represents the refractive index in the thickness direction, nx represents the refractive index in the direction that produces the maximum refractive index in the plane, and ny represents the refractive index in the direction orthogonal to the direction of nx in the plane. Represents) The retardation film according to claim 13, wherein the retardation film (II) and the retardation film (I) are laminated, and no vertical alignment film is provided between the retardation film (II) and the retardation film (I). The retardation film according to claim 13 or 14, wherein the retardation film (I) and the retardation film (II) are laminated via an adhesive layer. The retardation film according to claim 13, wherein the retardation film (I) and the retardation film (II) are directly laminated in this order. A method for producing an optically anisotropic substance, wherein the polymerizable liquid crystal composition according to any one of claims 1 to 10 is applied onto a substrate having no vertically oriented film and, if necessary, dried. A polarizing film containing the retardation film (I) made of the optically anisotropic substance according to claim 11 or 12 and a linear polarizing plate. The polarizing film according to claim 17, wherein the linear polarizing plate contains a dichroic dye. A display device containing the polarizing film according to claim 17 and 18. A light emitting device containing the polarizing film according to claim 17 and 18.