JP5638347B2 - Novel polymerizable liquid crystal compound and polymerizable liquid crystal composition containing the polymerizable liquid crystal compound - Google Patents

Description

  The present invention provides a novel polymerizable liquid crystal compound having a plurality of linear structures arranged in a straight line and having a plurality of polymerizable functional groups such as a (meth) acryloyloxy group, and a polymerization containing the polymerizable liquid crystal compound The present invention relates to a liquid crystal composition. The polymerizable liquid crystal compound is a polymerizable liquid crystal composition and is suitably used for forming an optical film.

  A liquid crystal compound having a polymerizable functional group (hereinafter referred to as “polymerizable liquid crystal compound”) or a liquid crystal composition containing at least one polymerizable liquid crystal compound (hereinafter referred to as “polymerizable liquid crystal composition”) After uniform alignment in the state, when irradiated with active energy rays such as ultraviolet rays while maintaining the liquid crystal state, an optically anisotropic film containing a polymer in which the alignment state structure of liquid crystal molecules is fixed semi-permanently is created. I can do it. The polymer obtained in this manner has anisotropy of physical properties such as refractive index, dielectric constant, magnetic susceptibility, elastic modulus, and thermal expansion coefficient. It can be applied as a molded body having optical anisotropy such as a plate, a polarizing prism, a brightness enhancement film, a low-pass filter, various optical filters, an optical fiber coating material, a waveguide, a piezoelectric element, and a nonlinear optical element. In the optical anisotropic body (polymer) obtained by polymerization, characteristics other than anisotropy are also important. The properties include polymerization rate, polymer transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, melting point, glass transition point, clearing point, chemical resistance, heat resistance. And the like.

  In the above polymerizable liquid crystal composition, when the liquid crystal phase expression temperature is high, not only photopolymerization by active energy rays such as ultraviolet rays but also unintentional thermal polymerization is induced, and the uniform alignment state of liquid crystal molecules is lost. It is difficult to fix the orientation. Accordingly, there is a need for a polymerizable liquid crystal composition that exhibits a liquid crystal phase near room temperature in order to facilitate temperature control during curing.

  Patent Documents 1 to 3 disclose a polymerizable liquid crystal compound in which the polymerizable functional group is a (meth) acryl group, the polymerizable liquid crystal compound has high polymerization reactivity, and the obtained polymer is highly transparent. Since bifunctional and trifunctional monomers have improved heat resistance after polymerization, they are actively studied for use as optical anisotropic bodies. Patent Documents 4 to 7 disclose polymerizable liquid crystal compounds in which the polymerizable functional group is an oxirane group or an oxetane group.

  However, the polymerizable liquid crystal compounds described in Patent Documents 1 to 3 have a problem that polymerization time is long due to polymerization inhibition due to oxygen. Further, the polymerizable liquid crystal compounds described in Patent Documents 4 to 7 have a problem that the liquid crystal phase expression temperature is high.

JP-A-11-116534 Japanese Patent Laid-Open No. 11-130729 JP 2005-309255 A JP 2005-171235 A Japanese Patent Laying-Open No. 2005-320317 JP 2008-239873 A Japanese Patent No. 4347553

  Accordingly, an object of the present invention is to provide a polymer that exhibits a liquid crystal phase near room temperature (a wide temperature range showing a liquid crystal phase), does not precipitate crystals, exhibits rapid hardness by UV irradiation in the atmosphere, and has excellent heat resistance. Is to provide a polymerizable liquid crystal compound.

  In order to solve the above problems, the present invention has been studied for various polymerizable liquid crystal compounds, and as a result, has found that the above object can be achieved by a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a specific chemical structure. The present invention has been completed.

  That is, the present invention achieves the above object by providing a polymerizable liquid crystal compound represented by the following general formula (I).

（式中、環Ａ¹、Ａ²、Ａ³及びＡ⁴は、それぞれ独立に、ベンゼン環又はナフタレン環を表し、環Ａ ¹ 、環Ａ ² 、環Ａ ³ 及び環Ａ ⁴ の少なくとも１つがナフタレン環であり、
Ｓ¹及びＳ²は、それぞれ独立に、炭素原子数１〜８のアルキレン基を表し、該アルキレン基の水素原子はハロゲン原子で置換されてもよく分岐を有してもよく酸素原子で中断されてもよく、
Ｘ¹は、水素原子又はメチル基を表し、
Ｚ¹ は直接結合であり、Ｚ²、Ｚ³及びＺ⁴は、それぞれ独立に、−Ｏ−ＣＯ−又は−ＣＯ−Ｏ−であり、
Ｙ¹、Ｙ²、Ｙ³及びＹ⁴は、それぞれ独立に、炭素原子数１〜６のアルキル基、ハロゲン原子又はシアノ基を表し、該アルキル基の水素原子はハロゲン原子又はシアノ基で置換されてもよく、該アルキル基のメチレン基は酸素原子又は−ＣＯ−で中断されてもよく、
ａ、ｂ、ｃ及びｄは、それぞれ独立に、０〜８であり、
ｎは、１又は２であり、
Ｇは、下記式（２）又は（３）で表される置換基を表す。）

(In the formula, each of rings A ¹ , A ² , A ³ and A ⁴ independently represents a benzene ring or a naphthalene ring, and at least one of ring A ¹ , ring A ² , ring A ³ and ring A ⁴ is naphthalene. A ring,
S ¹ and S ² each independently represents an alkylene group having 1 to 8 carbon atoms, and the hydrogen atom of the alkylene group may be substituted with a halogen atom or may be branched and interrupted by an oxygen atom. You can,
X ¹ represents a hydrogen atom or a methyl group,
Z ¹ is a direct bond, Z ^2, Z ³ and Z ⁴ are each independently, - O-CO- or -CO-O - a Oh is,
Y ¹ , Y ² , Y ³ and Y ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, a halogen atom or a cyano group, and the hydrogen atom of the alkyl group is substituted with a halogen atom or a cyano group. The methylene group of the alkyl group may be interrupted by an oxygen atom or -CO-,
a, b, c and d are each independently 0 to 8,
n is 1 or 2,
G represents a substituent represented by the following formula ( 2) or (3 ) . )

（式（２）中、Ｒ¹は、水素原子又は炭素原子数１〜６のアルキル基を表し、式（３）中、Ｒ²は、水素原子又は炭素原子数１〜６のアルキル基を表す。）

(In Formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and in Formula (3), R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It is.)

  The present invention also provides a polymerizable liquid crystal composition containing one or more of the polymerizable liquid crystal compounds, and an optical film formed from a polymer obtained by photopolymerizing the polymerizable liquid crystal composition. It is.

  The polymerizable liquid crystal compound of the present invention exhibits a liquid crystal phase near room temperature (the temperature range showing the liquid crystal phase is wide) and no crystal is precipitated. In addition, since the polymerizable liquid crystal compound of the present invention has a radical polymerizable functional group, it exhibits fast curing by UV irradiation in the atmosphere. From the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound, heat resistance is improved. An excellent polymer is obtained.

  Hereinafter, the present invention will be described in detail based on preferred embodiments.

First, the polymerizable liquid crystal compound of the present invention will be described.
In the rings A ¹ , A ² , A ³ and A ⁴ in the above general formula (I), the bond (Z ¹ , Z ² , Z ³ , Z ⁴ or —O—S ² —G) of each ring is included. The position of the bond) may be any position on the ring, but ring A ¹ , A ² and A ³ and ring A ⁴ when n is 1 are a 1,4-phenylene group, 1,4 -A cyclohexylene group, a cyclohexene-1,4-diyl group, a naphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group or a tetrahydronaphthalene-2,6-diyl group is preferred. When n is 2, ring A ⁴ is a benzene-1,3,4-triyl group, cyclohexane-1,3,4-triyl group or cyclohexene-1,3,4-triyl group, A bond is bonded to Z _4, and a bond at the 3rd and 4th positions is bonded to —O—S ² —G, or a naphthalene-2,5,6-triyl group, decahydronaphthalene-2,5 , 6-triyl group or tetrahydronaphthalene-2,5,6-triyl group, the bond at the 2-position is bonded to Z _4, and the bond at the 5- and 6-positions is —O—S ² —G Bonding is preferred.

Examples of the alkylene group having 1 to 8 carbon atoms represented by S ¹ , S ² and L ¹ in the general formula (I) include ethylene, propylene, trimethylene, tetramethylene, butane-1,3-diyl, 2 -Methylpropane-1,3-diyl, 2-methylbutane-1,3-diyl, pentane-2,4-diyl, pentane-1,4-diyl, 3-methylbutane-1,4-diyl, 2-methylpentane -1,4-diyl, pentamethylene, hexamethylene, heptamethylene, octamethylene and the like. Among these, the S ¹ and S ² is preferably an alkylene group having 2 to 6 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms represented by Y ¹ , Y ² , Y ³ and Y ⁴ in the general formula (I) include methyl, chloromethyl, trifluoromethyl, cyanomethyl, ethyl and dichloroethyl. Propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, cyclopentyl, hexyl, 2-methylpentyl, 3-methylpentyl, cyclohexyl, bicyclohexyl, 1-methyl Examples of the halogen atom represented by Y ¹ , Y ² , Y ^3, and Y ⁴ include fluorine, chlorine, bromine, and iodine. Y ¹ , Y ² , Y ^3, and Y ⁴ are preferably alkyl groups having 1 to 3 carbon atoms and having no substitution by a halogen atom or a cyano group and no interruption by an oxygen atom or —CO—.

The polymerizable liquid crystal compound of the present invention represented by the general formula (I) preferably has at least one substituent on the ring. That is, in the general formula (I), it is preferable that at least one of a, b, c and d indicating the numbers of Y ¹ , Y ² , Y ³ and Y ⁴ is 1 or more. It is preferable to have at least one substituent on the ring in terms of improving solubility in a solvent, reducing crystallinity, and improving liquid crystal stability at room temperature.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ¹ in formula ( ² ), R ² in formula (3), and R ³ in formula (4) include Y in the general formula (I). ^1, Y ^2, include those exemplified as Y ³ and Y ^4.

As the polymerizable liquid crystal compound of the present invention, those in which the ring A ¹ , the ring A ² , the ring A ³ and the ring A ^{4 in the} general formula (I) are a benzene ring or a naphthalene ring have particularly low crystallinity. It is preferable because a liquid crystal phase is exhibited at a temperature of ℃ or lower.
In the general formula (I), at least one of ring A ¹ , ring A ² , ring A ³ and ring A ⁴ is a condensed ring (that is, naphthalene ring, decahydronaphthalene ring or tetrahydronaphthalene ring) The liquid crystal phase expression temperature range is wide, which is preferable.
Moreover, in the said general formula (I), when G is represented by the said Formula (2) or the said Formula (3), since the quick-hardness by UV irradiation in air | atmosphere is especially high, it is preferable.
Furthermore, in the above general formula (I), those in which Z ¹ is a direct bond and Z ² , Z ³ and Z ⁴ are —CO—O— or —OCO— are preferable because the liquid crystal orientation is further improved. .

Among the polymerizable liquid crystal compounds of the present invention represented by the above general formula (I), those represented by the following general formula (II) have a particularly wide liquid crystal expression temperature range, and particularly low crystallinity and a low temperature range. Since the liquid crystal phase stability in is high, it is preferable. In the following general formula (II), at least one of R ^{4 to} R ²⁴ is preferably an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. In the following general formula (II), when one of R ^{20 to} R ²⁴ is —O—S ² —G, R ²² is preferably —O—S ² —G. ^{When two of 20 to} R ²⁴ are —O—S ² —G, R ²² and R ²¹ or R ²³ are preferably —O—S ² —G.

（式中、Ｓ¹、Ｘ¹、Ｚ¹、Ｚ²、Ｚ³及びＺ⁴は、上記一般式（Ｉ）と同じであり、
Ｒ⁴〜Ｒ¹⁹は、それぞれ独立に、水素原子、炭素原子数１〜６のアルキル基、ハロゲン原子又はシアノ基を表し、
Ｒ²⁰〜Ｒ²⁴は、それぞれ独立に、水素原子、炭素原子数１〜６のアルキル基、ハロゲン原子、シアノ基又は−Ｏ−Ｓ²−Ｇを表し、Ｒ²⁰〜Ｒ²⁴のうち１つ又は２つは−Ｏ−Ｓ²−Ｇであり、
Ｒ⁴〜Ｒ²⁴で表されるアルキル基の水素原子は、ハロゲン原子又はシアノ基で置換されてもよく、Ｒ⁴〜Ｒ²⁴で表されるアルキル基のメチレン基は、酸素原子又は−ＣＯ−で中断されてもよく、Ｓ²及びＧは上記一般式（Ｉ）と同じである。）

(In the formula, S ¹ , X ¹ , Z ¹ , Z ² , Z ³ and Z ⁴ are the same as those in the general formula (I),
R ^{4 to} R ¹⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or a cyano group,
R ^{20 to} R ²⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, or —O—S ² —G, and one of R ^{20 to} R ²⁴ or two is -O-S ² -G,
The hydrogen atom of the alkyl group represented by R ^{4 to} R ²⁴ may be substituted with a halogen atom or a cyano group, and the methylene group of the alkyl group represented by R ^{4 to} R ²⁴ is an oxygen atom or —CO—. And S ² and G are the same as those in the general formula (I). )

Among the compounds represented by the above general formula (I), those represented by the following general formula (III) also have a wide liquid crystal expression temperature range, low crystallinity, and high liquid crystal phase stability in a low temperature range. preferable. In the following general formula (III), it is preferable that at least one of R ^{25 to} R ⁴³ is an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. In the following general formula (III), when one of R ^{39 to} R ⁴³ is —O—S ² —G, R ⁴¹ is preferably —O—S ² —G. ^{When two of 39 to} R ⁴³ are —O—S ² —G, R ⁴¹ and R ⁴⁰ or R ⁴² are preferably —O—S ² —G.

（式中、Ｓ¹、Ｘ¹、Ｚ¹、Ｚ²、Ｚ³及びＺ⁴は、上記一般式（Ｉ）と同じであり、
Ｒ²⁵〜Ｒ³⁸は、それぞれ独立に、水素原子、炭素原子数１〜６のアルキル基、ハロゲン原子又はシアノ基を表し、
Ｒ³⁹〜Ｒ⁴³は、それぞれ独立に、水素原子、炭素原子数１〜６のアルキル基、ハロゲン原子、シアノ基又は−Ｏ−Ｓ²−Ｇを表し、Ｒ³⁹〜Ｒ⁴³のうち１つ又は２つは−Ｏ−Ｓ²−Ｇであり、
Ｒ²⁵〜Ｒ⁴³で表されるアルキル基の水素原子は、ハロゲン原子又はシアノ基で置換されてもよく、Ｒ²⁵〜Ｒ⁴³で表されるアルキル基のメチレン基は、酸素原子又は−ＣＯ−で中断されてもよく、Ｓ²及びＧは上記一般式（Ｉ）と同じである。）

(In the formula, S ¹ , X ¹ , Z ¹ , Z ² , Z ³ and Z ⁴ are the same as those in the general formula (I),
R ^{25 to} R ³⁸ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or a cyano group,
R ^{39 to} R ⁴³ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, or —O—S ² —G, and one of R ^{39 to} R ⁴³ or two is -O-S ² -G,
The hydrogen atom of the alkyl group represented by R ^{25 to} R ⁴³ may be substituted with a halogen atom or a cyano group, and the methylene group of the alkyl group represented by R ^{25 to} R ⁴³ is an oxygen atom or —CO—. And S ² and G are the same as those in the general formula (I). )

Among the compounds represented by the above general formula (I), those represented by the following general formula (IV) also have a wide liquid crystal expression temperature range, low crystallinity, and high liquid crystal phase stability in a low temperature range. preferable. In the following general formula (IV), at least one of R ^{44 to} R ⁶² is preferably an alkyl group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. In the following general formula (IV), when one of R ^{58 to} R ⁶² is —O—S ² —G, R ⁶⁰ is preferably —O—S ² —G. ⁵⁸ two of the to R ⁶² in the case is a -O-S ² -G, it is preferable that the R ⁶⁰ and R ⁵⁹ or R ⁶¹ is -O-S ² -G.

（式中、Ｓ¹、Ｘ¹、Ｚ¹、Ｚ²、Ｚ³及びＺ⁴は、上記一般式（Ｉ）と同じであり、
Ｒ⁴⁴〜Ｒ⁵⁷は、それぞれ独立に、水素原子、炭素原子数１〜６のアルキル基、ハロゲン原子又はシアノ基を表し、
Ｒ⁵⁸〜Ｒ⁶²は、それぞれ独立に、水素原子、炭素原子数１〜６のアルキル基、ハロゲン原子、シアノ基又は−Ｏ−Ｓ²−Ｇを表し、Ｒ⁵⁸〜Ｒ⁶²のうち１つ又は２つは−Ｏ−Ｓ²−Ｇであり、
Ｒ⁴⁴〜Ｒ⁶²で表されるアルキル基の水素原子は、ハロゲン原子又はシアノ基で置換されてもよく、Ｒ⁴⁴〜Ｒ⁶²で表されるアルキル基のメチレン基は、酸素原子又は−ＣＯ−で中断されてもよく、Ｓ²及びＧは上記一般式（Ｉ）と同じである。）

(In the formula, S ¹ , X ¹ , Z ¹ , Z ² , Z ³ and Z ⁴ are the same as those in the general formula (I),
R ⁴⁴ to R ⁵⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or a cyano group,
R ^{58 to} R ⁶² each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, or —O—S ² —G, and one of R ^{58 to} R ⁶² or two is -O-S ² -G,
The hydrogen atom of the alkyl group represented by R ^{44 to} R ⁶² may be substituted with a halogen atom or a cyano group, and the methylene group of the alkyl group represented by R ^{44 to} R ⁶² is an oxygen atom or —CO—. And S ² and G are the same as those in the general formula (I). )

  Specific examples of the polymerizable liquid crystal compound of the present invention represented by the general formula (I) include compounds having the structures shown below. However, the present invention is not limited by the following compounds.

The production method of the polymerizable liquid crystal compound of the present invention is not particularly limited, and can be produced by applying a known reaction. For example, first, a (meth) acryloyloxy group intermediate produced by the method described in JP 2007-119415 A is hydrolyzed according to the following reaction formula 1 to obtain an intermediate having a phenolic hydroxyl group. Next, the obtained intermediate is reacted according to the following reaction formula 2 to form Z ⁴ , whereby the polymerizable liquid crystal compound of the present invention can be obtained. The following reaction formula 2 shows the case where Z ⁴ is —OCO— in the above general formula (I).

  The polymerizable liquid crystal compound of the present invention is preferably blended in a liquid crystal material as necessary, and is preferably used as a material for producing an optical anisotropic body excellent in heat resistance, liquid crystal alignment fixing ability, optical characteristics, hardness, solvent resistance, and the like. Besides being used, it can also be used as a monomer for polymer dispersed liquid crystal (PDLC), a liquid crystal alignment film, a liquid crystal alignment control agent, a coating material, a protective plate preparation material, and the like.

Next, the polymerizable liquid crystal composition of the present invention will be described.
The polymerizable liquid crystal composition of the present invention contains the polymerizable liquid crystal compound of the present invention and is preferably used as a material for producing an optical anisotropic body. The polymerizable liquid crystal composition of the present invention can further contain a liquid crystal compound in addition to the polymerizable liquid crystal compound of the present invention. The liquid crystal compounds referred to here include conventionally known liquid crystal compounds, liquid crystal analogs, and mixtures thereof.

In the polymerizable liquid crystal composition of the present invention, the content of the polymerizable liquid crystal compound represented by the general formula (I) is 100 masses of the total content of the polymerizable liquid crystal compound and the content of the liquid crystal compound. The amount is preferably 3 to 100 parts by mass, more preferably 5 to 100 parts by mass. If the content of the polymerizable liquid crystal compound of the present invention is less than 3 parts by mass, sufficient solvent solubility and liquid crystal phase stability may not be obtained.
In particular, when it is desired to increase the hardness of the polymer obtained from the polymerizable liquid crystal composition of the present invention, the ratio of the polymerizable liquid crystal compound of the present invention is increased (specifically, 70 to 100 parts by mass). preferable. In particular, when it is desired to increase the homogeneity of alignment, the ratio of the polymerizable liquid crystal compound of the present invention is preferably 30 to 100 parts by mass.

In order for the polymerizable liquid crystal composition of the present invention to exhibit a liquid crystal phase even at 25 ° C. or lower, as the polymerizable liquid crystal compound of the present invention, ring A ¹ and ring A ^{2 in the} above general formula (I) are used. , Ring A ³ and ring A ⁴ are at least one benzene ring or naphthalene ring, and the polymerizable liquid crystal compound contains the total content of the polymerizable liquid crystal compound of the present invention and the content of the liquid crystal compound When the total amount is 100 parts by mass, it is preferably 30 to 100 parts by mass.

As the liquid crystal compound, a generally used liquid crystal compound can be used, and specific examples of the liquid crystal compound are not particularly limited, and examples thereof include the following compounds.
In the compounds shown below, W ¹ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a branch, an alkoxy group having 1 to 8 carbon atoms which may have a branch, or a branch. An alkenyl group having 1 to 8 carbon atoms, a alkenyloxy group having 1 to 8 carbon atoms that may have a branch, and an alkynyl group having 1 to 8 carbon atoms that may have a branch An alkynyloxy group having 1 to 8 carbon atoms which may have a branch, an alkoxyalkyl group having 1 to 8 carbon atoms which may have a branch, and 1 to 8 carbon atoms which may have a branch. Represents an alkanoyloxy group or an alkoxycarbonyl group having 1 to 8 carbon atoms which may have a branch, or these may be substituted with a halogen atom, a cyano group or the like, and W ² represents a cyano group, a halogen atom An atom or a group represented by W ¹ is shown, and W ³ , W ⁴ and W ^{5 each} represents a hydrogen atom, a halogen atom or a cyano group.

  In the polymerizable liquid crystal composition of the present invention, a liquid crystal compound having a polymerizable functional group is preferably used as the liquid crystal compound. Examples of the polymerizable functional group include (meth) acryloyloxy group, fluoroacryl group, chloroacryl group, trifluoromethylacryl group, oxirane ring (epoxy), oxetane ring, styrene compound (styryl group), vinyl group, vinyl ether group. , Vinyl ketone group, maleimide group, phenylmaleimide group and the like are preferable, and (meth) acryloyloxy group, oxirane ring (epoxy) and oxetane ring are particularly preferable. As the liquid crystal compound having a polymerizable functional group, those generally used can be used, and specific examples thereof are not particularly limited, but are described in paragraph [0172] of JP-A-2005-15473. To [0314] and the compounds shown below.

  In the polymerizable liquid crystal composition of the present invention, a liquid crystal compound other than the above-described polymerizable liquid crystal compound of the present invention, for example, a liquid crystal single molecule having an ethylenically unsaturated bond other than the polymerizable liquid crystal compound of the present invention exemplified above. In addition to the monomer, a monomer having an optically active group and a compound having an ethylenically unsaturated bond such as (meth) acrylic acid ester can also be added. However, among these, the addition amount of the compound having an ethylenically unsaturated bond means that the heat resistance of the polymer prepared using the polymerizable liquid crystal composition is maintained, and the polymerizable liquid crystal compound of the present invention and the liquid crystal 30 mass parts or less with respect to 100 mass parts of total amounts of a compound, Especially 10 mass parts or less are preferable.

  For the purpose of improving the polymerization reactivity, a polymerization initiator such as a radical polymerization initiator and a cationic polymerization initiator can be added to the polymerizable liquid crystal composition of the present invention. When adding these, it is preferable that the addition amount is 40 mass parts or less with respect to 100 mass parts of total amounts of the polymeric liquid crystal compound of this invention, and the said liquid crystal compound, and it is 15 mass parts or less. More preferably, 10 parts by mass or less is even more preferable, and the range of 0.5 to 8 parts by mass is most preferable.

  As the polymerization initiator, it is preferable to use a radical polymerization initiator and a cationic polymerization initiator in combination. It is preferable that both are within the range of said preferable addition amount as a total amount. The ratio of the radical polymerization initiator to the cationic polymerization initiator (the former: the latter, based on mass) is preferably in the range of 10: 1 to 1:10.

As the radical polymerization initiator, conventionally known compounds can be used. For example, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1,1-di (t-butylperoxy) -3, Peroxides such as 3,5-trimethylcyclohexane, 4,4-di (t-butyl-peroxy) butyl valerate, dicumyl peroxide; azo compounds such as 2,2′-azobisisobutyronitrile Benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane, benzyl, benzyldimethyl ketal, 1-benzyl-1-dimethylamino-1- (4′-morpholinobenzoyl) propane, 2-morpholyl-2- (4 '-Methylmercapto) benzoylpropane, thioxanthone, 1-chloro-4- Lopoxythioxanthone, isopropylthioxanthone, diethylthioxanthone, ethyl anthraquinone, 4-benzoyl-4'-methyldiphenyl sulfide, tetramethyltyradium disulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4 '-Isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyldichloromethane, methyl benzoylformate, 1,7-bis (9'-acridinyl) heptane, 9-n-butyl-3,6-bis (2 '-Morpholinoisobutyroyl) carbazole, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, p-methoxyphenyl-2,4-bis (trichloromethyl) -s- Liazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-butoxystyryl) -s-triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9, 10-dimethylbenzphenazine, benzophenone / Michler's ketone, hexaarylbiimidazole / mercaptobenzimidazole, thioxanthone / amine, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and JP 2000-80068, JP 2001-233842, JP-A-2005-97 141, Japanese Patent Publication No. 2006-516246, Japanese Patent No. 3860170, Japanese Patent No. 3798008, and International Publication No. 2006/018933. Among these, the compound represented by the following general formula (A) is preferable.

（式中、Ｘ⁷¹は、ハロゲン原子又はアルキル基を表し、Ｘ⁷²は、水素原子、ハロゲン原子、アルキル基又は下記一般式（Ｂ）で表される置換基を表し、Ｒ⁷¹、Ｒ⁷²及びＲ⁷³は、各々独立に、Ｒ、ＯＲ、ＣＯＲ、ＳＲ、ＣＯＮＲＲ’又はＣＮを表し、Ｒ及びＲ’は、アルキル基、アリール基、アリールアルキル基又は複素環基を表し、これらはハロゲン原子及び／又は複素環基で置換されていてもよく、これらのうちアルキル基及びアリールアルキル基のアルキレン部分は、不飽和結合、エーテル結合、チオエーテル結合、エステル結合により中断されていてもよく、また、Ｒ及びＲ’は一緒になって環を形成していてもよく、ｇは０〜４の整数であり、ｇが２以上の時、複数のＸ⁷¹は異なる基でもよい。）

Wherein X ⁷¹ represents a halogen atom or an alkyl group, X ⁷² represents a hydrogen atom, a halogen atom, an alkyl group or a substituent represented by the following general formula (B), R ⁷¹ , R ⁷² and R ⁷³ each independently represents R, OR, COR, SR, CONRR ′ or CN, and R and R ′ represent an alkyl group, an aryl group, an arylalkyl group or a heterocyclic group, and these represent a halogen atom and May be substituted with a heterocyclic group, and among these, the alkylene part of the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, an ether bond, a thioether bond, an ester bond, and R And R ′ may be combined to form a ring, g is an integer of 0 to 4, and when g is 2 or more, the plurality of X ⁷¹ may be different groups.)

（式中、環Ｍはシクロアルカン環、芳香環又は複素環を表し、Ｘ⁷³はハロゲン原子又はアルキル基を表し、Ｙ⁷¹は酸素原子、硫黄原子又はセレン原子を表し、Ｚ⁷¹は炭素原子数１〜５のアルキレン基を表し、ｈは０〜４の整数であり、ｈが２以上の時、複数のＸ⁷³は異なる基でもよい。）

(In the formula, ring M represents a cycloalkane ring, an aromatic ring or a heterocyclic ring, X ⁷³ represents a halogen atom or an alkyl group, Y ⁷¹ represents an oxygen atom, a sulfur atom or a selenium atom, and Z ⁷¹ represents the number of carbon atoms. 1 represents an alkylene group of 1 to 5, h is an integer of 0 to 4, and when h is 2 or more, the plurality of X ⁷³ may be different groups.

The cationic polymerization initiator may be any compound that can generate an acid upon irradiation with energy rays, but is preferably an onium salt that releases a Lewis acid upon irradiation with energy rays. It is a double salt or a derivative thereof. Typical examples of such compounds include salts of cations and anions represented by the general formula [M] ^{m +} [N] ^m− .

Here, the cation [M] ^{m +} is preferably onium, and the structure can be represented by, for example, the general formula [(R ³⁰ ) _f Q] ^{m +} .

Here, R ³⁰ is an organic group having 1 to 60 carbon atoms and optionally containing any number of atoms other than carbon atoms. f is an integer of 1-5. The f R ^{30 s} are independent and may be the same or different. Further, at least one is preferably an organic group as described above having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [M] ^{m +} is q, it is necessary that the relationship m = f−q holds (where N = N is treated as valence 0).

The anion [N] ^m− is preferably a halide complex, and the structure thereof can be represented by, for example, the general formula [LT _g ] ^m− .

Here, L is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V , Cr, Mn, Co and the like. T is a halogen atom. g is an integer of 3-7. Further, when the valence of L in the anion [N] ^m− is p, it is necessary that the relationship m = gp is established.

Specific examples of the anion [N] ^m- include, for example, a halogen anion such as a chlorine anion, a bromine anion, an iodine anion, a fluorine anion; a perchlorate anion, a chlorate anion, and a thiocyanate. Inorganic anions such as anion, hexafluorophosphate anion, antimony hexafluoride anion, arsenic hexafluoride anion, boron tetrafluoride anion; methanesulfonate ion, fluorosulfonate ion, benzenesulfone Acid anion, toluenesulfonic acid anion, 1-naphthylsulfonic acid anion, 2-naphthylsulfonic acid anion, trifluoromethanesulfonic acid anion, pentafluoroethanesulfonic acid anion, heptafluoropropanesulfonic acid anion, nona Fluorobutane sulfonate anion, undecafluoropentane sulfonate anion , Tridecafluorohexanesulfonic acid anion, pentadecafluoroheptanesulfonic acid anion, heptadecafluorooctanesulfonic acid ion, perfluoro-4-ethylcyclohexanesulfonic acid ion, N-alkyl (or aryl) diphenylamine-4-sulfone Acid anion, 2-amino-4-methyl-5-chlorobenzenesulfonic acid anion, 2-amino-5-nitrobenzenesulfonic acid anion, sulfonic acid anion described in JP-A-2004-53799, camphorsulfone Acid anion, fluorobenzenesulfonic acid anion, difluorobenzenesulfonic acid anion, trifluorobenzenesulfonic acid anion, tetrafluorobenzenesulfonic acid anion, pentafluorobenzenesulfonic acid anion, Organic sulfonate anions of: octyl phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, nonylphenyl phosphate anion, 2,2′-methylenebis (4,6-di- Organophosphate anions such as t-butylphenyl) phosphonic acid anion, bis (trifluoromethanesulfone) imide ion, bis (pentafluoroethanesulfone) imide ion, bis (heptafluoropropanesulfone) imide ion, bis (nonafluorobutanesulfone) ) Imido ion, bis (undecafluoropentanesulfone) imide ion, bis (pentadecafluoroheptanesulfone) imide ion, bis (tridecafluorohexanesulfone) imide ion, bis (heptadecafluorooctanesulfonimide) Organic fluorosulfonimide ions such as ON, (trifluoromethanesulfone) (nonafluorobutanesulfone) imide ion, (methanesulfone) (trifluoromethanesulfone) imide ion, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide anion Tetrakis (pentafluorophenyl) borate anion, tetrakis (4-fluorophenyl) borate ion, tetraphenylborate ion, borate anion described in JP-A-2008-81470, JP-A-2007-112854 Borate anion described in JP-A-6-184170, borate anion described in JP-A-6-184170, borate anion described in JP-T-2002-526391, international application PCT / JP2008 / 0669562 In the issue statement Tetraarylborate anions such as described borate anions, various aliphatic or aromatic carboxylate anions, organic sulfonylmethide ions such as tris (trifluoromethanesulfonyl) methide, tris (methanesulfonyl) methide; In addition, alkyl sulfonate ions, fluoro-substituted alkyl sulfonate ions, alkyl sulfonimides, fluoro-substituted alkyl sulfonimides substituted with acryloyloxy groups and methacryloyloxy groups, and fatty acids such as norbornyl groups and adamantyl groups And those substituted with a cyclic alkyl group. In addition, quencher anions that have the function of deexciting (quenching) active molecules in the excited state, and ferrocenes having an anionic group such as a carboxyl group, phosphonic acid group, or sulfonic acid group on the cyclopentadienyl ring. Metallocene compound anions such as luteocene can also be used as necessary.

  In the present invention, among these onium salts, it is particularly effective to use the following aromatic onium salts (a) to (c). Among these, one of them can be used alone, or two or more can be mixed and used.

  (I) Aryl diazonium salts such as phenyldiazonium hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate

  (B) Diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, di (4-methylphenyl) iodonium hexafluorophosphate, di (4-tert-butylphenyl) iodonium hexafluorophosphate, tricumyliodonium tetrakis (pentafluoro) Diaryl iodonium salts such as phenyl) borate

(C) Triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, 4, 4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4,4′-bis [di ( β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis [di (β-hydroxyethoxy) phenylsulfonio] pheny Sulfide-bis-hexafluorophosphate, 4- [4 ′-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4 ′-(benzoyl) phenylthio] phenyl-di- Triarylsulfonium salts such as (4-fluorophenyl) sulfonium hexafluorophosphate, 4- (2-chloro-4-benzoylphenylthio) phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, and diphenyl-4- Mixture of thiophenoxyphenylsulfonium hexafluoroantimonate and 4,4'-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate

Other preferable examples include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Iron-arene complexes such as hexafluorophosphate, aluminum complexes such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and silanols such as triphenylsilanol The mixture of these can also be mentioned.

  Among these, from the viewpoint of practical use and photosensitivity, it is preferable to use an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex.

  An optically active compound can also be added to the polymerizable liquid crystal composition of the present invention for the purpose of obtaining a polymer having a helical structure of a liquid crystal skeleton inside. By adding the optically active compound, the polymerizable liquid crystal composition of the present invention exhibits a cholesteric liquid crystal phase. Examples of the optically active compound include the following compounds. The optically active compound has a polymerizable functional group such as (meth) acryloyloxy group, oxirane ring (epoxy), oxetane ring, styrene group, vinyl group, vinyl ether group, vinyl ketone group, maleimide group, phenylmaleimide group, etc. Is preferred. When the optically active compound is added, the addition amount is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound of the present invention and the liquid crystal compound. More preferably, it is 25 parts by mass.

  When the polymerizable liquid crystal compound of the present invention is used for a polarizing film or a raw material for an alignment film, or for printing inks, paints, protective films, etc., the polymerizable liquid crystal composition of the present invention includes a metal , Metal complexes, dyes, pigments, pigments, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, titanium oxide It is also possible to add optional components such as metal oxides such as metal oxides, polymerization inhibitors, storage stabilizers, photosensitizers, crosslinking agents, liquid crystal alignment aids, fine particles such as inorganic and organic substances, and functional compounds such as polymers. it can.

  The above-mentioned surfactant has an excluded volume effect distributed on the air interface side, and has an effect of facilitating application of the polymerizable liquid crystal composition to a support substrate or the like, or controlling the alignment of the liquid crystal phase. Preferred are those obtained, for example, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, amines of lauryl sulfate, alkyl substitution Aromatic sulfonates, alkyl phosphates, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl trimethyl ammonium salts and the like can be mentioned. A preferable use ratio of the surfactant depends on the kind of the surfactant, the component ratio of the composition, and the like, but is 0.001 with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound of the present invention and the liquid crystal compound. It is preferable that it is the range of -5 mass parts, and the inside of the range of 0.01-1 mass part is more preferable.

  The said storage stabilizer can provide the effect which improves the storage stability of a polymeric liquid crystal composition. Examples of the stabilizer that can be used include hydroquinone, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, 2-naphthylamines, 2-hydroxynaphthalenes, and the like. When adding these, it is preferable that it is 1 mass part or less with respect to 100 mass parts of total amounts of the polymeric liquid crystal compound of this invention, and the said liquid crystal compound, and 0.5 mass part or less is especially preferable.

  The antioxidant is not particularly limited and a known compound can be used. Examples thereof include hydroquinone, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, Examples thereof include phenyl phosphite and trialkyl phosphite.

  The ultraviolet absorber is not particularly limited, and a known compound can be used. For example, a salicylic acid ester compound, a benzophenol compound, a benzotriazole compound, a cyanoacrylate compound, a nickel complex compound, or the like It may have absorptive capacity.

  Examples of the photosensitizer include thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, and lupine. When the photosensitizer is added, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound of the present invention and the liquid crystal compound. A range of 0.1 to 3 parts by mass is more preferable.

  The fine particles can be used for adjusting the optical (refractive index) anisotropy (Δn) and increasing the strength of the polymer film. Examples of the material of the fine particles include inorganic substances, organic substances, metals, and the like. To prevent aggregation, the fine particles can preferably have a particle diameter of 0.001 to 0.1 μm, and more preferably 0.001 to 0. .05 μm particle size. A sharp particle size distribution is preferred. The finely divided product can be preferably used within a range of 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound of the present invention and the liquid crystal compound.

Examples of the inorganic material include ceramics, fluorine phlogopite, fluorine tetrasilicon mica, teniolite, fluorine vermiculite, fluorine hectorite, hectorite, saponite, stevensite, montmorillonite, beidellite, kaolinite, frypontite, ZnO, TiO ₂ , _{CeO 2, Al 2 O 3,} Fe 2 O 3, ZrO 2, MgF 2, SiO 2, SrCO 3, Ba (OH) 2, Ca (OH) 2, Ga (OH) 3, Al (OH) 3, Mg (OH) ₂ , Zr (OH) _{4 and the} like. Fine particles such as calcium carbonate needle crystals have optical anisotropy, and the optical anisotropy of the polymer can be adjusted by such fine particles. Examples of the organic substance include carbon nanotubes, fullerenes, dendrimers, polyvinyl alcohol, polymethacrylates, and polyimides.

  The polymer can control the electrical properties and orientation of the polymer film, and a polymer compound soluble in a solvent can be preferably used. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyepoxide, polyester, polyester polyol, and the like.

  In the polymerizable liquid crystal composition of the present invention, optional components other than the polymerizable liquid crystal compound of the present invention described above (excluding the liquid crystal compound, the polymerization initiator, the optically active compound and the solvent described later) are particularly Although there is no limitation, it can be appropriately used as long as the properties of the polymer to be produced are not impaired. Preferably, the total amount of the polymerizable liquid crystal compound of the present invention and the liquid crystal compound is 100% by mass. The total amount of components is 10 parts by mass or less.

  By polymerizing the polymerizable liquid crystal compound of the present invention, an optically anisotropic film formed from a polymer of the polymerizable liquid crystal compound can be obtained. The optically anisotropic film is useful as an optical film. The optically anisotropic film contains, for example, the above-described various additive components such as the polymerizable liquid crystal compound of the present invention and other liquid crystal compounds as necessary, and further dissolves them by adding a solvent as necessary. The polymerizable liquid crystal composition of the present invention is coated on a support, dried, and then supplied with heat or irradiated with ultraviolet rays, etc., to obtain the polymerizable liquid crystal compound of the present invention contained in the polymerizable liquid crystal composition, etc. It can be produced by polymerizing a polymerizable compound and aligning and fixing a polymerizable liquid crystal compound such as the polymerizable liquid crystal compound of the present invention. The optically anisotropic film may be formed on the support, or may be transferred after being formed on the support.

  The support is not particularly limited, but preferred examples thereof include glass plates, polyethylene terephthalate plates, polycarbonate plates, polyimide plates, polyamide plates, polymethyl methacrylate plates, polystyrene plates, polyvinyl chloride plates, cycloolefin polymer plates. , Polytetrafluoroethylene plates, cellulose plates, silicon plates, reflectors, calcite plates and the like. As a method for applying the polymerizable liquid crystal composition of the present invention containing the polymerizable liquid crystal compound of the present invention to the support, known methods can be used, for example, curtain coating method, extrusion coating method, roll coating method. , Spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, blade coating method, gravure coating method, print coating method and the like can be used.

  Examples of the solvent that can be used in the polymerizable liquid crystal composition of the present invention include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; Ether solvents such as ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n-propyl, Ester solvents such as isopropyl acetate, n-butyl acetate, methoxybutyl acetate, methyl lactate, and ethyl lactate; ethylene glycol monomethyl ether, ethylene glycol mono Cellsolve solvents such as tilether, ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, butyl cellosolve; methanol, ethanol, iso- or n-propanol, Alcohol solvents such as iso- or n-butanol, amyl alcohol, t-butyl alcohol, diacetone alcohol, glycerin, monoacetylene, ethylene glycol, triethylene glycol, hexylene glycol; benzene, toluene, xylene, n-butylbenzene Aromatic hydrocarbon solvents such as diethylbenzene, methoxybenzene, 1,2-dimethoxybenzene, mesitylene, tetralin; Aliphatic hydrocarbon solvents such as benzene, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 Paraffin solvents such as (Exxon Chemical Co., Ltd.); Halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, tetrachloroethylene, and methylene chloride; Halogenated aromatic hydrocarbons such as chlorobenzene Solvent; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, γ-butyrolactone, N, N-dimethylformamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, etc. Ketones Cellosolve-based solvents are preferred because a good safety soluble. These solvents can be used as one or a mixture of two or more. Although the usage-amount of a solvent is not restrict | limited in particular, from a viewpoint of making solubility and applicability | paintability favorable, solid content (all components other than a solvent) is 1-60 in the polymeric liquid crystal composition of this invention. It is preferable to use a solvent so that it becomes mass%.

  As a method for aligning the polymerizable liquid crystal compound when preparing an optically anisotropic film containing a polymer of the polymerizable liquid crystal compound of the present invention, for example, a method of performing an alignment treatment on the above-mentioned support in advance. Is mentioned. As a preferred method of performing an alignment treatment on the support, a method of performing a rubbing or the like by providing a liquid crystal alignment layer composed of various polyimide alignment films, polyamide alignment films, polyvinyl alcohol alignment films, etc. on the support. Is mentioned. Examples of the method for aligning the polymerizable liquid crystal compound also include a method of applying a magnetic field or an electric field to the polymerizable liquid crystal compound on the support. In addition, although the film thickness of the said optically anisotropic film is suitably selected according to the use etc. of the molded object which has optical anisotropy, Preferably it selects from the range of 0.01-100 micrometers. Also, when a plurality of optically anisotropic films are used in a stacked manner, the film thickness is preferably within the above range.

  The polymerizable liquid crystal compound of the present invention can be polymerized by a known method using heat or electromagnetic waves. As the polymerization reaction by electromagnetic waves, radical polymerization in which ultraviolet light is irradiated using a photopolymerization initiator is preferable. It is also preferable to perform polymerization while applying a magnetic field or an electric field. The liquid crystal polymer formed on the support may be used as it is, but if necessary, it may be peeled off from the support or transferred to another support.

The polymerizable liquid crystal composition of the present invention is used by polymerizing a polymerizable compound such as the polymerizable liquid crystal compound of the present invention by applying a known method using light, electromagnetic waves or heat. Preferred types of the light are ultraviolet rays, visible rays, infrared rays and the like. You may use electromagnetic waves, such as an electron beam and an X-ray. Usually, ultraviolet rays or visible rays are preferable. A preferable wavelength range is 150 to 500 nm. A more preferable range is 250 to 450 nm, and a most preferable range is 300 to 400 nm. Low light mercury lamps (sterilization lamps, fluorescent chemical lamps, black lights), high pressure discharge lamps (high pressure mercury lamps, metal halide lamps), short arc discharge lamps (super high pressure mercury lamps, xenon lamps, mercury xenon lamps), etc. Among them, a high-pressure mercury lamp and an ultra-high pressure mercury lamp can be preferably used. The polymerizable liquid crystal composition of the present invention may be irradiated with light from the light source as it is, and the specific wavelength (or specific wavelength region) selected by the filter may be irradiated to the polymerizable liquid crystal composition of the present invention. . A preferable irradiation energy density is 10 to 50000 mJ / cm ² , and a more preferable range is 10 to 20000 mJ / cm ² . A preferable illuminance is 0.1 to 5000 mW / cm ² , and a more preferable illuminance is 1 to 2000 mW / cm ² . When the exposure amount is small, polymerization is insufficient, and when the exposure amount is large, rapid curing may cause yellowing or deterioration.

  An optically anisotropic film formed from a polymer obtained by polymerizing the polymerizable liquid crystal composition of the present invention is useful as an optical film. The optical film includes a retardation plate (1/2 wavelength plate, 1/4 wavelength plate, etc.), polarizing element, dichroic polarizing plate, liquid crystal alignment film, antireflection film, selective reflection film, viewing angle compensation film, etc. It can be used for optical compensation. In addition, it can be used as a molded article having optical anisotropy, such as an optical lens such as a liquid crystal lens and a microlens, an information recording material such as a polymer dispersed liquid crystal (PDLC) electronic paper and a digital paper.

  EXAMPLES Hereinafter, although an Example etc. are shown and this invention is demonstrated further in detail, this invention is not limited by these Examples.

In the following Examples 1 to 10, the polymerizable liquid crystal compound No. 1 of the present invention. 1-No. 10 was synthesized.
In the following Examples 11-20 and Comparative Examples 1-2, an optical film was prepared by preparing a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of the present invention or a polymerizable liquid crystal compound for comparison and a polymerization initiator. In Evaluation Example 1, the heat resistance of these optical films was evaluated. In Examples 21 to 24, the polymerizable liquid crystal composition of the present invention containing an optically active compound was prepared to prepare an optical film. In Evaluation Example 2, the alignment uniformity and selective reflection of these optical films were prepared. Was evaluated.

Example 1 Compound No. 1 Synthesis of 1 To 2.42 g (3.74 mmol) of phenol compound 1 shown below and 1.09 g (5.61 mmol) of 4- (2-oxiranylmethoxy) benzoic acid dissolved in 22 ml of tetrahydrofuran (THF) Then, 0.23 g (1.87 mmol) of 4-dimethylaminopyridine (DMAP) and 0.85 g (6.74 mmol) of diisopropylcarbodiimide were added under ice cooling, and the mixture was stirred for 2.5 hours under ice cooling. After adding 80 ml of toluene to the reaction solution and filtering the precipitate, the solvent was distilled off. 80 ml of methanol was added to the residue and ultrasonic irradiation was performed for 1 hour, methanol was removed, 80 ml of methanol was added again, and ultrasonic irradiation was performed for 30 minutes. After removing methanol, the residue was dissolved in 20 ml of chloroform, and the solvent was distilled off. The residue was subjected to silica gel column chromatography with a flow of ethyl acetate / n-hexane = 1/3 (v / v), the obtained low polarity component was allowed to stand overnight, and the resulting crystal was used with methanol. Washed and dried under reduced pressure at 40 ° C. for 1 hour to obtain 0.29 g (yield 9.4%) of a colorless solid. The obtained colorless solid was analyzed to obtain the target compound No. 1 was confirmed. The analysis results are shown below.

[result of analysis]
TG: 97.0 ° C. (peak top), 399.0 ° C. (mass decrease start point)
IR (neat) n _max : 2935, 1731, 1626, 1604, 1509, 1473, 1390, 1259, 1191, 1168, 1148, 1065, 1027, 764, 745 cm ^−1
1 H NMR (400 MHz, CDCl ₃ ): d 8.83 (s, 1H), 8.70 (s, 1H), 8.24 (dd, J = 8.5, 1.2 Hz, 1H), 8.21 (D, J = 8.5 Hz, 2H), 8.16 (dd, J = 8.5, 1.2 Hz, 1H), 8.08 (d, J = 8.5 Hz, 1H), 7.95 ( d, J = 8.5 Hz, 1H), 7.89 (d, J = 8.5 Hz, 1H), 7.82-7.76 (m, 2H), 7.47 (dd, J = 8.5) , 1.8 Hz, 1H), 7.30-7.15 (m, 5H), 7.05 (d, J = 9.1 Hz, 2H), 6.40 (dd, J = 17.7, 1. 2 Hz, 1H), 6.13 (dd, J = 17.7, 10.4 Hz, 1H), 5.81 (d, J = 10.4 Hz, 1H), 4.37 (dd, J = 11.0) , 3.0Hz, 1H), 4.19 (t, J = 6.7 Hz, 2H), 4.12 (t, J = 6.1 Hz, 2H), 4.05 (dd, J = 11.0, 6.1 Hz, 1H) ), 3.44-3.39 (m, 1H), 2.96 (t, J = 4.3 Hz, 1H), 2.81 (dd, J = 4.9, 2.4 Hz, 1H), 2 .64 (t, J = 7.6 Hz, 2H), 1.94-1.45 (m, 10H), 0.95 (t, J = 7.3 Hz, 3H).

  The obtained compound was measured from 25 ° C. to 180 ° C. at a temperature rising rate of 5 ° C./min under a nitrogen atmosphere (50 ml / min) with a differential scanning calorimeter (DSC7; manufactured by Perkin Elmer), The following thermal transition behavior was confirmed. Furthermore, the type of liquid crystal phase was identified by raising the temperature of a sample sandwiched between glass plates on a hot stage and observing the optical structure with a polarizing microscope.

Example 2 Compound No. Synthesis of Compound No. 2 Compound No. 2 was prepared according to the method of Example 1 using starting materials corresponding to 2 was obtained. The analysis results are shown below.

[result of analysis]
TG: 123.3 ° C. (peak top), 127.5 ° C. (peak top), 399.1 ° C. (mass reduction start point)
DSC: 123.5 ° C. (peak top), 128.1 ° C. (peak top), ΔH = + 41.0 [kJ / mol]
IR (neat) n _max : 2942, 2872, 1730, 1626, 1604, 1509, 1473, 1389, 1256, 1191, 1167, 1148, 1065, 11009, 764, 742 cm ^−1
1 H NMR (400 MHz, CDCl ₃ ): d 8.83 (s, 1H), 8.71 (s, 1H), 8.24 (dd, J = 8.5, 1.8 Hz, 1H), 8. 20 (d, J = 9.1 Hz, 2H), 8.16 (dd, J = 8.5, 1.8 Hz, 1H), 8.08 (d, J = 9.1 Hz, 1H), 7.95 (D, J = 9.1 Hz, 1H), 7.89 (d, J = 8.5 Hz, 1H), 7.82-7.78 (m, 3H), 7.47 (dd, J = 9. 1, 2.4 Hz, 1H), 7.30-7.15 (m, 4H), 7.01 (d, J = 9.1 Hz, 2H), 6.41 (dd, J = 17.7, 1 .2 Hz, 1 H), 6.13 (dd, J = 17.1, 10.4 Hz, 1 H), 5.82 (dd, J = 10.4, 1.2 Hz, 1 H), 4.19 (t, J = 6.7 Hz, H), 4.19-4.08 (m, 4H), 3.05-2.99 (m, 1H), 2.81 (t, J = 4.6 Hz, 1H), 2.64 (t, J = 7.3 Hz, 2H), 2.54 (dd, J = 4.9, 3.0 Hz, 1H), 2.09-1.45 (m, 14H), 0.95 (t, J = 7) .3Hz, 3H).

Example 3 Compound No. Synthesis of compound No. 3 Compound No. 3 was prepared according to the method of Example 1 using starting materials corresponding to 3 was obtained. The analysis results are shown below.

[result of analysis]
TG: 108.0 ° C. (peak top), 111.9 ° C. (peak top), 392.5 ° C. (mass reduction start point)
DSC: 107.4 ° C. (peak top), 111.3 ° C. (peak top), ΔH = + 38.2 [kJ / mol]
IR (neat) n _max : 2935, 2851, 1730, 1625, 1604, 1509, 1473, 1390, 1255, 1191, 1167, 1146, 1064, 1009 cm ^−1
1 H NMR (400 MHz, CDCl ₃ ): d 8.83 (s, 1H), 8.71 (s, 1H), 8.24 (dd, J = 8.5, 1.8 Hz, 1H), 8.20 (D, J = 8.5 Hz, 2H), 8.16 (dd, J = 8.5, 1.8 Hz, 1H), 8.08 (d, J = 9.1 Hz, 1H), 7.96 ( d, J = 9.1 Hz, 1H), 7.90 (d, J = 9.1 Hz, 1H), 7.81 (d, J = 8.5 Hz, 1H), 7.79 (d, J = 2) .4 Hz, 1H), 7.48 (dd, J = 9.1, 2.4 Hz, 1H), 7.31-7.15 (m, 5H), 7.00 (d, J = 8.5 Hz, 2H), 6.41 (dd, J = 17.1, 1.2 Hz, 1H), 6.13 (dd, J = 17.7, 10.4 Hz, 1H), 5.82 (dd, J = 10 .4,1.8H z, 1H), 4.20 (t, J = 6.7 Hz, 2H), 4.13 (t, J = 6.7 Hz, 2H), 4.07 (t, J = 6.7 Hz, 2H), 2.94-2.89 (m, 1H), 2.76 (t, J = 4.9 Hz, 1H), 2.64 (t, J = 7.9 Hz, 2H), 2.48 (dd, J = 4.9, 3.0 Hz, 1H), 1.93-1.42 (m, 24H), 0.95 (t, J = 7.3 Hz, 3H)

Example 4 Compound No. Synthesis of Compound No. 4 Compound No. 4 was prepared according to the method of Example 1 using starting materials corresponding to 4 was obtained. The analysis results are shown below.

[result of analysis]
TG: 104.9 ° C. (peak top), 114.7 ° C. (peak top), 394.5 ° C. (mass reduction start point)
DSC: 94.2 ° C. (peak top), 103.0 ° C. (peak top), 113.6 ° C. (peak top)
IR (neat) n _max : 2946, 2862, 1730, 1625, 1604, 1509, 1473, 1390, 1270, 1255, 1191, 1167, 1148, 1064, 1009, 764, 745 cm ^−1
1 H NMR (400 MHz, CDCl ₃ ): d 8.83 (s, 1H), 8.71 (s, 1H), 8.27-8.13 (m, 4H), 8.08 (d, J = 9 .1 Hz, 1H), 7.96 (d, J = 9.1 Hz, 1H), 7.90 (d, J = 9.1 Hz, 1H), 7.84-7.77 (m, 2H), 7 .48 (dd, J = 9.1, 2.4 Hz, 1H), 7.31-7.15 (m, 5H), 7.01 (d, J = 9.1 Hz, 2H), 6.41 ( dd, J = 17.4, 1.5 Hz, 1H), 6.13 (dd, J = 17.1, 10.4 Hz, 1H), 5.82 (dd, J = 10.4, 1.2 Hz, 1H), 4.19 (t, J = 6.7 Hz, 2H), 4.17-4.08 (m, 4H), 3.78 (dd, J = 11.3, 2.7 Hz, 1H), 3.66-3. 55 (m, 2H), 3.40 (dd, J = 11.3, 5.8 Hz, 1H), 2.84-2.79 (m, 1H), 2.68-2.59 (m, 3H) ), 1.99-1.45 (m, 14H), 0.95 (t, J = 7.3 Hz, 3H)

Example 5 Compound no. Synthesis of Compound No. 5 Compound No. 5 was prepared according to the method of Example 1 using starting materials corresponding to 5 was obtained. The analysis results are shown below.

[result of analysis]
TG: 85.7 ° C. (peak top), 97.5 ° C. (peak top), 400.9 ° C. (mass reduction start point)
DSC: 84.7 ° C. (peak top), 87.1 ° C. (peak top), 96.9 ° C. (peak top)
IR (neat) n _max : 2946, 2872, 1731, 1625, 1604, 1509, 1473, 1390, 1256, 1191, 1167, 1148, 1064 cm ^−1
1 H NMR (400 MHz, CDCl ₃ ): d 8.83 (s, 1H), 8.71 (s, 1H), 8.24 (dd, J = 8.5, 1.8 Hz, 1H), 8. 19 (d, J = 9.1 Hz, 2H), 8.16 (dd, J = 8.5, 1.8 Hz, 1H), 8.08 (d, J = 9.1 Hz, 1H), 7.95 (D, J = 8.5 Hz, 1H), 7.89 (d, J = 9.1 Hz, 1H), 7.84-7.78 (m, 2H), 7.47 (dd, J = 8. 5, 2.1 Hz, 1H), 7.31-7.15 (m, 5H), 7.00 (d, J = 8.5 Hz, 2H), 6.40 (dd, J = 17.1, 1) .2 Hz, 1 H), 6.13 (dd, J = 17.4, 10.7 Hz, 1 H), 5.82 (dd, J = 10.4, 1.2 Hz, 1 H), 4.19 (t, J = 6.7 Hz, H), 3.74 (dd, J = 11.6, 3.0 Hz, 1H), 3.58-3.47 (m, 2H), 3.38 (dd, J = 11.6, 6.1 Hz) , 1H), 3.18-3.14 (m, 1H), 2.81 (t, J = 4.6 Hz, 1H), 2.67-2.58 (m, 3H), 1.94-1 .80 (m, 4H), 1.80-1.43 (m, 14H), 0.95 (t, J = 7.6 Hz, 3H)

Example 6 Compound no. Synthesis of Compound No. 6 Compound No. 6 was prepared according to the method of Example 1 using starting materials corresponding to 6 was obtained. The analysis results are shown below.

[result of analysis]
TG: 121.8 ° C. (peak top), 126.1 ° C. (peak top), 182.7 ° C. (peak top), 185.9 ° C. (peak top), 404.2 ° C. (mass reduction starting point)
DSC: 121.3 ° C. (peak top), 124.5 ° C. (peak top; ΔH = + 10.1 [kJ / mol]), 181.6 ° C. (peak top), 184.4 ° C. (peak top; ΔH = +43.3 [kJ / mol])
IR (neat) n _max : 2935, 2872, 1729, 1626, 1606, 1509, 1473, 1265, 1191, 1167, 1148, 1067, 1033, 764, 745 cm ^−1
1 H NMR (400 MHz, CDCl ₃ ): d 8.83 (s, 1H), 8.71 (s,
1H), 8.38-8.19 (m, 3H), 8.16 (dd, J = 8.5, 1.8 Hz, 1H), 8.09 (d, J = 9.1 Hz, 1H), 7.93 (d, J = 8.5 Hz, 1H), 7.90 (d, J = 9.1 Hz, 1H), 7.81 (d, J = 8.5 Hz, 1H), 7.80 (s) , 2H), 7.48 (dd, J = 8.8, 2.1 Hz, 1H), 7.30-7.15 (m, 4H), 7.06 (d, J = 9.1 Hz, 2H) 6.41 (dd, J = 17.1, 1.2 Hz, 1H), 6.13 (dd, J = 17.4, 10.7 Hz, 1H), 5.82 (dd, J = 10.4). , 1.2 Hz, 1H), 4.66 (d, J = 6.1 Hz, 2H), 4.51 (d, J = 6.1 Hz, 2H), 4.19 (t, J = 6.7 Hz, 2H), 2.64 (t, J = 7 6 Hz, 2H), 1.90 (tt, J = 7.3, 6.7 Hz, 2H), 1.79-1.44 (m, 8H), 1.49 (s, 3H), 0.95 ( t, J = 7.3 Hz, 3H)

Example 7 Compound no. Synthesis of Compound No. 7 Compound No. 7 was prepared according to the method of Example 1 using starting materials corresponding to 7 was obtained. The analysis results are shown below.

[result of analysis]
TG: 93.0 ° C. (peak top), 99.4 ° C. (peak top), 405.3 ° C. (mass reduction start point)
DSC: 93.0 ° C. (peak top), 99.1 ° C. (peak top); ΔH = + 46.2 [kJ / mol]
IR (neat) n _max : 2939, 2869, 1731, 1626, 1604, 1509, 1472, 1273, 1255, 1191, 1166, 1144, 1063, 1008 cm ^−1
1 H NMR (400 MHz, CDCl ₃ ): d 8.83 (s, 1H), 8.71 (s, 1H), 8.24 (dd, J = 8.5, 1.2 Hz, 1H), 8.20 (D, J = 8.5 Hz, 2H), 8.16 (dd, J = 8.5, 1.8 Hz, 1H), 8.08 (d, J = 9.1 Hz, 1H), 7.96 ( d, J = 8.5 Hz, 1H), 7.90 (d, J = 9.1 Hz, 1H), 7.83-7.78 (m, 2H), 7.48 (dd, J = 9.1). , 2.4 Hz, 1H), 7.31-7.17 (m, 5H), 7.00 (d, J = 9.1 Hz, 2H), 6.41 (dd, J = 17.1, 1.. 8 Hz, 1 H), 6.13 (dd, J = 17.1, 11.0 Hz, 1 H), 5.82 (dd, J = 10.4, 1.8 Hz, 1 H), 4.47 (d, J = 5.5 Hz, 2 H), 4.39 (d, J = 6.1 Hz, 2H), 4.20 (t, J = 6.1 Hz, 2H), 4.13 (t, J = 6.7 Hz, 2H), 4. 11 (t, J = 6.7 Hz, 2H), 3.56 (t, J = 6.1 Hz, 4H), 2.64 (t, J = 7.6 Hz, 2H), 1.98-1.45 (M, 16H), 0.95 (t, J = 7.3 Hz, 3H), 0.90 (t, J = 7.3 Hz, 3H)

Example 8 Compound No. Synthesis of Compound No. 8 Compound No. 8 was prepared according to the method of Example 1 using starting materials corresponding to 8 was obtained. The analysis results are shown below.

[result of analysis]
TG: 93.5 ° C. (peak top), 99.0 ° C. (peak top), 223.5 ° C. (peak top), 408.0 ° C. (mass reduction start point)
DSC: 93.7 ° C. (peak top), 98.4 ° C. (peak top); ΔH = + 40.3 [kJ / mol]
IR (neat) n _max : 2935, 2872, 1731, 1625, 1604, 1509, 1472, 1256, 1191, 1167, 1148, 1063 cm ^−1
1 H NMR (400 MHz, CDCl ₃ ): d 8.83 (s, 1H), 8.71 (s, 1H), 8.24 (dd, J = 8.5, 1.8 Hz, 1H), 8. 20 (d, J = 9.1 Hz, 2H), 8.16 (dd, J = 8.5, 1.8 Hz, 1H), 8.08 (d, J = 9.1 Hz, 1H), 7.96 (D, J = 8.5 Hz, 1H), 7.90 (d, J = 9.1 Hz, 1H), 7.83-7.77 (m, 2H), 7.48 (dd, J = 9. 1, 2.4 Hz, 1H), 7.29 (d, J = 8.5 Hz, 1H), 7.25-7.17 (m, 4H), 7.00 (d, J = 9.1 Hz, 2H) ), 6.41 (dd, J = 17.4, 1.5 Hz, 1H), 6.13 (dd, J = 17.7, 10.4 Hz, 1H), 5.82 (dd, J = 10. 4, 1.2Hz, H), 4.46 (d, J = 6.1 Hz, 2H), 4.39 (d, J = 5.5 Hz, 2H), 4.20 (t, J = 6.4 Hz, 2H), 4. 13 (t, J = 6.4 Hz, 2H), 4.07 (t, J = 6.7 Hz, 2H), 3.54 (s, 2H), 3.49 (t, J = 6.4 Hz, 2H) ), 2.64 (t, J = 7.6 Hz, 2H), 1.90-1.42 (m, 20H), 0.95 (t, J = 7.3 Hz, 3H), 0.89 (t , J = 7.6 Hz, 3H)

Example 9 Compound No. Synthesis of Compound No. 9 Compound No. 9 was prepared according to the method of Example 1 using starting materials corresponding to 9 was obtained. The analysis results are shown below.

[result of analysis]
TG: 97.1 ° C. (peak top), 102.9 ° C. (peak top), 408.9 ° C. (mass reduction start point)
DSC: 96.3 ° C. (peak top), 101.6 ° C. (peak top); ΔH = + 35.78 [kJ / mol]
IR (neat) n _max : 2939, 2862, 1731, 1625, 1604, 1509, 1473, 1388, 1256, 1191, 1167, 1146, 1064 cm ^−1
1 H NMR (400 MHz, CDCl ₃ ): d 8.83 (s, 1H), 8.70 (s, 1H), 8.24 (dd, J = 8.5, 1.8 Hz, 1H), 8. 19 (d, J = 8.5 Hz, 2H), 8.16 (dd, J = 8.5, 1.8 Hz, 1H), 8.08 (d, J = 9.1 Hz, 1H), 7.95 (D, J = 9.1 Hz, 1H), 7.89 (d, J = 9.1 Hz, 1H), 7.83-7.77 (m, 2H), 7.47 (dd, J = 8. 8, 2.1 Hz, 1H), 7.29 (d, J = 9.1 Hz, 1H), 7.26-7.15 (m, 4H), 7.00 (d, J = 9.1 Hz, 2H) ), 6.40 (dd, J = 17.4, 1.5 Hz, 1H), 6.12 (dd, J = 17.1, 10.4 Hz, 1H), 5.81 (dd, J = 10. 4, 1.2Hz, H), 4.52 (d, J = 5.5 Hz, 2H), 4.36 (d, J = 5.5 Hz, 2H), 4.19 (t, J = 6.7 Hz, 2H), 4. 12 (t, J = 6.4 Hz, 2H), 4.07 (t, J = 6.4 Hz, 2H), 4.07 (t, J = 6.4 Hz, 2H), 3.49 (t, J = 6.7 Hz, 2H), 3.48 (s, 2H), 2.64 (t, J = 7.6 Hz, 2H), 1.94-1.41 (m, 18H), 1.32 (s) , 3H), 0.95 (t, J = 7.3 Hz, 3H)

Example 10: Compound no. Synthesis of Compound No. 10 Compound No. 10 was prepared according to the method of Example 1 using starting materials corresponding to 10 was obtained. The analysis results are shown below.

[result of analysis]
TG: 59.1 ° C. (peak top), 65.3 ° C. (peak top), 118.7 ° C. (peak top), 413.4 ° C. (weight loss starting point)
DSC: 52.0 ° C. (peak top), 57.7 ° C. (peak top); ΔH = + 22.60 [kJ / mol], 116.0 ° C. (peak top); ΔH = + 1.22 [kJ / mol]
IR (neat) n _max : 2937, 2862, 1731, 1626, 1509, 1473, 1271, 1191, 1170, 1148, 1069, 980 cm ⁻¹ .
¹ H NMR (400 MHz, CDCl ₃ ): d 8.83 (s, 1H), 8.71 (s, 1H), 8.25 (dd, J = 8.5, 1.8 Hz, 1H), 8 6.16 (dd, J = 8.5, 1.8 Hz, 1H), 8.09 (d, J = 9.1 Hz, 1H), 7.96 (d, J = 8.5 Hz, 1H), 7. 93-7.85 (m, 2H), 7.81 (d, J = 9.1 Hz, 1H), 7.78 (d, J = 1.8 Hz, 1H), 7.70 (d, J = 1) .8 Hz, 1H), 7.47 (dd, J = 8.8, 2.1 Hz, 1H), 7.29 (d, J = 9.1 Hz, 1H), 7.27-7.15 (m, 4H), 6.96 (d, J = 8.5 Hz, 1H), 6.41 (dd, J = 17.1, 1.2 Hz, 1H), 6.13 (dd, J = 17.1, 10 .4Hz, H), 5.82 (dd, J = 10.4, 1.8 Hz, 1H), 4.46 (d, J = 5.5 Hz, 2H), 4.44 (d, J = 4.9 Hz, 2H) ), 4.39 (d, J = 5.5 Hz, 2H), 4.37 (d, J = 5.5 Hz, 2H), 4.19 (t, J = 6.7 Hz, 2H), 4.16. -4.05 (m, 6H), 3.53 (s, 2H), 3.52 (s, 2H), 3.51-3.44 (m, 4H), 2.64 (t, J = 7 .6 Hz, 2H), 1.94-1.84 (m, 6H), 1.78-1.40 (m, 24H), 0.95 (t, J = 7.3 Hz, 3H), 0.89 (T, J = 7.3 Hz, 3H), 0.88 (t, J = 7.3 Hz, 3H).

[Examples 11 to 20 and Comparative Examples 1 to 3]
[1] Polymerizable liquid crystal composition No. 1-No. 10 and comparative polymerizable liquid crystal composition no. 1-No. Preparation of Compound No. 3 which is the polymerizable liquid crystal compound of the present invention obtained in Examples 1-10. 1-No. 10 and the following comparative compound no. 1-No. 3 is mixed with 0.2 g of cyclopentanone and 0.8 g of cyclopentanone to prepare a cyclopentanone solution, and 0.03 g of a radical polymerization initiator (N-1919; manufactured by ADEKA Corporation) and 6 phenyl fluoride of diphenyliodonium. After 0.03 g of phosphorylated phosphate was added and completely dissolved, filtration treatment was performed with a 0.45 μm filter to obtain a polymerizable liquid crystal composition.

[2] Application to substrate and curing The polymerizable liquid crystal composition solution prepared in [1] above was applied on a glass substrate on which polyimide was applied and rubbed with a spin coater (1200 rpm × 10 seconds). The coating was performed by adjusting the rotation speed and time of the spin coater so that the film thickness was about 1.0 μm. After coating, it is dried at 100 ° C. for 3 minutes using a hot plate, then cooled at room temperature for 1 minute, and then irradiated with light corresponding to 300 mJ / cm ² using a high-pressure mercury lamp to cure the coating film, An optical film was obtained.

[Evaluation Example 1]
About the optical film obtained in the said Examples 15, 18-20, and Comparative Examples 1-3, heat resistance evaluation was implemented as follows. These results are shown in [Table 1].

<Heat resistance evaluation method>
The obtained optical film was heated in an oven at 230 ° C. for 30 minutes, and the retardation (R) before and after heating was measured. Before and after heating, the retardation (R) was measured, and the ratio of R after heating when the value of R before heating was 100% was calculated to evaluate heat resistance.
R was measured at a room temperature of 25 ° C. and a wavelength of 546 nm based on the Senarmon method using a polarizing microscope.

  From the above results, the optical film using the polymerizable liquid crystal composition of the present invention is excellent in heat resistance, but the optical film using the polymerizable liquid crystal composition containing the comparative compound has poor heat resistance, and the polymerization of the present invention. It is clear that the liquid crystalline compound is useful.

[Examples 21 to 24] Preparation of polymerizable liquid crystal composition and optical film containing optically active compound The following procedure [1] Preparation of polymerizable liquid crystal composition solution, [2] Application to substrate and curing The polymerizable liquid crystal compound of the invention was prepared, and an optical film as an optically anisotropic film was prepared from the polymerizable liquid crystal composition.

[1] Preparation of polymerizable liquid crystal composition solution Polymerizable liquid crystal compound No. 1 formulated according to the formulation described in [Table 2]. 5 or No. 9 and optically active compound No. 1 to 3 of a mixture of 1 to 3 is added to 2.0 g of a solvent (cyclopentanone) and dissolved, 0.03 g of a radical polymerization initiator (N-1919; manufactured by ADEKA Corporation) and diphenyliodonium After 0.03 g of hexafluorophosphate was added and completely dissolved, filtration treatment was performed with a 0.45 μm filter to prepare a polymerizable liquid crystal composition solution.

[2] Application to substrate and curing The polymerizable solution prepared in [1] above was applied onto a glass substrate coated with polyimide and rubbed with a spin coater. The coating was performed by adjusting the rotation speed and time of the spin coater so that the film thickness was about 2.0 μm. After coating, after drying at 100 ° C. for 3 minutes using a hot plate, cooling at room temperature for 3 minutes, using a high-pressure mercury lamp, irradiating light corresponding to 300 mJ / cm ² to cure the coating film, An optical film which is an optically anisotropic film was obtained.

[Evaluation Example 2]
About the optical film obtained in the said Examples 21-24, the physical property (homogeneity of orientation and selective reflection wavelength) was evaluated as follows. The results are shown in [Table 2] below.

<Uniformity of orientation>
The homogeneity of the obtained optical film was evaluated using a polarizing microscope. The alignment state of the polymer was observed by rotating the stage on which the polymer sample was placed under crossed Nicols, and the uniformity of the alignment was evaluated. If selective reflection is uniform and no orientation defect is confirmed, ○, selective reflection can be confirmed, but if orientation defect due to oily streak structure is confirmed, Δ, if crystallization or orientation unevenness is confirmed, × It was.

<Selective reflection wavelength measurement>
Using a spectrophotometer (manufactured by Hitachi High-Technologies Corp .; U-3010 type) equipped with a 5 ° specular reflection accessory, the reflectance was measured in the range of 25 ° C. and wavelength of 800 to 400 nm. In the case where selective reflection was observed, it was marked as ◯, and in the case where selective reflection was not observed, it was marked as x. In Table 2 below, the selective reflection center wavelength (λ) is also shown when selective reflection is observed.

  From the above results, the polymerizable liquid crystal composition of the present invention has uniform selective reflection at a specific wavelength, has no alignment defect, and is formed from a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound of the present invention. It is clear that anisotropic films are particularly useful when used as optical films.

Claims (7)

A polymerizable liquid crystal compound represented by the following general formula (I).

(In the formula, each of rings A ¹ , A ² , A ³ and A ⁴ independently represents a benzene ring or a naphthalene ring, and at least one of ring A ¹ , ring A ² , ring A ³ and ring A ⁴ is naphthalene. A ring,
S ¹ and S ² each independently represents an alkylene group having 1 to 8 carbon atoms, and the hydrogen atom of the alkylene group may be substituted with a halogen atom or may be branched and interrupted by an oxygen atom. You can,
X ¹ represents a hydrogen atom or a methyl group,
Z ¹ is a direct bond, Z ^2, Z ³ and Z ⁴ are each independently, - O-CO- or -CO-O - a Oh is,
Y ¹ , Y ² , Y ³ and Y ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, a halogen atom or a cyano group, and the hydrogen atom of the alkyl group is substituted with a halogen atom or a cyano group. The methylene group of the alkyl group may be interrupted by an oxygen atom or -CO-,
a, b, c and d are each independently 0 to 8,
n is 1 or 2,
G represents a substituent represented by the following formula ( 2) or (3 ) . )

(In Formula (2), R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and in Formula (3), R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It is.) The polymerizable liquid crystal compound according to claim 1 represented by the following general formula (II).

(In the formula, S ¹ , X ¹ , Z ¹ , Z ² , Z ³ and Z ⁴ are the same as those in the general formula (I),
R ^{4 to} R ¹⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom or a cyano group,
R ^{20 to} R ²⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, or —O—S ² —G, and one of R ^{20 to} R ²⁴ or two is -O-S ² -G,
The hydrogen atom of the alkyl group represented by R ^{4 to} R ²⁴ may be substituted with a halogen atom or a cyano group, and the methylene group of the alkyl group represented by R ^{4 to} R ²⁴ is an oxygen atom or —CO—. And S ² and G are the same as those in the general formula (I). ) The polymerizable liquid crystal composition comprising one or more of claims 1 or 2 in the polymerizable liquid crystal compound according. The polymerizable liquid crystal composition according to claim 3, which exhibits a liquid crystal phase even at 25 ° C. or lower. Further contains an optically active compound, according to claim 3 or 4 polymerizable liquid crystal composition according to a cholesteric liquid crystal phase. Further polymerizable liquid crystal composition according to any one of claims 3-5 comprising a radical polymerization initiator and a cationic polymerization initiator. An optical film formed of a polymer obtained by photopolymerizing the polymerizable liquid crystal composition according to any one of claims 3 to 6 .