JP6318528B2 - Liquid crystal / polymer composite material, optical element, method for manufacturing optical element, and method for manufacturing liquid crystal / polymer composite material - Google Patents

Description

The present invention relates to a liquid crystal / polymer composite material useful as a liquid crystal display material , an optical element, a method for producing an optical element, and a method for producing a liquid crystal / polymer composite material .

Currently, a liquid crystal material called a nematic liquid crystal in the market is generally used in flat panel displays such as televisions, monitors, mobile phones, smartphones, and tablet terminals.
However, nematic liquid crystals have a response speed as low as about a dozen milliseconds, so improvement is desired. On the other hand, a ferroelectric liquid crystal (FLC) using a smectic liquid crystal can respond at a high speed of several hundred microseconds.

  Polymer Stabilized V-shaped-FLC (PSV-FLC) element, which is composed of a mixture of FLC and monomer, forms a fine polymer network in ferroelectric liquid crystal, and is a high-speed response characteristic of FLC. In addition to the above, intermediate display is possible, and the impact resistance is improved as compared with the conventional FLC (see, for example, Patent Documents 1 and 2).

  The liquid crystal display device described in Patent Document 1 includes a ferroelectric liquid crystal layer interposed between a pair of substrates, and electrode portions for applying a voltage to the ferroelectric liquid crystal layer are disposed on the inner surfaces of both substrates. In the liquid crystal display device, the ferroelectric liquid crystal layer applies an alternating electric field having a frequency of 2 kHz to 4 kHz to a ferroelectric liquid crystal composition containing a predetermined liquid crystal acrylate monomer while exhibiting a chiral smectic C phase. In addition, the apparatus is characterized in that it is polymerized with the liquid crystalline acrylate monomer by irradiation with ultraviolet rays or electron beams.

  The liquid crystal display element described in Patent Document 2 applies a bipolar pulse wave to a polymer-stabilized liquid crystal composition containing liquid crystalline (meth) acrylate, non-liquid crystalline (meth) acrylate, and ferroelectric liquid crystal. It is an element obtained by curing the acrylate by UV exposure.

JP 2002-31821 A JP 2008-248210 A

  However, in these devices, FLC, a composite material of FLC and a polymerizable monomer, and a phase sequence after polymerization of the polymerizable monomer in the composite material are liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase. Therefore, the transmittance of the device after polymerization of the polymerizable monomer at the time of voltage application is lower than that of the device using nematic liquid crystal, which is insufficient for market demand.

  The problem to be solved by the present invention is to provide a liquid crystal composite material in which the tilt angle is improved after polymerization of the polymerizable monomer and the transmittance at the time of voltage application of the device is improved.

  The present inventor has focused on the phase change of FLC and the phase change after the addition of the monomer in PSV-FLC, found a method for improving the transmittance, and has completed the present invention.

[1] A liquid crystal / polymer composite material obtained by polymerizing a polymerizable monomer in a liquid crystal / monomer composite material containing a liquid crystal composition and a polymerizable monomer,
The liquid crystal composition exhibits a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase, and when the polymerizable monomer is added to the liquid crystal composition, the liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase shows the phase sequence of,
A liquid crystal / polymer composite material characterized by showing a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase .

[ 2 ] An optical element comprising the liquid crystal / polymer composite material according to [ 1 ].
[ 3 ] The method of manufacturing an optical element according to [2],
Method for manufacturing an optical element comprising the step of said liquid crystal monomers composite obtain chiral smectic C phase by polymerizing the polymerizable monomer in the temperature range showing the liquid crystal-polymer composite.

[ 4 ] The method of manufacturing an optical element according to [3],
The optical element has a liquid crystal layer interposed between a pair of substrates , and has an electrode portion for applying a voltage to the liquid crystal layer on the inner surface of at least one substrate ,
By applying an alternating electric field in a temperature range in which the liquid crystal / monomer composite material exhibits a chiral smectic C phase to a liquid crystal composition containing a polymerizable monomer, the polymerizable monomer is increased by irradiating ultraviolet rays or electron beams. A method for producing an optical element , comprising a step of molecularizing the liquid crystal layer .
[ 5 ] The method of manufacturing an optical element according to [4],
A liquid crystal composition containing a polymerizable monomer is applied with an alternating electric field in a state showing a chiral smectic C phase, irradiated with ultraviolet rays or an electron beam, and then heated to polymerize the polymerizable monomer. The manufacturing method of an optical element including the process used as the said liquid-crystal layer .
[ 6 ] A liquid crystal showing a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase obtained by polymerizing a polymerizable monomer in a liquid crystal / monomer composite material containing a liquid crystal composition and a polymerizable monomer. A method for producing a polymer composite material, comprising:
The liquid crystal composition exhibits a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase, and when the polymerizable monomer is added to the liquid crystal composition, the liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase Shows the phase sequence of
A method for producing a liquid crystal / polymer composite material comprising a step of irradiating the liquid crystal / monomer composite material with ultraviolet rays or an electron beam.
[ 7 ] Liquid crystal showing a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase obtained by polymerizing a polymerizable monomer in a liquid crystal / monomer composite material containing a liquid crystal composition and a polymerizable monomer. A method for producing a polymer composite material, comprising:
The liquid crystal composition exhibits a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase, and when the polymerizable monomer is added to the liquid crystal composition, the liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase Shows the phase sequence of
A method for producing a liquid crystal / polymer composite material comprising a step of heating the liquid crystal / monomer composite material after being irradiated with ultraviolet rays or an electron beam.

  According to the present invention, FLC shows a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase, and the composite material of FLC and polymerizable monomer is liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase. After the polymerization of the polymerizable monomer in the composite material, the phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase is shown. In addition, the tilt angle is improved, and the transmittance of the element when a voltage is applied is improved.

[Liquid Crystal / Monomer Composite Material]
The liquid crystal / monomer composite material of the present invention is a liquid crystal / monomer composite material containing a liquid crystal composition and a polymerizable monomer, and the liquid crystal composition exhibits a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase, When the polymerizable monomer is added to the liquid crystal composition, it is a material showing a phase sequence of liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase.
Hereinafter, preferred embodiments of the liquid crystal / monomer composite material of the present invention will be described in detail.

<Liquid crystal composition>
The liquid crystal composition used in the present invention exhibits a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase. When a polymerizable monomer is added to the liquid crystal composition, the liquid phase-chiral nematic phase-chiral smectic A phase- There is no particular limitation as long as it shows a phase sequence of a chiral smectic C phase.

  The liquid crystal composition used in the present invention preferably contains two or more compounds represented by the following general formula (i).

(In the formula, R ⁱ¹ and R ⁱⁱ¹ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a fluorine atom, a chlorine atom, a trifluoromethyl group, a trifluoromethoxy group. Represents a group, a difluoromethyl group, or an isocyanate group, and one or non-adjacent two or more —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —O. —, —CO—, —COO—, —OCO—, —S—, —CO—S—, —S—CO—, —O—CO—O—, a cyclohexylene group, or —Si (CH ₃ ). ₂ - may be substituted by, one or more hydrogen atoms in the alkyl group may be substituted by a fluorine atom each independently, -CH ₂ having the R ^i1, and R ⁱⁱ¹ - out of, or a ⁱ¹ or a ⁱ³ -CH ₂ positioned away atom number of 4 or more - are 1,4-cyclohexylene group, 1,4-phenylene group, 1,4-bicyclo (2,2,2) octylene group, dialkylsilylene group Furthermore, one or more hydrogen atoms of the alkyl group may be replaced with a fluorine atom or a CN group, and A ⁱ¹ , A ⁱ² and A ⁱ³ are each independently 2, 3-difluorobenzene-1,4-diyl group, 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane -2,5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2 5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9, 10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group, fluorene-2,7-diyl group, or pyrimidine-2 , Represents a 5-diyl group,
The 1,4-phenylene group, 1,4-cyclohexylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-octahydrophenanthrene-2,7-diyl group and fluorene-2,7-diyl group are substituents. And may have one or more of F, CF ₃ , OCF ₃ , CH ₃ , CN, or a plurality of these groups,
Z ¹ and Z ² are each independently —O—, —CO—, —COO—, —CF ₂ O—, —OCF ₂ —, —OCO—, —CH ₂ CH ₂ —, —O—CH _{2. -, - CH 2 O -,} - CH = CH -, - C≡C -, - CF 2 CF 2 -, or a single bond. a and b each independently represent 0-2. When a and b are 2, a plurality of A ¹ and A ² may be the same or different. )

  By combining two or more compounds represented by the general formula (i), a liquid crystal composition showing a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase can be obtained.

  Examples of the compound represented by the general formula (i) include a compound represented by the following general formula (X), a compound represented by the following general formula (i-1), and a compound represented by the following general formula (i-2). A compound represented by the following general formula (i-3), a compound represented by the following general formula (i-4), and a compound represented by the following general formula (i-5) Two or more selected from the group consisting of compounds are preferred.

(In Formula (X), R ¹⁰¹ and R ¹⁰² each independently represent a linear or branched alkyl group having 1 to 18 carbon atoms, and one or two or more adjacent non-adjacent alkyl groups in the alkyl group. —CH ₂ — represents —O—, —S—, —CO—, —CO—O—, —O—CO—, —CO—S—, —S—CO—, —O—CO—O—, — CH 1 —CH—, —C≡C—, a cyclohexylene group, or —Si (CH ₃ ) ₂ — may be substituted, and among the —CH ₂ — of R ¹⁰¹ and R ¹⁰² , A ^1a or —CH ₂ — located at a position 4 or more away from A ^3a is 1,4-cyclohexylene group, 1,4-phenylene group, 1,4-bicyclo (2,2,2) octylene group, It may be substituted with a dialkylsilylene group, and one or more hydrogen atoms of the alkyl group It may be replaced with a fluorine atom or a CN group.
A ^1a represents a 1,4-phenylene group, and A ^2a and A ^3a each independently represent one or two hydrogen atoms replaced with F, CF ₃ , OCF ₃ , CN, or a plurality of these groups And represents a 1,4-phenylene group or a 1,4-cyclohexylene group, m ¹ and n ¹ represent an integer of 0 or 1, and m ¹ + n ¹ = 0-2. )

(Wherein R ⁱ¹ and R ⁱⁱ¹ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, and one or non-adjacent 2 in the alkyl group) _Two or more —CH ₂ — are each independently substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO—, —OCO—, or a cyclohexylene group. In addition, one or two or more hydrogen atoms in the alkyl group may be each independently substituted with a fluorine atom, and among the —CH ₂ — of R ⁱ¹ and R ⁱⁱ¹ , 1, 4 —Cyclohexylene group or —CH ₂ — located at a position 4 or more away from the 1,4-phenylene group is 1,4-cyclohexylene group, 1,4-phenylene group, 1,4 -Bicyclo (2,2,2) octylene group, di Good .Z ¹ and Z ² may be substituted in Rukirushiriren groups are the same as those in formula (i).)

  A compound represented by the general formula (X), a compound represented by the general formula (i-1), a compound represented by the general formula (i-2), and a compound represented by the general formula (i-3). A combination of two or more selected from the group consisting of the compound represented by formula (i-4), and the compound represented by formula (i-5). A liquid crystal composition showing a phase sequence of chiral nematic phase-chiral smectic C phase is obtained. Here, “a combination of two or more types” may be used in a combination of two or more compounds represented by the general formula (X), and is selected from the general formulas (i-1) to (i-5). Two or more of the compounds represented by the general formula may be used, and two of the compounds represented by the general formula (X) and the compounds represented by the general formulas (i-1) to (i-5) are mixed. This means that the above may be used.

  Specific examples of the compound represented by the general formula (X) are represented by the general formulas (Xa) to (Xc).

(In the general formulas (Xa) to (Xc), R ¹⁰¹ and R ¹⁰² represent the same as those in the general formula (X),
X ⁸¹ to X ⁹⁶ each independently represents a hydrogen atom, a fluorine atom, or a methyl group. )

  Specific examples of the compounds represented by the general formula (Xa) to the general formula (Xc) can be given in the following (X-1) to (X-17).

Among these, it is represented by the general formula (X-1), the general formula (X-2), the general formula (X-4), the general formula (X-6), or the general formula (X-9). It is preferable to use a compound.
Examples of the compound represented by the general formula (X-1) include compounds represented by the following formulas (X-1-1) to (X-1-7).

(In the formula, R ¹ and R ² each independently represents a linear or branched alkyl group having 4 to 12 carbon atoms.)

(In the formula, R ³ and R ⁴ each independently represents a linear or branched alkyl group having 6 to 12 carbon atoms.)

(Wherein R ⁵ and R ⁹ each independently represents a linear or branched alkyl group having 4 to 12 carbon atoms, and R ⁷ is a linear or branched group having 2 to 12 carbon atoms. Represents a chain alkyl group, and R ⁶ and R ⁸ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms.)

(Wherein R ¹⁰ and R ¹¹ each independently represent a linear or branched alkyl group having 6 to 12 carbon atoms, and R ¹² is a linear or branched chain having 2 to 12 carbon atoms. Represents an alkyl group.

  Examples of the compound represented by the general formula (X-2) include compounds represented by the following formulas (X-2-1) to (X-2-2).

(In the formula, R ¹ and R ² each independently represents a linear or branched alkyl group having 4 to 12 carbon atoms.)
Examples of the compound represented by the general formula (X-4) include compounds represented by the following formulas (X-4-1) to (X-4-2).

(In the formula, R ¹ and R ² each independently represents a linear or branched alkyl group having 4 to 12 carbon atoms.)

In the compound represented by the general formula (X-6), R ¹⁰¹ is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, and a linear chain having 4 to 12 carbon atoms. An alkyl group is more preferred.
In the compound represented by the general formula (X-6), R ¹⁰² is preferably a linear or branched alkoxy group having 1 to 18 carbon atoms, and a branched chain having 4 to 12 carbon atoms. An alkoxy group is more preferable.
Examples of the compound represented by the general formula (X-6) include compounds represented by the following formulas (X-6-1) to (X-6-2).

(In the formula, R ¹³ represents a linear or branched alkyl group having 4 to 12 carbon atoms.)
In the compound represented by the general formula (X-9), R ¹⁰¹ is preferably a linear or branched alkyl group or alkoxy group having 1 to 18 carbon atoms, and a straight chain having 4 to 12 carbon atoms. A chain alkyl group or an alkoxy group is more preferable. R ¹⁰² is preferably a linear or branched alkyl group or alkoxy group having 1 to 18 carbon atoms, and more preferably a branched alkyl group or alkoxy group having 4 to 12 carbon atoms.
Examples of the compound represented by the general formula (X-9) include compounds represented by the following formulas (X-9-1) to (X-9-4).

(In the formula, R ¹³ represents a linear or branched alkyl group having 4 to 12 carbon atoms.)

  Moreover, the compound represented by the said general formula (i) also includes the compound represented by the following general formula (i-1).

(Wherein R ⁱ¹ and R ⁱⁱ¹ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, and one or non-adjacent 2 in the alkyl group) _Two or more —CH ₂ — are each independently substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO—, —OCO—, or a cyclohexylene group. In addition, one or two or more hydrogen atoms in the alkyl group may be each independently substituted with a fluorine atom, and among the —CH ₂ — of R ⁱ¹ and R ⁱⁱ¹ , 1, 4 —Cyclohexylene group or —CH ₂ — located at a position 4 or more away from the 1,4-phenylene group is 1,4-cyclohexylene group, 1,4-phenylene group, 1,4 -Bicyclo (2,2,2) octylene group, di Good .Z ¹ and ^{Z 2} may be substituted in Rukirushiriren groups are each _{independently, -O -, - CO -,} - COO -, - CF 2 O -, - OCF 2 -, - OCO -, - CH 2 (CH ₂ —, —O—CH ₂ —, —CH ₂ O—, —CH═CH—, —C≡C—, —CF ₂ CF ₂ —, or a single bond)
Specifically, the compound represented by the general formula (i-1) is preferably a compound represented by the formula (i-1.1) to the formula (i-1.6).

(Wherein R ²¹ represents a linear or branched alkyl group having 3 to 10 carbon atoms, and R ²² is independently a linear or branched alkyl group having 4 to 12 carbon atoms. Represents a group.)

  The compound represented by the general formula (i-1) is also preferably a compound represented by the following general formula (i-1-7).

(In the formula, R ⁱ¹ , Z ¹ and Z ² are the same as those in the general formula (i). R ^ii2a represents a linear alkyl group having 3 to 8 carbon atoms, and in the alkyl group, And two or more non-adjacent —CH ₂ — are each independently replaced by —CH═CH—, —C≡C—, —O—, —CO—, —COO—, or —OCO—. R ^ii2b represents a hydrogen atom or a linear or branched alkyl group having 2 to 12 carbon atoms, and one or non-adjacent two or more —CH in the alkyl group _2- may be each independently substituted by -CH = CH-, -C≡C-, -O-, -CO-, -COO-, or -OCO-.

  The compound represented by the general formula (i-1-7) is preferably a compound represented by the following general formula (i-1-7-1).

(In the formula, R ⁱ¹ and R ^ii2b are the same as those in the general formula (i-1-7), and n ⁱ¹ represents an integer of 3 to 7).

  The compound represented by the general formula (i-1-7-1) is specifically represented by the formula (i-1-7-1.1) to the formula (i-1-7-1.4). It is preferable that it is a compound.

(In the formula, R ²³ represents a linear or branched alkyl group having 3 to 10 carbon atoms, and n ⁱ¹ represents the same as in general formula (i-1-7-1). R ²⁴ represents a single bond or a linear or branched alkyl group having 1 to 3 carbon atoms.)

  Moreover, it is also preferable that the compound represented by the said general formula (i-1-7) is a compound represented by the following general formula (i-1-7-2).

(In the formula, R ⁱ¹ and R ^ii2b are the same as those in the general formula (i-1-7). N ⁱ² represents an integer of 3 to 8.)

  The compound represented by the general formula (i-1-7-2) is specifically represented by the formula (i-1-7-2.1) to the formula (i-1-7-2.4). It is preferable that it is a compound.

(Wherein R ²³ and R ²⁴ represent the same as those in the general formulas (i-1-7-1.1) to (i-1-7-1.4), and n ⁱ² represents (i The same thing as in -1-7-2) is represented.

  Moreover, as a compound represented by the said general formula (i), the compound represented by the following general formula (i-2) is also mentioned.

(In the formula, R ⁱ¹ , R ⁱⁱ¹ , Z ¹ and Z ² are the same as those in the general formula (i-1).)

  Specifically, the compound represented by the general formula (i-2) is preferably a compound represented by the formula (i-2.1) to the formula (i-2.8).

(In the formula, R ²⁵ represents a linear or branched alkyl group having 3 to 10 carbon atoms, and R ²⁶ represents a linear or branched alkyl group having 4 to 12 carbon atoms. )

  The compound represented by the general formula (i-2) is also preferably a compound represented by the following general formula (i-2-9).

(In the formula, R ⁱ¹ , Z ¹ and Z ² are the same as those in the general formula (i). R ^ii2a represents a linear alkyl group having 3 to 8 carbon atoms, and in the alkyl group, And two or more non-adjacent —CH ₂ — are each independently replaced by —CH═CH—, —C≡C—, —O—, —CO—, —COO—, or —OCO—. R ^ii2b represents a hydrogen atom or a linear or branched alkyl group having 2 to 12 carbon atoms, and one or non-adjacent two or more —CH in the alkyl group _2- may be each independently substituted by -CH = CH-, -C≡C-, -O-, -CO-, -COO-, or -OCO-.

  The compound represented by the general formula (i-2-9) is preferably a compound represented by the following general formula (i-2-9-1).

(Wherein R ⁱ¹ and R ^ii2b are the same as those in the general formula (i-2-9), and n ⁱ¹ represents an integer of 3 to 7)

  The compound represented by the general formula (i-2-9-1) is specifically represented by the formula (i-2-9-1.1) to the formula (i-2-9-1.4). It is preferable that it is a compound.

(In the formula, R ²⁷ represents a linear or branched alkyl group having 3 to 10 carbon atoms, and R ²⁸ represents a single bond or a linear or branched alkyl group having 1 to 3 carbon atoms. And n ⁱ¹ is the same as that in the general formula (i-2-9-1).)

  The compound represented by the general formula (i-2-9) is also preferably a compound represented by the following general formula (i-2-9-2).

(In the formula, R ⁱ¹ and R ^ii2b are the same as those in the general formula (i-2-9), and n ⁱ² represents an integer of 3 to 8.)

  The compound represented by the general formula (i-2-9-2) is specifically represented by the formula (i-2-9-2.1) to the formula (i-2-9-2.5). It is preferable that it is a compound.

(Wherein R ²⁷ and R ²⁸ are the same as those in formulas (i-2-9-1.1) to (i-2-9-1.4), and n ⁱ² is (Same as in general formula (i-2-9-2).)

  Moreover, as a compound represented by the said general formula (i), the compound represented by general formula (i-3) is also mentioned.

(In the formula, R ⁱ¹ , R ⁱⁱ¹ , Z ¹ and Z ² are the same as those in the general formula (i-1).)

In the compound represented by the general formula (i-3), Z ⁱ¹ and Z ⁱ² are preferably single bonds.
The compound represented by the general formula (i-3) is preferably a compound represented by the following general formula (i-3-1).

(In the formula, R ⁱ¹ and R ⁱⁱ¹ are the same as those in the general formula (i-3).)
The compound represented by the general formula (i-3-1) is preferably a compound represented by the following general formulas (i-3-1.1) to (i-3-1.4).

(In the formula, R ³¹ represents a linear or branched alkyl group having 3 to 10 carbon atoms, and R ³² represents a linear or branched alkyl group having 4 to 12 carbon atoms. )

  The compound represented by the general formula (i-3) is also preferably a compound represented by the following general formula (i-3-5).

(In the formula, R ⁱ¹ , Z ¹ and Z ² are the same as those in the general formula (i). R ^ii2a represents a linear alkyl group having 3 to 8 carbon atoms, and in the alkyl group, One or two or more non-adjacent —CH ₂ — are each independently replaced by —CH═CH—, —C≡C—, —O—, —CO—, —COO—, or —OCO—. R ^ii2b represents a hydrogen atom or a linear or branched alkyl group having 2 to 12 carbon atoms, and one or non-adjacent two or more —CH _{2 in the} alkyl group. -May be each independently substituted by -CH = CH-, -C≡C-, -O-, -CO-, -COO-, or -OCO-.

    The compound represented by the general formula (i-3-5) is preferably a compound represented by the following general formula (i-3-5-1).

(In the formula, R ^ii2b and R ⁱ¹ are the same as those in the general formula (i-3-5). N ⁱ¹ is an integer of 3 to ^7. )

  The compound represented by the general formula (i-3-5-1) is specifically represented by the formula (i-3-5-1.1) to the formula (i-3-5-1.4). It is preferable that it is a compound.

(In the formula, R ³⁴ represents a linear or branched alkyl group having 3 to 10 carbon atoms, and R ³⁵ represents a single bond or a linear or branched alkyl group having 1 to 3 carbon atoms. N ⁱ¹ is the same as that in the general formula (i-3-5-1).)

  The compound represented by the general formula (i-3-5) is also preferably a compound represented by the following general formula (i-3-5-2).

(In the formula, R ^ii2b and R ⁱ¹ are the same as those in the general formula (i-3-5). N ⁱ² is an integer of 4 to 8.)

  The compound represented by the general formula (i-3-5-2) is specifically represented by the formula (i-3-5-2.1) to the formula (i-3-5-2.4). It is preferable that it is a compound.

Wherein R ³⁴ and R ³⁵ are the same as those in the general formula (i-3-5-1.1) to general formula (i-3-5-1.4), and n ⁱ² is the general formula (Same as in (i-3-5-2).)

  Moreover, as a compound represented by the said general formula (i), the compound represented by general formula (i-4) is also mentioned.

(In the formula, R ⁱ¹ , R ⁱⁱ¹ , Z ¹ and Z ² are the same as those in the general formula (i-3).)

In the compound represented by the general formula (i-4), Z ¹ and Z ² are preferably a single bond or —CH ₂ O—.
The compound represented by the general formula (i-4) is preferably a compound represented by the following general formula (i-4-1).

(In the formula, R ⁱ¹ and R ⁱⁱ¹ are the same as those in the general formula (i-4).)

The compound represented by the general formula (i-4-1) is preferably a compound represented by the following general formula (i-4-1.1).

(In the formula, R ⁱ¹ is the same as that in the general formula (i-4). R ^ii1a represents a linear or branched alkyl group having 1 to 18 carbon atoms.)
Specifically, a compound represented by the formula (i-4-1.1.1) to the formula (i-4-1.1.3) is preferable.

(In the formula, R ³⁶ represents a linear or branched alkyl group having 3 to 10 carbon atoms, and R ³⁷ represents a linear or branched alkyl group having 4 to 12 carbon atoms. )

  Moreover, the compound represented by the said general formula (i-4) has a preferable compound represented by the following general formula (i-4-2).

(In the formula, R ⁱ¹ and R ⁱⁱ¹ are the same as those in the general formula (i-4).)

  Specifically, the compound represented by the general formula (i-4-2) is preferably a compound represented by the formula (i-4-2.1) to the formula (i-4-2.4).

(In the formula, R ⁴¹ represents a linear or branched alkyl group having 3 to 10 carbon atoms, and R ⁴² represents a linear or branched alkyl group having 4 to 12 carbon atoms. )

  Moreover, as a compound represented by the said general formula (i-4), the compound represented by the following general formula (i-4-7) is also mentioned.

(In the formula, R ⁱ¹ , R ^ii2a , R ^ii2b , R ⁱ¹ , Z ¹ , and Z ² are the same as those in the general formula (i-3-5).)

  The compound represented by the general formula (i-4-7) is preferably a compound represented by the following general formula (i-4-7-1).

(In the formula, R ^ii1b and R ⁱ¹ are the same as those in the general formula (i-4-7). N ⁱ¹ is an integer of 3 to ^7. )

  The compounds represented by the general formula (i-4-7-1) are specifically represented by the formulas (i-4-7-1.1) to (i-4-7-1.4). It is preferable that it is a compound.

(In the formula, R ⁴³ represents a linear or branched alkyl group having 3 to 10 carbon atoms, and R ⁴⁴ is a single bond or a linear or branched alkyl group having 1 to 3 carbon atoms. And n ⁱ¹ is the same as that in the general formula (i-4-7-1).)

  Moreover, as a compound represented by the said general formula (i), the compound represented by general formula (i-5) is also mentioned.

(In the formula, R ⁱ¹ , R ⁱⁱ¹ , Z ¹ and Z ² are the same as those in the general formula (i-1).)

In the compound represented by the general formula (i-5), Z ¹ and Z ² are preferably single bonds.
The compound represented by the general formula (i-5) is preferably a compound represented by the following general formula (i-5-1).

  Specifically, the compound represented by the general formula (i-5-1) is preferably a compound represented by the formula (i-5-1.1) to the formula (i-5-1.4).

(In the formula, R ⁴⁵ represents a linear or branched alkyl group having 3 to 10 carbon atoms, and R ⁴⁶ represents a linear or branched alkyl group having 4 to 12 carbon atoms. )

  Moreover, as a compound represented by the said general formula (i-5), the compound represented by the following general formula (i-5-8) is also mentioned.

(In the formula, R ^ii2a , R ^ii2b , R ⁱ¹ , Z ¹ , and Z ² are the same as those in the general formula (i-4-7).)

  The compound represented by the general formula (i-5-8) is preferably a compound represented by the following general formula (i-5-8-1).

(In the formula, R ^ii1b , R ⁱ¹ , and n ⁱ¹ are the same as those in the general formula (i-4-7-1).)

  The compounds represented by the general formula (i-5-8-1) are specifically represented by the formulas (i-5-8-1.1) to (i-5-8-1.4). It is preferable that it is a compound.

(In the formula, R ⁴⁷ represents a linear or branched alkyl group having 3 to 10 carbon atoms, and R ⁴⁸ is a single bond or a linear or branched alkyl group having 1 to 13 carbon atoms. Represents.)

The liquid crystal composition used in the present invention preferably further contains one or more compounds having an optically active substance.
The compound having an optically active substance may be any of a compound having an asymmetric atom, a compound having axial asymmetry, a compound having surface asymmetry, and an atropisomer, and a compound having a polymerizable group may have a polymerizable group. You may not have it.
In a compound having an asymmetric atom, it is preferable that the asymmetric atom is an asymmetric carbon atom because steric inversion hardly occurs, but a hetero atom may be an asymmetric atom. The asymmetric atom may be introduced into a part of the chain structure or may be introduced into a part of the cyclic structure.
Specific examples of such a compound include compounds represented by the following general formula (ii).

(In the formula (ii), R ¹ and R ² each independently represents a linear or branched alkyl group having 1 to 30 carbon atoms, a hydrogen atom or a fluorine atom, and one or two of the alkyl groups When two or more non-adjacent —CH ₂ — groups are —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, —CO—O—, —O—CO—, — O—CO—O—, —S—CO—, —CO—S—, —O—SO ₂ —, —SO ₂ —O—, —CH═CH—, —C≡C—, cyclopropylene group or — Si (CH ₃ ) ₂ — may be substituted, and one or more hydrogen atoms of the alkyl group may be substituted with a fluorine atom or a bromine atom, or may have a polymerizable group. The group may comprise a fused or spirocyclic system and the alkyl group is one or more heterogeneous May be those containing one or more aromatic or aliphatic rings can contain child, and these cyclic alkyl group, an alkoxy group, it may be optionally substituted with halogen,
Either one or both of R ¹ and R ² is a group having an asymmetric atom,
Z is each independently —O—, —S—, —CO—, —CO—O—, —O—CO—, —O—CO—O—, —CO—N (R ^a ) —, —N ( R ^a ) —CO—, —OCH ₂ —, —CH ₂ O—, —SCH ₂ —, —CH ₂ S—, —CF ₂ O—, —OCF ₂ —, —CF ₂ S—, —SCF ₂ — _{, -CH 2 CH 2 -, -} CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CH -, - CH = CF -, - CF = CF—, —C≡C—, —CH═CH—CO—O—, —O—CO—CH═CH— or a single bond, —CO—N (R ^a ) — or —N (R ^a ) R ^{a in} —CO— represents ^a hydrogen atom or ^a linear or branched alkyl group having 1 to 4 carbon atoms,
A ¹ and A ² are each independently a phenylene group, cyclohexylene group, dioxolanediyl group, cyclohexenylene group, bicyclo [2.2.2] octylene group, piperidinediyl group, naphthalenediyl group, decahydronaphthalenediyl group, Represents a cyclic group selected from a tetrahydronaphthalenediyl group or an indanediyl group, wherein the phenylene group, naphthalenediyl group, tetrahydronaphthalenediyl group, or indanediyl group has one or more —CH═ groups in the ring. May be replaced by a nitrogen atom, the cyclohexylene group, dioxolanediyl group, cyclohexenylene group, bicyclo [2.2.2] octylene group, piperidinediyl group, decahydronaphthalenediyl group, tetrahydronaphthalenediyl group, or Indandiyl group is 1 in the ring Or two non-adjacent -CH 2 _- groups may be replaced by -O- and / or -S-, 1 or more hydrogen atoms of the cyclic group, a fluorine atom, a bromine atom , NO ₂ group, or one or two or more hydrogen atoms may be replaced with fluorine atoms, substituted with alkyl groups having 1 to 7 carbon atoms, alkoxy groups, alkylcarbonyl groups or alkoxycarbonyl groups You may,
m is 1, 2, 3, 4 or 5. ) Is preferred.

A dichiral compound in which both R ¹ and R ² in the general formula (ii) are chiral groups is more preferable. Specific examples of the dichiral compound include compounds represented by the following general formulas (ii-a1) to (ii-a11).

In the general formulas (ii-a1) to (ii-a11), each R ³ independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, and one or two of the alkyl groups When two or more non-adjacent —CH ₂ — groups are —O—, —S—, —NH—, —N (CH ₃ ) —, —CO—, —CO—O—, —O—CO—, — O—CO—O—, —S—CO—, —CO—S—, —O—SO ₂ —, —SO ₂ —O—, —CH═CH—, —C≡C—, cyclopropylene group or — It may be replaced with Si (CH ₃ ) ₂ —, and one or more hydrogen atoms of the alkyl group may be replaced with a fluorine atom or a bromine atom, or may have a polymerizable group. Examples of the polymerizable group include a vinyl group, an allyl group, and a (meth) acryloyl group.
X ³ and X ⁴ are each independently a halogen atom or a phenyl group (one or more arbitrary hydrogen atoms of the phenyl group are a halogen atom, a methyl group, a methoxy group, —CF ₃ , —OCF ₃ And may be a methyl group, a methoxy group, —CF ₃ , or —OCF ₃ . Further, a plurality of X ³ and X ⁴ existing in the molecule may be the same or different. However, in general formulas (ii-a3) and (ii-a8), a group different from X ³ is selected for X ⁴ so that the position marked with * becomes an asymmetric atom.
A ¹ , Z, A ² and m are the same as those in the general formula (ii).
When m is 2 to 5, a plurality of Z and A ² may be the same or different.
Moreover, _{n 3} is an integer of 0 to 20.
R ⁵ in the general formulas (ii-a4) and (ii-a9) represents a hydrogen atom or a methyl group.
Examples of Q in the general formulas (ii-a5) and (ii-a10) include divalent hydrocarbon groups such as a methylene group, an isopropylidene group, and a cyclohexylidene group.
K in general formula (ii-a11) is an integer of 0-5.

More preferable examples include linear or branched alkyl groups having 4 to 8 carbon atoms such as R ³ = C ₄ H ₉ , C ₆ H ₁₃ , C ₈ H ₁₇ and the like. X ³ is preferably CH ₃ .

More preferably, the partial structural formulas in the general formulas (ii) and (ii-a1) to (ii-a11), -A ^1- (ZA ² ) _m- ,

(In the formula, rings A, B and C are each independently a phenylene group, a cyclohexylene group or a naphthalenediyl group, and in these groups, any one or two or more arbitrary hydrogen atoms of the benzene ring are halogen atoms. An atom, a methyl group, a methoxy group, —CF ₃ , —OCF ₃ may be substituted, and any one or more carbon atoms of the benzene ring may be substituted with a nitrogen atom. Is the same as in formula (ii)), more preferably

(However, in these formulas, any one or two or more arbitrary hydrogen atoms of the benzene ring may be substituted with a halogen atom, a methyl group, a methoxy group, —CF ₃ , —OCF ₃ , Any one or more of the carbon atoms may be substituted with a nitrogen atom, the definition of Z being the same as in formula (ii)). In terms of reliability, a benzene ring or a cyclohexane ring is preferable to a heterocyclic ring such as a pyridine ring or a pyrimidine ring. In terms of increasing the dielectric anisotropy, it is preferable to use a compound having a heterocyclic ring such as a pyridine ring or a pyrimidine ring. In this case, the polarizability of the compound is relatively large, and the benzene ring or cyclohexane ring In the case of a hydrocarbon ring such as a compound, the polarizability of the compound is low. For this reason, it is preferable to select an appropriate content according to the polarizability of the compound having an optically active substance.
More preferable examples include compounds represented by the following general formula (ii-a6-1).

(In the formula, R ³ , X ³ , Z, and n ₃ are the same as those in the general formula (ii-a6).)

By adding the chiral chiral compound represented by the general formula (ii) to the host liquid crystal composition containing the compound group represented by the general formula (X) as a main component, the host liquid crystal composition exhibits ferroelectricity. become. In order to obtain a large spontaneous polarization, the concentration of the chiral compound may be increased, and the amount of the chiral chiral compound can be adjusted for the purpose of obtaining necessary physical properties such as spontaneous polarization, phase transition temperature, and phase sequence. . In order to suppress crystallization, the addition amount has an upper limit, but the use of a compound in which the optically active group of the chiral chiral compound is different in the terminal group structure of the host liquid crystal is preferable because the crystallization temperature is lowered. In order to increase the stability (maximum temperature) of the ferroelectric phase, it is preferable to use a compound having three rings so long as the effect of suppressing crystallization is maintained. In order to obtain good orientation in parallel alignment cells, it is important to increase the helical pitch of the chiral nematic phase, especially to increase the helical pitch of the chiral nematic phase during the transition between the nematic phase and the smectic phase. When the phase is changed to the smectic A phase in a state where the helix is broken, a good uniaxial orientation can be obtained.
The amount of addition of the chiral compound group represented by the general formula (ii) (hereinafter referred to as (ii) group) increases, and the helical pitch of the chiral nematic phase at the time of transition between the nematic phase and the smectic phase disturbs the orientation. In the case of shortening, (ii) a chiral compound having an effect of inducing a sense opposite to the chirality (sense) of the spiral of the chiral nematic phase induced by the compound of the group (ii) is used in addition to the group (ii). It is preferable to increase the helical pitch of the chiral nematic phase. There is no restriction | limiting in particular in the use of the chiral compound at this time, Although a well-known and usual chiral compound can be used, the compound (ii) used and the same polarity of the spontaneous polarization or the value of spontaneous polarization was used ( A compound that is sufficiently smaller than the group ii) is preferable because it can suppress a decrease due to cancellation of spontaneous polarization.

Further, in the ferroelectric phase, when the orientation is performed using the surface stabilization effect, it is preferable that the helical pitch in the ferroelectric phase is long. In this case, the ferroelectric phase is induced by the group (ii) compound. It is preferable to increase the helical pitch of the ferroelectric phase by using, in addition to the group (ii), a chiral compound that has an effect of inducing sense opposite to the palmarity (sense) of the spiral of the ferroelectric phase. There is no restriction | limiting in particular in the use of the chiral compound at this time, Although a well-known and usual chiral compound can be used, the compound (ii) used and the same polarity of the spontaneous polarization or the value of spontaneous polarization was used ( A compound that is sufficiently smaller than the group ii) is preferable because it can suppress a decrease due to cancellation of spontaneous polarization. When the polymer stabilizing effect is simply used without using the surface stabilizing effect, it is not particularly necessary to add a chiral compound having such an effect of inducing reverse sense to the group (ii).
When used in a relatively thick cell thickness (3 μm or more), the polymer stabilization process or the state after the polymer stabilization is improved, the mobility of the liquid crystal molecules is increased and the polymer stabilization process is facilitated. When a short helical pitch is required to facilitate the development of the gray scale after stabilization or polymer stabilization, it is preferable to add a compound having a short helical pitch of the ferroelectric phase. There is no particular limitation on the use of the chiral compound used for the addition, and a known and commonly used chiral compound can be used. However, the compound having the same polarity of spontaneous polarization as the group (ii) used, or the value of spontaneous polarization is used. A compound that is sufficiently smaller than the group (ii) is preferable because a decrease due to cancellation of spontaneous polarization can be suppressed. As the additive, it is more preferable to select a chiral compound that has a sufficiently long helical pitch induced in the chiral nematic liquid crystal or that can cancel the helical pitch induced in the group (ii).
Therefore, in the liquid crystal composition of the present invention, it is important that the content of the compound represented by the general formula (ii) is determined in consideration of the description regarding the group (ii) described above. 1-35 mass% is preferable with respect to the total mass of a composition, 5-30 mass% is more preferable, and 5-20 mass% is especially preferable.

<Polymerizable monomer>
The polymer-stabilized ferroelectric liquid crystal display device using the liquid crystal / monomer composite material of the present invention has low driving voltage, high transmittance, and high contrast display due to the improvement of uniaxial orientation. It is possible to obtain a halftone display, which is impossible with a display element composed of a single ferroelectric liquid crystal, and has excellent thermal and mechanical stability.
In the ferroelectric liquid crystal composition, while an alternating voltage is applied, a radical polymerizable compound contained therein is polymerized by heat or active energy rays such as ultraviolet rays, and accordingly, phase separation from the liquid crystal composition or liquid crystal A polymer-stabilized liquid crystal display device comprising a transparent polymer substance and a liquid crystal composition in a state dispersed in the composition.
This element is a liquid crystal element having an alignment control film and a liquid crystal layer between a substrate having a pair of electrode layers, wherein the liquid crystal layer contains at least a liquid crystalline polymer precursor (polymerizable liquid crystal). It contains a photocured material and a ferroelectric liquid crystal material, and the orientation direction of the mesogenic group of the polymerizable liquid crystal and the orientation direction of the ferroelectric liquid crystal material are the orientation direction of the orientation control film between the pair of electrode layers. The liquid crystal display element is a polymer stabilized so as to be aligned in a uniaxial orientation. In the liquid crystal display element, a photocured product of a polymerizable liquid crystal is dispersed in a liquid crystal layer, and no voltage is applied due to the alignment stabilization effect of a ferroelectric liquid crystal material by a polymer chain having a liquid crystal skeleton. In this state, an alignment state in which the major axis direction of the liquid crystal skeleton of the liquid crystalline monomer and the alignment direction of the ferroelectric liquid crystal material or the averaged alignment direction of the ferroelectric liquid crystal molecules is uniform is realized. When a voltage is applied, the orientation direction of the ferroelectric liquid crystal material is not the orientation direction of the liquid crystal skeleton of the liquid crystalline polymer precursor due to the spontaneous polarization of the ferroelectric liquid crystal. Or the average orientation direction and the angle formed by the orientation direction of the liquid crystal skeleton of the liquid crystalline monomer are continuously changed.
For example, by arranging the element between two polarizing plates and changing the applied voltage, the amount of transmitted light can be controlled continuously, such as area gradation performed by a single element of ferroelectric liquid crystal. A halftone display proportional to the applied voltage can be displayed without using any special means.

The uniaxial orientation described above is a method using a polymer orientation film such as polyimide that has been rubbed so as to obtain a uniaxial orientation, a method using an inorganic orientation film, a method using a photo-alignment film, and a method using an external field such as an electric field or a magnetic field. The polymer is stabilized by exposing the ultraviolet light to a state in which the long axis of the mesogenic group or polymer main chain is aligned by a method using an alignment film and the external field in combination.
In the case of polymer-stabilized liquid crystals, the size of the voids indicated by the polymer cross-linked structure is avoided from about 500 nm to about 1500 nm, where the average gap interval is in the visible light wavelength range, so that light scattering does not occur. Thus, it is important to form it in the liquid crystal. In order to reduce the thickness to 500 nm or less, a method using a phase separation process by spinodal decomposition, a method in which a UV polymerization rate is increased (a method by a UV polymerization process or a method by adjusting a polymer precursor composition), a low molecular liquid crystal, Examples include a method of polymerizing in a compatible state with almost no phase separation, and it is preferable to use these techniques effectively to form a fine network polymer that does not cause light scattering. Further, it is also preferable to form a polymer layer with an unevenness on the surface of the liquid crystal cell substrate, to form a polymer protrusion, or to form a fine fiber polymer so as not to cause scattering.
When the monomer is compatible with the low-molecular liquid crystal, it is more preferable that the network polymer can be formed in a dispersed state in the low-molecular liquid crystal and a fine structure at the molecular level can be obtained.
However, when polymerization microphase separation occurs minimally when the polymerizable monomer used in the present invention is polymerized in the liquid crystal phase, the order of orientation is not high, but the network-like high height is aligned along the liquid crystal molecular director. The formation of molecules is observed with an electron microscope or the like. This is because when the polymerizable monomer comes into contact with the liquid crystal, the major axis of the monomer molecule tends to be aligned in the direction of the liquid crystal molecule director, and the alignment of the liquid crystal is fixed by the polymerization of the polymerizable monomer. However, when the concentration of the polymerizable monomer is increased, a phase separation structure caused by spinodal decomposition or binodal decomposition that occurs in polymerization microphase separation is formed ignoring the alignment of the liquid crystal. become unable. The above-mentioned method may disturb the orientation of the low-molecular liquid crystal. In this case, the electric field, the orientation regulating force of the orientation film, the external magnetic field, etc. are utilized so as to obtain the desired stabilizing orientation. The external field can also be adjusted so as to obtain the target polymer-stabilized liquid crystal element. Further, a regular periodic structure may be formed by applying a self-organization property based on a self-organization property of a mesogen group or a hydrogen bond group in a copolymer of a plurality of polymerizable liquid crystals. If necessary to obtain desired characteristics, a structure in which fine polymer particles are dispersed in a low-molecular liquid crystal may be used.

In order to fix the alignment state of the liquid crystal with the alignment film or the like without alignment defects, it is preferable to remove at least the nematic phase and to make the phase transition to the smectic phase, and the substrate surface of the liquid crystal cell to be used is flat It is more preferable. Further, it is necessary to polymerize the monomer in a network or dispersed state in a liquid crystal phase such as a nematic phase or a smectic phase. Furthermore, in order to avoid the formation of the phase separation structure, the content of the polymer precursor is reduced so that a network polymer can be formed between the liquid crystal molecules while the content of the monomer is reduced and the liquid crystal is aligned. It is preferable to adjust the composition of the precursor. Further, in the case of photopolymerization, the UV exposure time, UV exposure intensity, and temperature are adjusted to form a network polymer so that there are no liquid crystal alignment defects. It is preferable to do.
In addition, in order to obtain a desired liquid crystal alignment when polymerizing the monomers in the composition, an alignment film subjected to vertical alignment, parallel alignment or antiparallel alignment rubbing alignment treatment or photo-alignment treatment, or an inorganic shape It is possible to use a liquid crystal cell having an alignment film utilizing the effect, a liquid crystal cell in which the upper and lower substrates are a vertical alignment film, or a combination of a vertical alignment film and a parallel alignment. Furthermore, a twisted alignment obtained by applying an external field such as light, heat, voltage, magnetic field, bent alignment, splay alignment, parallel alignment, etc., or a liquid crystal alignment state that is difficult to obtain with only an alignment film, By polymerizing the monomers, the alignment state thereof can be fixed, and the target polymer-stabilized liquid crystal display element can be obtained.
For example, in the smectic phase, the alignment state in which the directors are aligned in a certain direction due to the external field is stabilized, or the excessive alignment state is fixed by polymerizing by switching and the desired polymer stabilized liquid crystal display An element can also be obtained.
Examples of the polymerizable compound that can be used in such an element include a photopolymerizable monomer that undergoes polymerization by energy rays such as light, and the structure includes, for example, a plurality of six-membered rings such as biphenyl derivatives and terphenyl derivatives. And polymerizable compounds having a liquid crystal skeleton.
Hereinafter, the polymerizable monomer used in the present invention will be specifically described.

≪Polymerizable compound (I) ≫
The polymerizable compound (I) used in the present invention has the general formula (Ia)

(In the formula (Ia),
A ¹ represents a hydrogen atom or a methyl group,
A ² represents a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups present in the alkylene group are each independently an oxygen atom on the assumption that oxygen atoms are not directly bonded to each other). , —CO—, —COO— or —OCO— may be substituted, and one or two or more hydrogen atoms present in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group May be)
A ³ and A ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms (one or two or more methylene groups present in the alkyl group are such that oxygen atoms are not directly bonded to each other) Each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms present in the alkyl group are each independently a halogen atom or carbon. Which may be substituted with an alkyl group of 1 to 17 atoms).
A ⁴ and A ⁷ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups present in the alkyl group are such that oxygen atoms are not directly bonded to each other). Each independently substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms present in the alkyl group are each independently a halogen atom or a carbon atom. Which may be substituted with an alkyl group of the formula 1 to 9),
k represents 1 to 40;
B ¹ , B ² and B ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups present in the alkyl group are The oxygen atoms may be independently substituted with oxygen atoms, —CO—, —COO—, or —OCO— as those in which oxygen atoms are not directly bonded to each other), or the general formula (Ib)

(In formula (Ib), A ⁹ represents a hydrogen atom or a methyl group,
A ⁸ is a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups present in the alkylene group are each independently an oxygen atom, assuming that oxygen atoms are not directly bonded to each other). , —CO—, —COO— or —OCO— may be substituted, and one or two or more hydrogen atoms present in the alkylene group are each independently substituted with a fluorine atom, a methyl group or an ethyl group Represents a group represented by: When k is 2 or more, a plurality of B ² and B ³ may be the same or different. However, the number of the groups represented by the general formula (Ib) among B ¹ , B ^2, and B ³ that are 2k + 1 is 0 to 3. ) Is preferred. Moreover, it is preferable that the glass transition temperature of the polymeric compound of this polymeric compound is -100 degreeC to 25 degreeC.

In the present invention, unless otherwise specified, the “alkylene group” is a divalent group “— (CH ₂ ) _n, wherein one hydrogen atom is removed from carbon atoms at both ends of an aliphatic linear hydrocarbon. -"(Where n is an integer of 1 or more), and the substitution from a hydrogen atom to a halogen atom or an alkyl group, or from a methylene group to an oxygen atom, -CO-, -COO- or -OCO- If there is a substitution, this shall be specifically refused. Further, the “alkylene chain length” refers to n in the general formula “— (CH ₂ ) _n —” of the “alkylene group”.

  The non-liquid crystalline monomer (I) may contain a plurality of non-liquid crystalline monomers (Ia) having different main chain lengths or alkyl side chain lengths.

  As a preferable structure of the polymerizable compound (I) represented by the general formula (Ia), the following general formula (Ic)

(In formula (Ic), A ¹¹ and A ¹⁹ each independently represent a hydrogen atom or a methyl group, and A ¹² and A ¹⁸ each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms ( One or more methylene groups present in the alkylene group are each independently substituted with an oxygen atom, -CO-, -COO- or -OCO-, assuming that the oxygen atoms are not directly bonded to each other. And one or two or more hydrogen atoms present in the alkylene group may each independently be substituted with a fluorine atom, a methyl group or an ethyl group).
A ¹³ and A ¹⁶ are each independently a linear alkyl group having 2 to 20 carbon atoms (one or two or more methylene groups present in the linear alkyl group are such that oxygen atoms are not directly bonded to each other) And may be independently substituted with an oxygen atom, -CO-, -COO-, or -OCO-).
A ¹⁴ and A ¹⁷ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups present in the alkyl group are such that oxygen atoms are not directly bonded to each other) Each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms present in the alkyl group are each independently a halogen atom or carbon. Which may be substituted with an alkyl group of 1 to 9 atoms).
A ¹⁵ represents an alkylene group having 9 to 16 carbon atoms (in the alkylene group, at least 1 to 5 methylene groups, one of the hydrogen atoms in the methylene group is independently 1 carbon atom) To one or more methylene groups present in the alkylene group are each independently an oxygen atom, assuming that the oxygen atoms are not directly bonded to each other. , -CO-, -COO- or -OCO- may be substituted). ), A compound represented by the general formula (Id)

(In Formula (Id), A ²¹ and A ²² each independently represents a hydrogen atom or a methyl group, and a represents an integer of 6 to 22), a general formula (I- e)

(In Formula (Ie), A ³¹ and A ³² each independently represent a hydrogen atom or a methyl group, b and c each independently represent an integer of 1 to 10, and d is an integer of 1 to 10) And e represents an integer of 0 to 6), and the general formula (If)

(In formula (If), A ⁴¹ and A ⁴² each independently represents a hydrogen atom or a methyl group, and m, n, p and q each independently represents an integer of 1 to 10). 1 type or more chosen from the group which consists of a compound to be mentioned. Among these, it is preferable that the compound represented by Formula (Ic) is included.

As a preferable structure of the polymerizable compound represented by the general formula (Ic), both A ¹¹ and A ¹⁹ are preferably hydrogen atoms. Although the effect of the present invention is exhibited even in a compound in which these substituents A ¹¹ and A ¹⁹ are methyl groups, a compound in which a hydrogen atom is used is advantageous in that the polymerization rate becomes faster.

A ¹² and A ¹⁸ are preferably each independently a single bond or an alkylene group having 1 to 3 carbon atoms. The distance between the two polymerizable functional groups can be adjusted by independently changing the number of carbon atoms of the alkylene group in A ¹² and A ¹⁸ and A ¹⁵ . The feature of the compound represented by the general formula (Ic) is that the distance between the polymerizable functional groups (distance between the crosslinking points) is long, but if this distance is too long, the polymerization rate becomes extremely slow. Therefore, there is an upper limit on the distance between the polymerizable functional groups. On the other hand, the distance between the two side chains of A ¹³ and A ¹⁶ also affects the mobility of the main chain. That is, if the distance between A ¹³ and A ¹⁶ is short, the side chains A ¹³ and A ¹⁶ will interfere with each other, resulting in a decrease in mobility. Therefore, in the compound represented by the general formula (Ic), the distance between polymerizable functional groups is determined by the sum of A ¹² , A ¹⁸ , and A ¹⁵ , but among these, A ¹² and A ¹⁸ are made longer than A ¹² is made longer. It is preferable to lengthen ¹⁵ .

On the other hand, in the side chains A ¹³ , A ¹⁴ , A ¹⁶ and A ¹⁷ , it is preferable that the length of these side chains has the following aspect.

In the general formula (Ic), A ¹³ and A ¹⁴ are bonded to the same carbon atom of the main chain. When these lengths are different, the longer side chain is referred to as A ¹³ ( If the length and the length of ^{a 14} of a ¹³ are equal, one to one and ^{a 13).} Similarly, when the length of the length and A ¹⁷ of A ¹⁶ are different, if the length and the length of A ¹⁷ in the longer side chain of is referred to as A ¹⁶ (A ¹⁶ are equal, either the one and a ^16).

In the present application, such A ¹³ and A ¹⁶ are each independently a linear alkyl group having 2 to 20 carbon atoms (one or two or more methylene groups present in the linear alkyl group are oxygen As the atoms are not directly bonded to each other, each may be independently substituted with an oxygen atom, -CO-, -COO-, or -OCO-).
Preferably, each independently a linear alkyl group having 2 to 18 carbon atoms (one or two or more methylene groups present in the linear alkyl group are such that oxygen atoms are not directly bonded to each other, Each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-).
More preferably, each independently a linear alkyl group having 3 to 15 carbon atoms (one or two or more methylene groups present in the linear alkyl group are such that oxygen atoms are not directly bonded to each other). And each may be independently substituted with an oxygen atom, —CO—, —COO— or —OCO—.

  Since the side chain has higher mobility than the main chain, its presence contributes to improvement of the mobility of the polymer chain at low temperature, but as mentioned above, spatial interference occurs between the two side chains. On the contrary, motility decreases. In order to prevent such spatial interference between side chains, it is effective to increase the distance between the side chains and to shorten the side chain length within a necessary range.

Furthermore, for A ¹⁴ and A ¹⁷ , in the present application, each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (one or two or more methylene groups present in the alkyl group have an oxygen atom Each may be independently substituted with an oxygen atom, —CO—, —COO—, or —OCO— so that one or two or more hydrogen atoms present in the alkyl group are each independently May be substituted with a halogen atom or an alkyl group having 1 to 9 carbon atoms).
Preferably, each independently represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms (one or two or more methylene groups present in the alkyl group are independently represented as those in which oxygen atoms are not directly bonded to each other). An oxygen atom, -CO-, -COO- or -OCO- may be substituted).
More preferably, they are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (one or two or more methylene groups present in the alkyl group are independent as those in which oxygen atoms are not directly bonded to each other). May be substituted with an oxygen atom, -CO-, -COO- or -OCO-).
More preferably, they are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (one or two or more methylene groups present in the alkyl group are independent as those in which oxygen atoms are not directly bonded to each other). May be substituted with an oxygen atom, -CO-, -COO-, or -OCO-).

This A ¹⁴ and A ¹⁷ also, the possible length too long is not preferable for inducing the spatial interference between side chains. On the other hand, when A ¹⁴ and A ¹⁷ are alkyl chains having a short length, they can be side chains having high mobility and have a function of inhibiting the proximity of adjacent main chains. It is thought that it has an action to prevent interference between the main chains of the polymer and is considered to increase the mobility of the main chain. It can suppress the anchoring energy from increasing at a low temperature and stabilize the polymer. This is effective for improving the characteristics of the liquid crystal optical element in the low temperature range.

A ¹⁵ located between the two side chains is preferably longer in terms of changing the distance between the side chains and increasing the distance between the crosslinking points to lower the glass transition temperature. However to come formula compatibility with the liquid crystal composition has too high a molecular weight (I-c) compounds represented by is reduced when A ¹⁵ is too long, and the polymerization rate slows down too phase separation The length is naturally set to an upper limit because of adverse effects on the length.

Therefore, in the present invention, A ¹⁵ represents an alkylene group having 9 to 16 carbon atoms (in the methylene group of at least 1 to 5 carbon atoms present in the alkylene group, one of the hydrogen atoms in the methylene group is Independently substituted with a linear or branched alkyl group having 1 to 10 carbon atoms, wherein one or more methylene groups present in the alkylene group are such that oxygen atoms are not directly bonded to each other. And each may be independently substituted with an oxygen atom, —CO—, —COO— or —OCO—.

That is, in the present invention, the alkylene chain length of A ¹⁵ is preferably 9 to 16 carbon atoms. A ¹⁵ has a structure in which a hydrogen atom in an alkylene group is substituted with an alkyl group having 1 to 10 carbon atoms as a structural feature. The number of substitution of the alkyl group is 1 or more and 5 or less, preferably 1 to 3, and more preferably 2 or 3 substitutions. The number of carbon atoms of the alkyl group to be substituted is preferably 1 to 5, and more preferably 1 to 3.

  The compound represented by the general formula (Ia) is described in Tetrahedron Letters, Vol. 30, pp 4985, Tetrahedron Letters, Vol. 23, No. 6, pp 681-684, and Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 34, pp217-225 and the like.

For example, in the general formula (I-c), Compound A ¹⁴ and A ¹⁷ are hydrogen, a compound having a plurality of epoxy groups, polymerizable acrylic acid or methacrylic acid having an active hydrogen reactive with epoxy groups It can be obtained by reacting with a compound to synthesize a polymerizable compound having a hydroxyl group and then reacting with a saturated fatty acid.
Furthermore, by reacting a compound having a plurality of epoxy groups with a saturated fatty acid, synthesizing a compound having a hydroxyl group, and then reacting with a polymerizable compound such as an acrylate chloride having a group capable of reacting with a hydroxyl group. Can be obtained.

When the radically polymerizable compound is, for example, A ¹⁴ and A ^{17 in} the general formula (Ic) are alkyl groups and A ¹² and A ¹⁸ are methylene groups having 1 carbon atom, an oxetane group is selected. A method of reacting a compound having a plurality of compounds with a fatty acid chloride or a fatty acid capable of reacting with an oxetane group, and further reacting with a polymerizable compound having active hydrogen such as acrylic acid, a compound having one oxetane group, It can be obtained by a method of reacting a polyvalent fatty acid chloride or a fatty acid capable of reacting with an oxetane group, and further reacting with a polymerizable compound having active hydrogen such as acrylic acid.

In the case where A ¹² and A ¹⁸ in the general formula (Ic) are an alkylene group having 3 carbon atoms (propylene group; —CH ₂ CH ₂ CH ₂ —), a plurality of furan groups are used instead of the oxetane group. It can obtain by using the compound which has. Further, when A ¹² and A ¹⁸ in the general formula (Ic) are an alkylene group having 4 carbon atoms (butylene group; —CH ₂ CH ₂ CH ₂ CH ₂ —), a pyran group is used instead of the oxetane group. It can obtain by using the compound which has two or more.

<Polymerizable liquid crystal compound (II)>
The polymerizable liquid crystal compound (II) used in the present invention has the following general formula (II-a):

(In Formula (II-a), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and C ⁴ and C ⁵ each independently represent a 1,4-phenylene group or 1,4-cyclohexene. Xylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyridazine-3,6-diyl group, 1,3-dioxane-2,5-diyl group, cyclohexene-1,4-diyl Group, decahydronaphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group or indane-2,5-diyl group (these groups Of which 1,4-phenylene group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group and indan-2,5-diyl group are unsubstituted or Fluorine atom as a substituent, methyl 1 group, or two or more of a ru group, a trifluoromethyl group, or a trifluoromethoxy group).
Z ³ and Z ⁵ are each independently a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups present in the alkylene group are such that oxygen atoms are not directly bonded to each other) Each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms present in the alkylene group are each independently a fluorine atom, Which may be substituted with a methyl group or an ethyl group)
Z ⁴ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —CH ₂ CH ₂ O—, —OCH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ O—, _{-OCH 2 CH 2 CH 2 -,} - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH = CH -, - C≡C- _{, -CF 2 O -, - OCF} 2 -, - COO- or an -OCO-,
n ² represents 0, 1 or 2. However, when n ² represents 2, a plurality of C ⁴ and Z ⁴ may be the same or different. ),

  Formula (II-b)

(In Formula (II-b), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and C ⁶ represents a 1,4-phenylene group, a 1,4-cyclohexylene group, pyridine-2, 5-diyl group, pyrimidine-2,5-diyl group, pyridazine-3,6-diyl group, 1,3-dioxane-2,5-diyl group, cyclohexene-1,4-diyl group, decahydronaphthalene-2 , 6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group or indane-2,5-diyl group (among these groups, 1,4-phenylene Group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group and indan-2,5-diyl group are unsubstituted or substituted with fluorine atom, methyl Group, trifluoromethyl Or a trifluoromethoxy group may have one or two or more.) Represent,
C ⁷ is benzene-1,2,4-triyl group, benzene-1,3,4-triyl group, benzene-1,3,5-triyl group, cyclohexane-1,2,4-triyl group, cyclohexane-1 , 3,4-triyl group or cyclohexane-1,3,5-triyl group,
Z ⁶ and Z ⁸ are each independently a single bond or an alkylene group having 1 to 15 carbon atoms (one or two or more methylene groups present in the alkylene group are such that oxygen atoms are not directly bonded to each other) Each independently may be substituted with an oxygen atom, -CO-, -COO- or -OCO-, and one or more hydrogen atoms present in the alkylene group are each independently a fluorine atom, Which may be substituted with a methyl group or an ethyl group)
Z ⁷ is a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —CH ₂ CH ₂ O—, —OCH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ O—, _{-OCH 2 CH 2 CH 2 -,} - CH 2 CH 2 OCO -, - COOCH 2 CH 2 -, - CH 2 CH 2 COO -, - OCOCH 2 CH 2 -, - CH = CH -, - C≡C- _{, -CF 2 O -, - OCF} 2 -, - COO- or an -OCO-,
n ³ represents 0, 1 or 2. However, when n ³ represents 2, a plurality of C ⁶ and Z ⁷ may be the same or different. ),

  And general formula (II-c)

(In the formula (II-c), R ⁷ represents a hydrogen atom or a methyl group, and the 6-membered rings T ¹ , T ^2, and T ³ are each independently,

(Where m represents an integer of 1 to 4),
n ⁴ represents an integer of 0 or 1,
Y ^{0, Y 1} and ^{Y 2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) p1O -, - O (CH 2) p1 -, - COO -, - OCO -, - C ≡C—, —CH═CH—, —CF═CF—, — (CH ₂ ) ₄ —, —CH═CHCH ₂ CH ₂ — or —CH ₂ CH ₂ CH═CH— (where p1 is 1 to 1) 20 represents any integer of 20.), Y ³ represents a single bond, —O—, —COO—, or —OCO—,
R ⁸ is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Represents a hydrocarbon group. 1) or more selected from the group consisting of

  Specific examples of the compound represented by the general formula (II-a) include general formulas (II-d), (II-e), and (II-f).

(In the formulas (II-d), (II-e) and (II-f), m ¹ represents 0 or 1, Y ¹¹ and Y ¹² are each independently a single bond, —O—, —COO. -Or -OCO-
Y ¹³ and Y ¹⁴ each independently represent —COO— or —OCO—, Y ¹⁵ and Y ¹⁶ each independently represent —COO— or —OCO—, and r and s each independently represent 2 to 2 An integer of 14 is represented. The 1,4-phenylene group present in the formula is unsubstituted or can have one or more fluorine atoms, methyl groups, trifluoromethyl groups or trifluoromethoxy groups as substituents. It is preferable to use a compound represented by any one of (2), since an optically anisotropic body excellent in mechanical strength and heat resistance can be obtained.

  Furthermore, specific examples of the compound represented by the general formula (II-a) can be listed in the following (II-1) to (II-10).

(Wherein j and k each independently represents an integer of 2 to 14)

  Specific examples of the compound represented by any one of the general formulas (II-d), (II-e), and (II-f) are listed in the following (II-11) to (II-19). Can do.

  (Wherein j and k each independently represents an integer of 2 to 14)

  Moreover, the compound represented by general formula (II-g) is also mentioned.

(In formula (II-g), Y ¹¹ and Y ¹² each independently represent a single bond, —O—, —COO— or —OCO—, and Y ¹⁵ and Y ¹⁶ each independently represent —COO— or represents -OCO-, r and s are ^{.Z 10} represent each independently an integer of 2 to 14 is a group represented by the following formula.

The 1,4-phenylene group present in the formula is unsubstituted or can have one or more fluorine atoms, methyl groups, trifluoromethyl groups or trifluoromethoxy groups as substituents. )
Among these, compounds represented by the following formulas (II-g-1) to (II-g-2) are preferable.

<Photopolymerizable monomer exhibiting chirality>
The photopolymerizable monomer (polymerizable compound) is not limited to the above-described achiral substance, and a chiral substance may be used. As the photopolymerizable monomer exhibiting chirality, for example, a polymerizable compound represented by the following general formula (II-x) or (II-y) can be used.

In the above formula (II-x) and formula (II-y), X represents a hydrogen atom or a methyl group. N ⁴ represents an integer of 0 or 1, and n ⁵ represents an integer of 0, 1 or 2. However, when n ⁵ represents 2, a plurality of T ⁴ and Y ⁴ may be the same or different.
In addition, 6-membered rings T ¹ , T ² , T ³ and T ⁴ represent substituents having a 6-membered ring structure such as a 1,4-phenylene group and a trans-1,4-cyclohexylene group. However, the 6-membered rings T ¹ , T ² , T ³ are not limited to these substituents, and the following structures

As long as it has any one kind of substituent among the substituents having the above, they may be the same as or different from each other. In addition, in the said substituent, m shows the integer of 1-4.
T ⁵ in the formula (II-y) is benzene-1,2,4-triyl group, benzene-1,3,4-triyl group, benzene-1,3,5-triyl group, cyclohexane-1, It represents a cyclic trivalent group such as a 2,4-triyl group, a cyclohexane-1,3,4-triyl group, or a cyclohexane-1,3,5-triyl group.

Y ¹ , Y ² , and Y ⁴ in formula (II-x) and formula (II-y) are each independently a linear or branched chain having 1 to 10 carbon atoms. An alkylene group in which one CH ₂ group or _two non-adjacent CH ₂ groups are represented by —O—, —S—, —CO—O— or —O—CO—. May be substituted, single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CH—, —CF _{= CF -, - (CH 2} ) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH = CHCH 2 CH 2 -, or _-CH 2 _CH 2 _CH = CH- May be included. In addition, it may or may not contain an asymmetric carbon atom. That is, Y ¹ and Y ² may be the same or different as long as they have any of the structures described above.
Y ⁰ and Y ³ represent a single bond, —O—, —OCO—, or —COO—.
Z ¹¹ represents an alkylene group having 3 to 20 carbon atoms having an asymmetric carbon atom and having a branched chain structure.
Z ²¹ represents an alkylene group having 1 to 20 carbon atoms and may or may not contain an asymmetric carbon atom.

  The polymerizable compound used in the present invention may be used in any one or a combination of two or more of the above (I), (II), (II-x), and (II-y).

  As a polymerization method when the liquid crystal composition of the present invention contains a polymerizable compound, radical polymerization, anionic polymerization, cationic polymerization, or the like can be used, but polymerization is preferably performed by radical polymerization.

As the radical polymerization initiator, a thermal polymerization initiator or a photopolymerization initiator can be used, but a photopolymerization initiator is preferable. Specifically, the following compounds are preferable.
Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- ( 2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl- Acetophenone series such as 2-dimethylamino-1- (4-morpholinophenyl) -butanone;

Benzoins such as benzoin, benzoin isopropyl ether and benzoin isobutyl ether;
Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide;
Benzyl, methylphenylglyoxyesters;
Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4' -Benzophenone series such as tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone;
Thioxanthone systems such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone;
Aminobenzophenone series such as Michler's ketone and 4,4'-diethylaminobenzophenone;
10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like are preferable. Of these, benzyldimethyl ketal is most preferred.

  In the present invention, a polyfunctional liquid crystalline monomer may be added in addition to the polymerizable liquid crystal compound (II). As this polyfunctional liquid crystalline monomer, acryloyloxy group, methacryloyloxy group, acrylamide group, methacrylamide group, epoxy group, vinyl group, vinyloxy group, ethynyl group, mercapto group, maleimide group, RCH = CHCOO- (wherein R represents fluorine or a hydrocarbon group having 1 to 18 carbon atoms) is exemplified, among which acryloyloxy group, methacryloyloxy group, epoxy group, mercapto group, and vinyloxy group are preferable. A methacryloyloxy group or an acryloyloxy group is particularly preferred, and an acryloyloxy group is most preferred.

As the molecular structure of the polyfunctional liquid crystalline monomer, there are at least two liquid crystal skeletons having two or more ring structures, a polymerizable functional group, and a flexible group for connecting the liquid crystal skeleton and the polymerizable functional group. Those having three flexible groups are more preferable. Examples of the flexible group include an alkylene spacer group represented by — (CH ₂ ) _n — (where n represents an integer) or — (Si (CH ₃ ) ₂ —O) _n — (where n is A siloxane spacer group represented by the formula (4), and an alkylene spacer group is preferred. Bonds such as —O—, —COO—, and —CO— may be present in the bonding portion between these flexible groups and the liquid crystal skeleton or polymerizable functional group.

The liquid crystal / monomer composite material of the present invention is represented by the compound represented by the general formula (i), the compound having the optically active substance represented by the general formula (ii), and the general formula (II). It is preferable to contain a polymerizable monomer.
The composition ratio of the compound represented by the general formula (i), the total of the compounds having the optically active substance represented by the general formula (ii), and the polymerizable monomer represented by the general formula (II) is When the composition ratio of the polymerizable monomer is too large, the characteristics as the liquid crystal composition are impaired, so that an optimum composition ratio exists. Specifically, the total of the compound represented by the general formula (i) and the compound having the optically active substance represented by the general formula (ii) is 92% by mass to 99.9% by mass. The content is preferably 92% by mass to 99% by mass, and more preferably 94% by mass to 98% by mass.

The liquid crystal composition used in the present invention is represented by the compound represented by the general formula (X-1) and the general formula (X-6) as the compound represented by the general formula (i). It is preferable to contain a compound.
The liquid crystal composition used in the present invention is represented by the compound represented by the general formula (i-1) or the general formula (i-3) as the compound represented by the general formula (i). It is also preferable to contain the compound and the compound represented by the said general formula (i-4).
The liquid crystal composition used in the present invention is represented by the compound represented by the general formula (i-1) or the general formula (i-2) as the compound represented by the general formula (i). It is also preferable to contain the compound represented by the said general formula (i-3), and the compound represented by the said general formula (i-4).
The liquid crystal composition used in the present invention contains 50% by mass to 90% by mass of the compound represented by the general formula (i), and 5% by mass of the optically active substance represented by the general formula (ii). It is preferable to contain 40% by mass and 1% by mass to 6% by mass of the polymerizable monomer represented by the general formula (II).
The liquid crystal composition used in the present invention preferably contains a polymerization initiator. When the polymerization initiator is contained, the content other than the polymerization initiator is 98% by mass to 99.9% by mass, and the polymerization initiator is 0.1% by mass to 2% by mass. preferable.

[Liquid Crystal / Polymer Composite Material]
The liquid crystal / polymer composite material of the present invention is obtained by polymerizing the polymerizable monomer in the liquid crystal / monomer composite material described above. The polymerization reaction is preferably performed in a temperature range in which the liquid crystal / monomer composite material exhibits a chiral smectic C phase. The liquid crystal / polymer composite material obtained by such a polymerization reaction has a liquid phase-chiral nematic phase-chiral smectic C phase. It is preferable that the phase sequence is shown.
By adding a polymerizable monomer, a liquid crystal / monomer composite material showing a phase sequence of liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase is polymerized by polymerizing the polymerizable monomer in the composite material. The reason why the phase sequence of phase-chiral nematic phase-chiral smectic C phase is exhibited is not clear, but the polymerizable monomer is polymerized by heat or active energy rays such as ultraviolet rays and electron beams, Accordingly, it is considered that the liquid crystal composition is phase-separated and returns to the original state of the liquid crystal composition of liquid phase-chiral nematic phase-chiral smectic C phase, which is a phase sequence of the liquid crystal composition.

[Optical element]
The optical element of the present invention contains the above-described liquid crystal / polymer composite material of the present invention. The liquid crystal / polymer composite material is preferably obtained by polymerizing a polymerizable monomer in a temperature range in which the liquid crystal / monomer composite material exhibits a chiral smectic C phase.
The optical element of the present invention is preferably an optical element having a liquid crystal layer interposed between a pair of substrates and an electrode portion for applying a voltage to the liquid crystal layer on the inner surface of at least one substrate.
That is, the optical element of the present invention has a pair of pixel electrodes and a common electrode on at least one of a pair of substrates on which two polarizing plates whose polarization planes are orthogonal to each other are arranged, and a liquid crystal layer between the pair of substrates. Is preferably sandwiched. The electric field applied in the display element is preferably applied in the horizontal direction in a normal layer. As an electrode structure for realizing such an electric field, an electrode having a comb structure such as an IPS (In-Plane Switching) method. A structure is preferred. The direction of the horizontal electric field applied in the horizontal direction of the layer normal by bending the structure of the comb-shaped electrode such as S-IPS (Super IPS), AS-IPS (Advanced Super IPS), IPS-Pro (IPS-Products), etc. It is preferable from the viewpoint of lowering the drive voltage, improving the image quality, increasing the brightness, and increasing the brightness. The comb electrode can be a metal electrode, but in order to increase the light utilization efficiency of the electrode portion, it is preferable to use a transparent electrode such as ITO, indium gallium oxide zinc (IGZO), graphene or the like. . It is preferable to reduce the distribution of the electric field intensity without a display element from the viewpoints of lowering the driving voltage, improving the response speed, increasing the contrast, and improving the image quality. As a method for reducing the distribution of the electric field strength, a configuration in which a pair of pixel electrodes and a common electrode are provided on both of the pair of substrates can be employed.

Further, the liquid crystal layer applies an alternating electric field to a liquid crystal composition containing a polymerizable monomer in a temperature range in which the liquid crystal / monomer composite material exhibits a chiral smectic C phase, and is irradiated with ultraviolet rays or electron beams. It is preferable that the polymerizable monomer has a high molecular weight.
The optical element of the present invention is an optical element having a liquid crystal layer interposed between a pair of substrates and having an electrode portion for applying a voltage to the liquid crystal layer on the inner surface of at least one substrate, the liquid crystal layer comprising: A liquid crystal composition containing a polymerizable monomer is applied with an alternating electric field in a state showing a chiral smectic C phase, irradiated with ultraviolet rays or an electron beam, and then heated to polymerize the polymerizable monomer. It is preferable that it is the structure.

  The two substrates of the liquid crystal cell used for the optical element can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.

  The color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT or a thin film diode may be provided on the substrate.

  The said board | substrate is made to oppose so that a transparent electrode layer may become an inner side. In that case, you may adjust the space | interval of a board | substrate through a spacer. At this time, it is preferable to adjust so that the thickness of the light control layer obtained may be set to 1-100 micrometers. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d is adjusted so that the contrast is maximized. It is preferable to make it 2 or 1/4. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.

  As a method of sandwiching the liquid crystal / monomer composite material of the present invention between two substrates, a normal vacuum injection method or an ODF method can be used. However, in the vacuum injection method, there is a problem that an injection mark remains instead of a drop mark. In this invention, it can use more suitably for the optical element manufactured using ODF method. In the optical element manufacturing process of the ODF method, a sealant such as epoxy photothermal combination curing is drawn on a backplane or frontplane substrate using a dispenser in a closed-loop bank shape, and deaerated in it. An optical element can be manufactured by bonding a front plane and a back plane after dropping a predetermined amount of a liquid crystal / monomer composite material. The liquid crystal / monomer composite material of the present invention can be suitably used because the liquid crystal / monomer composite material can be stably dropped in the ODF process.

  As a method for polymerizing the polymerizable monomer, in order to obtain good alignment performance of the liquid crystal, an appropriate polymerization rate is desirable. Therefore, ultraviolet rays or electron beams, which are active energy rays, are irradiated singly or in combination or sequentially. The method of polymerizing by is preferred. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. In addition, when the polymerization is performed with the liquid crystal / monomer composite material sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency to the active energy rays. . In addition, it is preferable to apply an alternating electric field to the liquid crystal composition containing a polymerizable monomer in a temperature range in which the liquid crystal / monomer composite material exhibits a chiral smectic C phase, and to irradiate ultraviolet rays or electron beams. The alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 100 Hz to 5 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In a horizontal electric field type MVA mode liquid crystal display element, the pretilt angle is preferably controlled from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.

The temperature at the time of irradiation is preferably in a temperature range in which the liquid crystal / monomer composite material exhibits a chiral smectic C phase. Polymerization is preferably performed at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet-rays to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use an ultraviolet-ray as needed. Intensity of ultraviolet irradiation is ^preferably from ^{0.1mW / cm 2 ~100W / cm 2} , 2mW / cm 2 ~50W / cm 2 is more preferable. The amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm ² . When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiated ultraviolet rays, but is preferably from 10 seconds to 3600 seconds, and more preferably from 10 seconds to 600 seconds.

  Moreover, it is preferable to polymerize the polymerizable monomer by applying an alternating electric field in a state showing a chiral smectic C phase, and by heating after irradiation with ultraviolet rays or electron beams. As heating temperature, 40 to 160 degreeC is preferable, 50 to 140 degreeC is more preferable, and 60 to 120 degreeC is especially preferable.

  The optical element of the present invention is useful with improved transmittance when a voltage is applied.

  EXAMPLES The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.

[Example 1]
A composition represented by the formula (LC-1) was prepared as the ferroelectric liquid crystal composition (LC-1). A composition represented by the formula (Mo-1) was prepared as a radical polymerizable composition (Mo-1).
A polymer-stabilized ferroelectric liquid crystal composition (LCM-1) composed of 94% of a ferroelectric liquid crystal composition (LC-1) and 6% of a radical polymerizable composition (Mo-1) was prepared.
The phase sequence of the ferroelectric liquid crystal composition (LC-1) shows a liquid phase-chiral nematic phase-chiral smectic C phase, and the phase sequence of the polymer-stabilized ferroelectric liquid crystal composition (LCM-1) is A phase sequence of liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase was shown. The tilt angles (θ) of the ferroelectric liquid crystal composition (LC-1) and the polymer-stabilized ferroelectric liquid crystal composition (LCM-1) were 32.6 degrees and 27.3 degrees, respectively.
A parallel rubbing alignment cell with ITO coated with a polyimide alignment film with a cell gap of 2 μm was used so that liquid crystal uniaxial alignment (homogeneous alignment) was obtained.
The polymer-stabilized ferroelectric liquid crystal composition (LCM-1) was heated above the chiral nematic phase transition and injected into the glass cell by vacuum injection.
After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). While applying a rectangular wave of 8 V at a frequency of 1 KHz to the cell, irradiation with ultraviolet light having an irradiation intensity of 5 mW / cm ² through an ultraviolet cut filter L-37 (manufactured by Hoya Candeo Optronics) was performed for 300 seconds. As a result, the polymerizable compound of the polymer-stabilized ferroelectric liquid crystal composition was polymerized to obtain a polymer component-stabilized liquid crystal display element.
The transmittance was 0% when the two polarizing plates were perpendicular to each other and 100% when they were parallel, and the electro-optical characteristics were measured. The results are shown in Table 1.

  It was confirmed that the liquid crystal display device of Example 1 can achieve high transmittance.

[Comparative Example 1]
A composition represented by the formula (LC-2) was prepared as the ferroelectric liquid crystal composition (LC-2).
A polymer-stabilized ferroelectric liquid crystal composition (LCM-2) comprising 94% of a ferroelectric liquid crystal composition (LC-2) and 6% of a radical polymerizable composition (Mo-1) was prepared. The phase sequence of LC-2 indicates a liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase, and the phase sequence of LCM-2 is liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C. The phase sequence of the phases is shown.
Using a ferroelectric liquid crystal material (LCM-2), an element was fabricated in the same manner as in Example 1, and the transmittance (saturation value) was measured. The results are shown in Table 2.

  The liquid crystal display device of Comparative Example 1 had a lower transmittance than the liquid crystal display device of Example 1.

[Example 2]
A composition represented by the formula (LC-3) was prepared as a ferroelectric liquid crystal composition (LC-3). A composition represented by the formula (Mo-1) was prepared as a radical polymerizable composition (Mo-1).
A polymer-stabilized ferroelectric liquid crystal composition (LCM-3) comprising 94% of a ferroelectric liquid crystal composition (LC-3) and 6% of a radical polymerizable composition (Mo-1) was prepared.
The phase sequence of the ferroelectric liquid crystal composition (LC-3) indicates a liquid phase-chiral nematic phase-chiral smectic C phase, and the phase sequence of the polymer-stabilized ferroelectric liquid crystal composition (LCM-3) is: A phase sequence of liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase was shown.
The tilt angles (θ) of the ferroelectric liquid crystal composition (LC-3) and the polymer-stabilized ferroelectric liquid crystal composition (LCM-3) were 33.4 degrees and 28.2 degrees, respectively.
A parallel rubbing alignment cell with ITO coated with a polyimide alignment film with a cell gap of 2 μm was used so that liquid crystal uniaxial alignment (homogeneous alignment) was obtained.
The polymer-stabilized ferroelectric liquid crystal composition (LCM-3) was heated above the chiral nematic phase transition and injected into the glass cell by vacuum injection.
After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). While applying a rectangular wave of 8 V at a frequency of 1 KHz to the cell, irradiation with ultraviolet light having an irradiation intensity of 5 mW / cm ² through an ultraviolet cut filter L-37 (manufactured by Hoya Candeo Optronics) was performed for 300 seconds. As a result, the polymerizable compound of the polymer-stabilized ferroelectric liquid crystal composition was polymerized to obtain a polymer component-stabilized liquid crystal display element.
The transmittance was 0% when the two polarizing plates were perpendicular to each other and 100% when they were parallel, and the electro-optical characteristics were measured. The results are shown in Table 3.

  It was confirmed that the liquid crystal display device of Example 2 can achieve high transmittance.

[Example 3]
A composition represented by the formula (LC-4) was prepared as a ferroelectric liquid crystal composition (LC-4). A composition represented by the formula (Mo-1) was prepared as a radical polymerizable composition (Mo-1).
A polymer-stabilized ferroelectric liquid crystal composition (LCM-4) comprising 94% of a ferroelectric liquid crystal composition (LC-4) and 6% of a radical polymerizable composition (Mo-1) was prepared.
The phase sequence of the ferroelectric liquid crystal composition (LC-4) shows a liquid phase-chiral nematic phase-chiral smectic C phase, and the phase sequence of the polymer-stabilized ferroelectric liquid crystal composition (LCM-4) is A phase sequence of liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase was shown.
The tilt angles (θ) of the ferroelectric liquid crystal composition (LC-4) and the polymer-stabilized ferroelectric liquid crystal composition (LCM-4) were 38.3 degrees and 33.1 degrees, respectively.
A parallel rubbing alignment cell with ITO coated with a polyimide alignment film with a cell gap of 2 μm was used so that liquid crystal uniaxial alignment (homogeneous alignment) was obtained.
The polymer-stabilized ferroelectric liquid crystal composition (LCM-4) was heated above the chiral nematic phase transition and injected into the glass cell by vacuum injection.
After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). While applying a rectangular wave of 8V at a frequency of 1 KHz to the cell, irradiate it with ultraviolet light having an irradiation intensity of 5 mW / cm ² through an ultraviolet cut filter L-37 (manufactured by Hoya Candeo Optronics) for 300 seconds, and further at 80 ° C. for 48 hours. The heat treatment was performed. As a result, the polymerizable compound of the polymer-stabilized ferroelectric liquid crystal composition was polymerized to obtain a polymer component-stabilized liquid crystal display element.
The transmittance was 0% when the two polarizing plates were perpendicular to each other and 100% when they were parallel, and the electro-optical characteristics were measured. The results are shown in Table 4.

  It was confirmed that the liquid crystal display device of Example 3 can achieve high transmittance.

[Comparative Example 2]
A composition represented by the formula (LC-5) was prepared as a ferroelectric liquid crystal composition (LC-5). A composition represented by the formula (Mo-1) was prepared as a radical polymerizable composition (Mo-1).
A polymer-stabilized ferroelectric liquid crystal composition (LCM-5) composed of 94% of a ferroelectric liquid crystal composition (LC-5) and 6% of a radical polymerizable composition (Mo-1) was prepared.
The phase sequence of the ferroelectric liquid crystal composition (LC-5) is a liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase,
The phase sequence of the polymer-stabilized ferroelectric liquid crystal composition (LCM-5) was a phase sequence of liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase.
Using a ferroelectric liquid crystal material (LCM-5), an element was fabricated in the same manner as in Example 3, and the transmittance (saturation value) was measured. The results are shown in Table 5.

    The liquid crystal display device of Comparative Example 2 had a lower transmittance than the liquid crystal display device of Example 3.

[Example 4]
A composition represented by the formula (LC-5) was prepared as a ferroelectric liquid crystal composition (LC-5). A composition represented by the formula (Mo-1) was prepared as a radical polymerizable composition (Mo-1).
A polymer-stabilized ferroelectric liquid crystal composition (LCM-5) composed of 94% of a ferroelectric liquid crystal composition (LC-5) and 6% of a radical polymerizable composition (Mo-1) was prepared.
The phase sequence of the ferroelectric liquid crystal composition (LC-5) indicates a liquid phase-chiral nematic phase-chiral smectic C phase, and the phase sequence of the polymer-stabilized ferroelectric liquid crystal composition (LCM-5) is: A phase sequence of liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase was shown.
The tilt angles (θ) of the ferroelectric liquid crystal composition (LC-5) and the polymer-stabilized ferroelectric liquid crystal composition (LCM-5) were 37.7 degrees and 32.5 degrees, respectively.
A parallel rubbing alignment cell with ITO coated with a polyimide alignment film with a cell gap of 2 μm was used so that liquid crystal uniaxial alignment (homogeneous alignment) was obtained.
The polymer-stabilized ferroelectric liquid crystal composition (LCM-5) was heated above the chiral nematic phase transition and injected into the glass cell by vacuum injection.
After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). While applying a rectangular wave of 8 V at a frequency of 1 KHz to the cell, irradiation with ultraviolet rays having an irradiation intensity of 5 mW / cm ² through an ultraviolet cut filter L-37 (manufactured by Hoya Candeo Optronics Co., Ltd.) is performed for 300 seconds, and further at 80 ° C. for 48 hours. The heat treatment was performed. As a result, the polymerizable compound of the polymer-stabilized ferroelectric liquid crystal composition was polymerized to obtain a polymer component-stabilized liquid crystal display element.
The transmittance was 0% when the two polarizing plates were perpendicular to each other and 100% when they were parallel, and the electro-optical characteristics were measured. The results are shown in Table 6.

  It was confirmed that the liquid crystal display device of Example 4 can achieve high transmittance.

[Example 5]
A composition represented by the formula (Mo-2) was prepared as a radical polymerizable composition (Mo-2).
A polymer-stabilized ferroelectric liquid crystal composition (LCM-5) composed of 94% of a ferroelectric liquid crystal composition (LC-3) and 6% of a radical polymerizable composition (Mo-2) was prepared.
The phase sequence of the ferroelectric liquid crystal composition (LC-5) indicates a liquid phase-chiral nematic phase-chiral smectic C phase, and the phase sequence of the polymer-stabilized ferroelectric liquid crystal composition (LCM-5) is: A phase sequence of liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase was shown.
The tilt angles (θ) of the ferroelectric liquid crystal composition (LC-3) and the polymer-stabilized ferroelectric liquid crystal composition (LCM-5) were 33.4 ° and 27.9 °, respectively.
A parallel rubbing alignment cell with ITO coated with a polyimide alignment film with a cell gap of 2 μm was used so that liquid crystal uniaxial alignment (homogeneous alignment) was obtained.
The polymer-stabilized ferroelectric liquid crystal composition (LCM-3) was heated above the chiral nematic phase transition and injected into the glass cell by vacuum injection.
After the injection, the glass cell was taken out and the inlet was sealed with a sealing agent 3026E (manufactured by ThreeBond). While applying a rectangular wave of 8 V at a frequency of 1 KHz to the cell, irradiation with ultraviolet light having an irradiation intensity of 5 mW / cm ² through an ultraviolet cut filter L-37 (manufactured by Hoya Candeo Optronics) was performed for 300 seconds. As a result, the polymerizable compound of the polymer-stabilized ferroelectric liquid crystal composition was polymerized to obtain a polymer component-stabilized liquid crystal display element.
The transmittance was 0% when the two polarizing plates were perpendicular to each other and 100% when they were parallel, and the electro-optical characteristics were measured. The results are shown in Table 7.

  It was confirmed that the liquid crystal display device of Example 5 can achieve high transmittance.

Claims (7)

A liquid crystal / polymer composite material obtained by polymerizing a polymerizable monomer in a liquid crystal / monomer composite material containing a liquid crystal composition and a polymerizable monomer,
The liquid crystal composition exhibits a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase, and when the polymerizable monomer is added to the liquid crystal composition, the liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase shows the phase sequence of,
A liquid crystal / polymer composite material characterized by showing a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase . An optical element comprising the liquid crystal / polymer composite material according to claim 1 . It is a manufacturing method of the optical element according to claim 2,
Method for manufacturing an optical element comprising the step of said liquid crystal monomers composite obtain chiral smectic C phase by polymerizing the polymerizable monomer in the temperature range showing the liquid crystal-polymer composite. It is a manufacturing method of the optical element according to claim 3,
The optical element has a liquid crystal layer interposed between a pair of substrates , and has an electrode portion for applying a voltage to the liquid crystal layer on the inner surface of at least one substrate ,
By applying an alternating electric field in a temperature range in which the liquid crystal / monomer composite material exhibits a chiral smectic C phase to a liquid crystal composition containing a polymerizable monomer, the polymerizable monomer is increased by irradiating ultraviolet rays or electron beams. A method for producing an optical element , comprising a step of molecularizing the liquid crystal layer . It is a manufacturing method of the optical element according to claim 4,
A liquid crystal composition containing a polymerizable monomer is applied with an alternating electric field in a state showing a chiral smectic C phase, irradiated with ultraviolet rays or an electron beam, and then heated to polymerize the polymerizable monomer. The manufacturing method of an optical element including the process used as the said liquid-crystal layer . Liquid crystal / polymer composite material showing a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase obtained by polymerizing a polymerizable monomer in a liquid crystal / monomer composite material containing a liquid crystal composition and a polymerizable monomer A manufacturing method of
The liquid crystal composition exhibits a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase, and when the polymerizable monomer is added to the liquid crystal composition, the liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase Shows the phase sequence of
A method for producing a liquid crystal / polymer composite material comprising a step of irradiating the liquid crystal / monomer composite material with ultraviolet rays or an electron beam. Liquid crystal / polymer composite material showing a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase obtained by polymerizing a polymerizable monomer in a liquid crystal / monomer composite material containing a liquid crystal composition and a polymerizable monomer A manufacturing method of
The liquid crystal composition exhibits a phase sequence of liquid phase-chiral nematic phase-chiral smectic C phase, and when the polymerizable monomer is added to the liquid crystal composition, the liquid phase-chiral nematic phase-chiral smectic A phase-chiral smectic C phase Shows the phase sequence of
A method for producing a liquid crystal / polymer composite material comprising a step of heating the liquid crystal / monomer composite material after being irradiated with ultraviolet rays or an electron beam.