JP2021147410A - Polymerizable liquid crystal compound, polymerizable liquid crystal composition, liquid crystal polymer film, polarizing plate, and display element - Google Patents

Abstract

To improve the optical properties, in particular the front contrast, of a liquid crystal polymer film made from a polymerizable liquid crystal composition, thereby improving the display quality of a display element including the liquid crystal polymer film.MEANS FOR SOLVING THE PROBLEM: According to a discovery by the inventors, a liquid crystal polymer film is made from a polymerizable liquid crystal composition including a polymerizable liquid crystal compound having benzochromenone or a derivative thereof as its skeleton, leading to improvement in the optical properties, in particular the front contrast.SELECTED DRAWING: None

Description

The present disclosure relates to polymerizable liquid crystal compounds, polymerizable liquid crystal compositions, and liquid crystal polymerized films for obtaining a retardation film.

The liquid crystal polymerized film produced by polymerizing the polymerizable liquid crystal composition can be used as a material for a film having an optically anisotropic film or a display element having an element.

For example, a liquid crystal display device uses a retardation film for displaying a high-quality image. Since the liquid crystal polymer film exhibits birefringence, it can be used as a retardation film. Conventionally, a stretched polymer film exhibiting birefringence has been used as a retardation film. A retardation film using liquid crystal polymerized films has been studied for the purpose of facilitating film formation, thinning the film thickness, and improving durability.

Patent Document 1 describes liquid crystal polymerized films immobilized in the smectic phase. Patent Document 2 describes liquid crystal polymer films made from a polymerizable liquid crystal compound having a specific substituent at the lateral position.

Japanese Unexamined Patent Publication No. 2016-051178 International Publication No. 2018/030190

The disclosed problem is to improve the display quality of the display element incorporating the liquid crystal polymerized film by improving the optical properties of the liquid crystal polymerized film made from the polymerizable liquid crystal polymer composition, particularly improving the front contrast. be.

The inventors have found that when liquid crystal polymerized films are prepared from a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a skeleton of benzochromenone or a derivative thereof, the optical properties are improved, particularly the front contrast is improved. rice field.

The aspects to be disclosed are as follows.
[1] A polymerizable liquid crystal compound represented by the formula (1).

In equation (1),
A ¹ and A ² are independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, or naphthalene-2,6-diyl. , In this 1,4-phenylene or naphthalene-2,6-diyl, at least one hydrogen is fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, carbon number 1 May be replaced with ~ 5 alkoxycarbonyl, or 1-5 carbon alkanoyl;
X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are independently hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, alkyl with 1 to 12 carbon atoms, and 1 to 12 carbon atoms. Alkoxy, an alkoxycarbonyl having 1 to 12 carbon atoms, or an alkanoyl having 1 to 12 carbon atoms, and in this alkyl, alkoxy, alkoxycarbonyl, and alkanoyl, at least one -CH ₂ − is -O-, -CO-. , Or may be replaced with -S-;
Z ¹ and Z ² are independently single-bonded, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -OCH ₂ CH ₂ O-, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, -COOCH ₂ CH _2- , -CH = CH-, -N = CH-, -CH = N-, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, -N = N- , Or -C≡C-;
m and n are independently integers from 0 to 3;
R ¹ and R ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 1 to 12 carbon atoms, A hydrocarbylene ester having 1 to 12 carbon atoms, or a group represented by the formula (2), wherein at ^{least one of R 1} and R ² is a group represented by the formula (2).

In equation (2),
Y ¹ is a single bond, -O-, -COO-, -OCO-, or -OCOO-;
Q ¹ is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one −CH ₂ − is −O−, −COO−, −OCO−, −CH = CH−, or −CH≡ May be replaced by CH-;
P is a polymerizable functional group represented by any one of the formulas (P-1) to (P-9). )

(In equations (P-1) to (P-9),
R ³ is independently hydrogen, halogen, methyl, ethyl or trifluoromethyl.
.. )

[2] A ¹ and A ² are independently 1,4-phenylene or 1,4-cyclohexylene, in which at least one hydrogen is fluorine, trifluoromethyl, carbon. May be replaced with 21-5 alkyl;
X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ are independently hydrogen or alkyl with 1 to 5 carbon atoms;
m + n is greater than 1;
Z ¹ and Z ² are independently single-bonded, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -OCH ₂ CH ₂ O-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, or -COOCH ₂ CH _2- ;
The polymerizable liquid crystal compound according to [1], wherein R ¹ and R ² are independently one of an alkyl having 1 to 12 carbon atoms and a group represented by the formula (2).

[3] R ¹ is a group represented by the equation (2).
The polymerizable liquid crystal compound according to [1] or [2], wherein R ^{2 is a group represented by the formula (2).}

[4] Any of [1] to [3], wherein P is a polymerizable functional group represented by the formula (P-1), and R ^{3 is hydrogen or methyl in the formula (P-1).} The polymerizable liquid crystal compound according to item 1.

[5] A polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound according to any one of [1] to [4].

[6] A polymerizable liquid crystal composition in which the total amount of the polymerizable liquid crystal compound according to [1] is 1 to 50% by weight.

[7] Liquid crystal polymer films obtained by polymerizing the polymerizable liquid crystal composition according to [5] or [6].

[8] A polarizing plate containing the liquid crystal polymerized films according to [7].

[9] A display device including the liquid crystal polymerized film according to [7].

When any of [1] to [4] is added to the polymerizable liquid crystal composition which is a raw material of the liquid crystal polymerized films, the optical properties of the liquid crystal polymerized films, particularly the front contrast, are improved, and the liquid crystal polymerized films are improved. The display quality of the display element with built-in is improved.
When the raw material of the liquid crystal polymerized film is [5] or [6], the optical properties of the liquid crystal polymerized film, particularly the front contrast, is improved, and the display quality of the display element containing the liquid crystal polymerized film is improved. .. The optical properties of [7] and [8], particularly the front contrast, are improved, and the display quality of the display element incorporating the [7] or [8] is improved. The display quality of the display element of [9] is improved.

Cross-sectional view of the liquid crystal polymer film with a base material

Definitions of terms used in this disclosure are as follows:
The "front contrast" means a value of (brightness in the parallel Nicole state) / (brightness in the cross Nicole state) when the liquid crystal polymerized films with a base material are arranged between the two polarizing plates.
The "cross-nicol state" refers to a state in which the polarization axes of the polarizing plates arranged opposite to each other are orthogonal to each other.
The "parallel Nicole state" refers to a state in which the polarization axes of the polarizing plates arranged opposite to each other are aligned.

"Compound (X)" means a compound represented by the formula (X). Here, X in "Compound (X)" is a character string, a number, a symbol, or the like.

The "liquid crystal composition" is a mixture having a liquid crystal phase.
"Liquid crystal compound" is a general term for (A) a compound having a liquid crystal phase as a pure substance and (B) a compound which is a component of a liquid crystal composition.

The "polymerizable functional group" is a functional group that, when contained in a compound, polymerizes by means such as light, heat, and a catalyst to change into a polymer having a larger molecular weight.

The "monofunctional compound" is a compound having one polymerizable functional group.

The "polyfunctional compound" is a compound having a plurality of polymerizable functional groups.

The "X functional compound" is a compound having X polymerizable functional groups. Here, X in the "X functional compound" is an integer.

The "polymerizable compound" is a compound having at least one polymerizable functional group.

The "polymerizable liquid crystal compound" is a polymerizable compound which is a liquid crystal compound.

The "non-liquid crystal polymerizable compound" is a compound that does not have a liquid crystal phase in a pure substance and is a polymerizable compound.

The "polymerizable liquid crystal composition" means a composition containing a polymerizable compound and a liquid crystal compound, or a composition containing a "polymerizable liquid crystal compound".

The "liquid crystal polymerized film" means a portion obtained by polymerizing a polymerizable liquid crystal composition.

The "liquid crystal polymer film with a base material" means a material containing a base material obtained by polymerizing a polymerizable liquid crystal composition on the base material.

"Liquid crystal polymerized film" is a general term for a liquid crystal polymerized film and a liquid crystal polymerized film with a base material.

The "phase difference film" is a polarization conversion element having optical anisotropy. The retardation film is mainly used for optical elements.

The "tilt angle" is an angle between the orientation direction of the long axis of the liquid crystal molecule and the surface of the base material.

The "homogeneous orientation" refers to an orientation state in which the tilt angle is 0 to 5 degrees.
In the present disclosure, the "homeotropic orientation" refers to an orientation state in which the tilt angle is 85 degrees to 90 degrees.

The "tilt orientation" refers to an orientation state in which the orientation direction of the long axis of the liquid crystal molecules rises perpendicularly to the base material as the distance from the base material increases.

The "twisted orientation" refers to an orientation state in which the orientation direction of the liquid crystal molecules in the long axis direction is twisted in a stepwise manner about the perpendicular line on the surface of the base material as the liquid crystal molecules move away from the base material.

"Room temperature" refers to any temperature in the range of 15 ° C to 35 ° C.
"Improvement of optical properties" means improvement of frontal contrast of liquid crystal polymerized films, improvement of chromatic aberration, reduction of optical defects caused in the manufacturing process of liquid crystal polymerized films, and improvement of smoothness of liquid crystal polymerized films. The transparency of the polymerized films is improved, the chromatic aberration of visible light due to the liquid crystal polymerized films is improved, and / or the variation in optical properties is reduced by making the film thickness of the liquid crystal polymerized films uniform. By improving the optical properties of the members of the display element, the display quality of the display element is improved.
"Easy to prepare" means that the variation of the polymerizable liquid crystal composition as a raw material of the liquid crystal polymer films increases due to the fact that the liquid crystal phase is easily expressed or the compatibility with the organic solvent is improved, and the liquid crystal polymerization. By changing the composition of the polymerizable liquid crystal composition as a raw material for films, it becomes easier to control the wavelength dispersion, and / or the coatability of the polymerizable liquid crystal composition as a raw material for liquid crystal polymer films is improved. And so on.
"Durability" means chemical resistance of the surface, reduction of performance deterioration by suppressing stickiness, high mechanical strength of the surface, high surface hardness, and high adhesion between the base material and the liquid crystal polymerized film. And / or less deterioration of optical properties over time.
The term "preservability" includes that the performance of the raw material does not deteriorate over time.

In FIG. 1, 1 is a liquid crystal polymerized film and 2 is a base material.

When the following description is given in the chemical formula, it means that the wavy line portion is the bonding position of the group. Here, the following Arbitary is an arbitrary atom or group.

≪Polymerizable liquid crystal compound≫

When the polymerizable liquid crystal composition containing the compound (1) is polymerized to produce the liquid crystal polymerized films, the front contrast of the liquid crystal polymerized films is improved. Therefore, the compound (1) and the polymerizable liquid crystal composition are preferable. The liquid crystal polymerized films serve as materials for retardation films.

In formula (1), X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are independently hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, alkyl having 1 to 12 carbon atoms, respectively. An alkoxy having 1 to 12 carbon atoms, an alkoxycarbonyl having 1 to 12 carbon atoms, or an alkanoyl having 1 to 12 carbon atoms, and at least one of -CH ₂ − in the alkyl, alkoxy, alkoxycarbonyl and alkanoyl is -O-,-. It may be replaced with CO- or -S-.

When X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are alkyl having 1 to 12 carbon atoms or alkoxy having 1 to 12 carbon atoms, respectively, a polymerizable liquid crystal composition containing the compound (1) is used. This is preferable because defects of the optical element used as a raw material are unlikely to occur.

A ¹ and A ² are independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl or naphthalene-2,6-diyl, respectively. In this 1,4-phenylene or naphthalene-2,6-diyl, at least one hydrogen is fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. It may be replaced with alkoxycarbonyl or alkanoyl having 1 to 5 carbon atoms.

Z ¹ and Z ² are independently single-bonded, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -OCH ₂ CH ₂ O-, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, -COOCH ₂ CH _2- , -CH = CH-, -N = CH-, -CH = N-, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, -N = N- Or −C≡C−.

Since defects of optical elements made from the polymerizable liquid crystal composition containing the compound (1) are unlikely to occur, Z ¹ and Z ² are independently -COO-, -OCO-, and -CH ₂ CH ₂ COO-, respectively. Alternatively, −OCOCH ₂ CH ₂ − is preferable, and at least one of ^{Z 1} and Z ² _{is −CH 2} CH ₂ COO − or −OCOCH ₂ CH ₂ − is more preferable.

m and n are independently integers of 0 to 3. In order to increase the front contrast, it is preferable that m + n ≧ 3, and in order that the other liquid crystal compounds and the organic solvent in the polymerizable liquid crystal composition are difficult to phase-separate, it is preferable that m + n ≦ 5. , M and n are more preferably 2 or 3.

R ¹ and R ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 1 to 12 carbon atoms, respectively. An alkyl ester having 1 to 12 carbon atoms or a group represented by the formula (2), where ^{at least one of R 1} and R ² is a group represented by the formula (2).

In formula (2), Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-;
Q ¹ is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one −CH ₂ − is −O−, −COO−, −OCO−, −CH = CH− or −CH≡CH−. May be replaced by;
P is a polymerizable functional group represented by any one of the formulas (P-1) to (P-9). )

In formulas (P-1) to (P-9), R ³ is independently hydrogen, halogen, methyl, ethyl or trifluoromethyl, respectively.

Since defects in the optical element made from the polymerizable liquid crystal composition containing the compound (1) are unlikely to occur, it is difficult to cause defects.
^{Q 1} of the formula (2) is preferably an alkylene having 1 to 20 carbon atoms.

Since the functional groups represented by the formulas (P-1), (P-8) and (P-9) have the structure of α and β unsaturated ketones, they can be polymerized by various means. It is a polymerizable functional group that changes into a polymer having a larger molecular weight.

Since the formula (P-2) has a vinyl group adjacent to the electron donating group, it is a polymerizable functional group that polymerizes by various means and changes into a polymer having a larger molecular weight.

Since the functional groups represented by the formulas (P-3) to (P-7) have a strained cyclic ether, they are polymerized by various means and changed to a polymer having a larger molecular weight. It is a polymerizable functional group to be caused.

The functional groups represented by the formulas (P-1) to (P-9) can be appropriately selected depending on the production conditions of the film. For example, when a film is produced by photocuring, which is usually used, an acrylic group or a methacrylic group represented by the formula (P-1) is obtained from the viewpoints of high curability, solubility in a solvent, and ease of handling. However, it is preferable.

Of the polymerizable liquid crystal compounds represented by the formula (1), the formulas (1-1) to (1) are less likely to cause defects in the optical element made from the polymerizable liquid crystal composition containing the compound (1). The compound represented by -17) is preferable.

In equations (1-1) to (1-17),
Y ¹ is independently a single bond, -O-, -COO-, -OCO- or -OCOO-;
Q ¹ is independently a single bond or an alkylene with 1 to 20 carbon atoms, in which at least one -CH ₂ − may be replaced by -O-, -COO- or -OCO-;
P is any one functional group independently represented by the above formulas (P-1) to (P-9).

Compound (1) can be synthesized by combining known synthetic organic chemistry techniques.
For example, as a starting material, a substance synthesized in the same manner as described in ACS. Medicinal. Chemistry. Letters. 2010. 1 (7). 345-349. Is used, and synthesized according to the reaction scheme shown in Example 1 below. It can be performed.

<< Polymerizable liquid crystal composition >>
The polymerizable liquid crystal composition contains one or more compounds (1). In order to improve the liquid crystal polymer films made from the polymerizable liquid crystal composition as a raw material, particularly to improve the front contrast, in the polymerizable liquid crystal composition which is the raw material of the heavy crystal polymerized films, with respect to the total amount of the polymerizable liquid crystal composition. The compound (1) is preferably contained in an amount of 1 to 50% by weight, more preferably 3 to 30% by weight.

The polymerizable liquid crystal composition may contain a polymerizable liquid crystal compound other than the polymerizable liquid crystal compound represented by the compound (1). Since it is easy to prepare, the polymerizable liquid crystal compound is preferably a compound represented by the formula (3).

In equation (3),
A ³ is independently 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl or piperazine-1,4-diyl, in these, at least one of hydrogen, fluorine, carbon Alkyl group with 1 to 10 carbon atoms, alkenyl group with 2 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, alkoxycarbonyl group with 1 to 10 carbon atoms, alkanoyl group with 1 to 10 carbon atoms, 1 to 10 carbon atoms 2 alkanoyloxy group or ^P 2 ^-Q -Y ² - may be replaced by a monovalent radical having.
Z ² is independently a single _{bond, -CH 2 CH 2 -, -} COO -, - OCO -, - CH 2 O -, - OCH 2 -, - OCH 2 CH 2 O -, - CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH _{2 COO-, -OCOCH 2} CH _2- , -CH ₂ CH ₂ OCO- or -COOCH ₂ CH _2- . From the viewpoint of suppressing deterioration of the phase difference function of the liquid crystal polymer film in a high temperature environment, at least one is preferably _{-CH 2} CH ₂ COO- or -OCOCH ₂ CH _2-.
a and b are independently integers from 0 to 3, and the sum of a and b is 2 to 6.
Y ² is independently a single bond, -O-, -COO-, -OCO- or -OCOO-.
Q ² is independently an alkylene group of a single bond or a C 1 to 20, in the ^{Q 2,} at least one of -CH ₂ - -O -, - COO- or -OCO- be replaced by good.
P ² is an acryloyloxy group or a methacryloyloxy group.
G is 1,4-phenylene, 1,4-cyclohexylene, fluorene-2,-7-diyl or a group represented by the formulas (G-1) to (G-4). In the 1,4-phenylene, 1,4-cyclohexylene, and fluorene-2,-7-diyl, at least one hydrogen is fluorine, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 2 to 10 carbon atoms. , an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, alkanoyloxy group or ^{P 2 -Q} 2 -Y 2 of 1 to 10 carbon atoms - having It may be replaced with a monovalent group.

In equations (G-1) to (G-4),
_-CH 2 X ⁷ are independently -, - NH -, - O -, - an S- or -CO-, the -CH ₂ - in or -NH-, at least one hydrogen C1-5 May be replaced with an alkyl group of
X ⁸ is independently -CH = or -N =,
Z ³ is independently single bond, -CH = CH-, -C≡C-, -CH = N-, -N = CH-, -CH = N-NR ^6- , -C (CH ₃ ) = N -NR ^6- or -CH = NN = CH-,
Wherein, ^{R 6} is independently hydrogen, alkyl or ^{P 2 -Q} 2 -Y 2 of 1 to 10 carbon atoms - is a monovalent group having the
T ¹ , T ⁴ and T ⁵ are functional groups consisting of hydrogen, carbon, nitrogen, oxygen, sulfur, and / or halogen, respectively, having a total number of atoms of 10 to 40 and may be substituted aromatics. A monovalent group having a hydrocarbon or an aromatic heterocycle,
T ² and T ³ are independently hydrogen, trifluoromethyl group, cyano group, alkyl group having 1 to 5 carbon atoms, alkenyl group having 2 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, and carbon number of carbon atoms, respectively. 1 having - 1-5 alkoxycarbonyl group, an alkanoyl group having 1 to 5 carbon atoms, alkanoyloxy group having 1 to 5 carbon atoms, alkyl sulfide group having 1 to 5 carbon atoms, or ^{P 2 -Q} 2 -Y 2 A valent group or a 5- to 7-membered heterocyclic or cyclic ketone containing an oxygen atom, a nitrogen atom, and a sulfur atom.
T ⁶ is independently hydrogen, trifluoromethyl group, cyano group, alkyl group having 1 to 5 carbon atoms, alkenyl group having 2 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. is a monovalent group having a - alkoxycarbonyl group, an alkanoyl group having 1 to 5 carbon atoms, alkanoyloxy group having 1 to 5 carbon atoms, 1 to 5 carbon atoms alkyl sulfide group or ^{P 2 -Q} 2 -Y 2 ..

Of the compounds represented by the formula (3), the compounds represented by the formulas (3-A-1) to (3-A-20) are preferable because they are easy to prepare. Formulas (3-1-1) to (3-1-5), formulas (3-2-1) to formulas (3-2-6), formulas (3-3-3) to improve optical properties. Compounds represented by formulas 1) to (3-3-6) and formulas (3-4-1) to (3-4-5) are preferable.

Formulas (3-A-1) to formulas (3-A-20), formulas (3-1-1) to formulas (3-1-5), formulas (3-2-1) to formulas (3-2) -6), in formulas (3-3-1) to formulas (3-3-6) and formulas (3-4-1) to formulas (3-4-5),
Y ² is independently a single bond, -O-, -COO-, -OCO- or -OCOO-,
Q ² is an alkylene group of a single bond or a C 1-20 independently, at least one -CH ₂ in the ^{Q 2} - is -O -, - COO- or -OCO- may be replaced by,
P ² is an acryloyloxy group and a methacryloyloxy group independently.

≪Additives to polymerizable liquid crystal composition≫
One or more kinds of additives may be added to the polymerizable liquid crystal composition.

In order to improve the optical properties, the component added to the polymerizable liquid crystal composition which is a raw material of the liquid crystal polymerized film is preferably a surfactant, and more preferably a nonionic surfactant. The nonionic surfactant has an effect of suppressing the tilt orientation of the liquid crystal polymer film on the air interface side. Silicone-based nonionic surfactants, fluorine-based nonionic surfactants, vinyl-based nonionic surfactants, hydrocarbon-based nonionic surfactants, and the like are nonionic surfactants.

In order to improve the durability of the liquid crystal polymerized films, it is preferable to add a surfactant which is a polymerizable compound to the polymerizable liquid crystal composition, and a surfactant which starts the polymerization reaction with ultraviolet rays is more preferable.

The surfactant in the polymerizable liquid crystal composition is preferably 0.0001 to 0.5% by weight, preferably 0.01 to 0% by weight, based on the total amount of the polymerizable liquid crystal composition, because the optical properties can be improved and easily adjusted. 2% by weight is more preferable.

Titanate compounds, imidazolines, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycols, and their esters, sodium lauryl sulfate, ammonium lauryl sulfate, amines lauryl sulfate, alkyl-substituted fragrances. Group sulfonates, alkyl phosphates, aliphatic, or aromatic sulfonate formalin condensates, lauryl amide propyl betaine, lauryl aminoacetate betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkyl amines, perfluoroalkyl sulfonates , Perfluoroalkyl carboxylate and the like are ionic surfactants.

A silicone-based nonionic surfactant is a linear polymer composed of a siloxane bond, in which an organic group such as a polyether or a long-chain alkyl is introduced into a side chain and / or a terminal.

A compound having a perfluoroalkyl group or a perfluoroalkenyl group having 2 to 7 carbon atoms is a fluorine-based nonionic surfactant.

Examples of vinyl-based nonionic surfactants include (meth) acrylic polymers. In this case, the weight average molecular weight of the (meth) acrylic polymer is typically 1,000 to 1,000,000.

Addition of a surfactant having a polymerizable functional group to the polymerizable liquid crystal composition which is a raw material of the liquid crystal polymer film improves the surface hardness of the liquid crystal polymer films.

Fluorine-based nonionic surfactant, silicone-based nonionic surfactant, or carbon-hydrogen-based nonionic interface to the polymerizable liquid crystal composition that is the raw material of the liquid crystal polymer film in order to improve the optical properties. Addition of an activator is preferred.

The polymerizable liquid crystal composition may contain a non-liquid crystal polymerizable compound. Since it is easy to prepare, the total weight of the non-liquid crystal polymerizable compound in the polymerizable liquid crystal composition is preferably 1/5 or less of the total weight of the polymerizable compound in the polymerizable liquid crystal composition.

Durability can be expected by adding a compound having two or more polymerizable functional groups to the polymerizable liquid crystal composition.

The non-liquid crystal polymerizable compound is typically a compound having one or more vinyl-based polymerizable functional groups.

In order to improve the durability of the liquid crystal polymer films, it is preferable to add a non-liquid crystal polymerizable compound having a polar group at the side chain and / or the terminal to the polymerizable liquid crystal composition which is a raw material of the liquid crystal polymer film.

The carbon number of styrene, nuclear-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylpyrrolidone, vinylsulfonic acid, fatty acid vinyl, α, β-ethylene unsaturated carboxylic acid, and alkyl is 1 to 18. Alkyl ester of (meth) acrylic acid, hydroxyalkyl ester of (meth) acrylic acid having 1 to 18 carbon atoms, aminoalkyl ester of (meth) acrylic acid having 1 to 18 carbon atoms of aminoalkyl , Ether oxygen-containing alkyl ester of (meth) acrylic acid having ether oxygen-containing alkyl having 3 to 18 carbon atoms, N-vinylacetamide, pt-butyl benzoate vinyl, N, N-dimethylaminobenzoate vinyl, Vinyl benzoate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanate, 2-methyl-2-vinylbutate, vinyl propionate, vinyl stearate, 2-ethyl-2- Vinyl methylbutanoate, dicyclopentanyloxyl ethyl (meth) acrylate, isobornyloxyl ethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyl adamantyl (meth) acrylate, dicyclopentanyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxy Ethylphthalic acid, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, polyethylene glycol with a degree of polymerization of 2 to 100, polypropylene glycol, copolymer of ethylene oxide and propylene oxide, etc. Polyalkylylene glycol mono (meth) acrylic acid ester, or di (meth) acrylic acid ester or polyethylene glycol having a degree of polymerization of 2 to 100 capped with an alkyl having 1 to 6 carbon atoms at the end. Polyalkylene glycol and mono (meth) acrylic acid ester of polyalkylene glycol which is a copolymer of ethylene oxide and propylene oxide are non-liquidaceous polymerizable compounds which are monofunctional compounds. Vinyl acetate and the like are "vinyl fatty acid". Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and the like are "α, β-ethylenically unsaturated carboxylic acids". Methoxyethyl ester, ethoxyethyl ester, methoxypropyl ester, methyl carbyl ester, ethyl carbyl ester, butyl carbyl ester, etc. are described as "ether oxygen-containing alkyl of (meth) acrylic acid having 3 to 18 carbon atoms. Esther ".

1,4-Butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, dimethylol tricyclodecane diacrylate, triethylene glycol diacrylate, dipropylene glycol Diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, bisphenol A EO-added diacrylate, bisphenol A glycidyl diacrylate, polyethylene glycol diacrylate, and methacrylate compounds of these compounds are bifunctional compounds. It is a polymerizable compound.

Pentaeristol triacrylate, trimethylolpropan triacrylate, trimethylol EO-added triacrylate, trisacryloyloxyethyl phosphate, tris (acryloyloxyethyl) isocyanurate, alkyl-modified dipentaerythritol triacrylate, EO-modified trimethylolpropane triacrylate Rate, PO-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, alkyl-modified dipentaerythritol tetraacrylate, ditrimethylolpropanetetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate , Pentaeristol trimetaacrylate, trimethylolpropane trimetaacrylate, trimethylol EO-added trimetaacrylate, trimethacryloyloxyethyl phosphate, trimethacryloyloxyethyl isocyanurate, alkyl-modified dipentaerythritol trimetaacrylate, EO-modified Trimethylol Propane Trimethacrylate, PO Modified Trimethylol Propane Trimethacrylate, Pentaerythritol Tetramethacrylate, Alkyl Modified Dipentaerythritol Tetramethacrylate, Ditrimethylol Propanetetramethacrylate, Dipentaerythritol Hexamethacrylate, Dipentaerythritol Monohydroxy Pentamethacrylate, alkyl-modified dipentaerythritol pentamethacrylate and the like are non-liquidaceous polymerizable compounds of polyfunctional compounds that are not bifunctional compounds. The addition of a polymerizable compound having a bisphenol structure or a cardo structure to the polymerizable liquid crystal composition induces an improvement in the degree of curing of the polymer and a homeotropic orientation of the liquid crystal polymer film.

The compounds represented by the formulas (α-1) to (α-3) are polymerizable fluorene derivatives having a cardo structure.

In equations (α-1) to (α-3),
R ^α is independently hydrogen or methyl and
s is an independently integer from 0 to 4.

The addition of the polymerization initiator optimizes the polymerization rate of the polymerizable liquid crystal composition. Photoradical initiators and the like are polymerization initiators.

1-Hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one , P-Phenylphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystylyl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylaclysine, 9,10- Benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethylketal, 2-methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / p-dimethylaminomethyl benzoate mixture, benzophenone / methyltriethanolamine mixture, adecaoptomer N-1919, adeca Cruise NCI-831, Adeca Cruise NCI-930, Irgacure 127, Irgacure 369, Irgacure 379, Irgacure 500, Irgacure 754, Irgacure 784, Irgacure 819, Irgacure 907, Irgacure 1300, Irgacure 1700. , Irga Cure 1800, Irga Cure 1850, Irga Cure 1870, Irga Cure 2959, Irga Cure OXE01, Irga Cure OXE02, Daro Cure 4265, Daro Cure MBF, Daro Cure TPO and the like are photoradical initiators. Here, Adeka, Irgacure and DaroCure are registered trademarks.

In order to improve the optical properties and durability of the liquid crystal polymerized films, the total weight of the photoradical polymerization initiator in the polymerizable liquid crystal composition is 1 to 30% by weight based on the total amount of the polymerizable liquid crystal composition. Preferably, 1 to 15% by weight is more preferable, and 3 to 10% by weight is further preferable.

A sensitizer may be added to the polymerizable liquid crystal composition together with the photoradical polymerization initiator. Sensitizers include isopropylthioxanthone, diethylthioxanthone, ethyl-4 dimethylaminobenzoate and 2-ethylhexyl-4-dimethylaminobenzoate.

By adding the chain transfer agent to the polymerizable liquid crystal composition, the reaction rate of the polymerizable liquid crystal compound and the chain length of the polymer in the liquid crystal polymer film can be adjusted.
As the amount of the chain transfer agent increases, the reaction rate of the polymerizable liquid crystal compound decreases. As the amount of the chain transfer agent increases, the chain length of the polymer decreases. Thereby, the mechanical properties of the liquid crystal polymerized film can be adjusted.

Thiol derivatives, styrene dimer derivatives and the like are chain transfer agents.

A thiol derivative which is a monofunctional compound and a thiol derivative which is a polyfunctional compound are thiol derivatives.

Dodecanethiol, 2-ethylhexyl- (3-mercapto) propionate and the like are thiol derivatives that are monofunctional compounds. Trimethylol propanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate) , 1,3,5-Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is a thiol derivative that is a polyfunctional compound. be.

2,4-Diphenyl-4-methyl-1-pentene, 2,4-diphenyl-1-butene and the like are styrene dimer chain transfer agents.

For storage stability, it is preferable to add a polymerization inhibitor to the polymerizable liquid crystal composition. Phenol derivatives, phenothiazine derivatives, compounds having a nitroso group, benzothiazine derivatives and the like are polymerization inhibitors. 2,5-Di (t-butyl) hydroxytoluene, hydroquinone, o-hydroxybenzophenone, methylene blue, diphenylpicric acid hydrazide and the like are polymerization inhibitors which are phenol derivatives. Phenothiazine, methylene blue and the like are polymerization inhibitors that are phenothiazine derivatives. N, N-dimethyl-4-nitrosoaniline and the like are polymerization inhibitors which are compounds having a typical low nitroso group.

For storage stability, it is preferable to add a polymerization inhibitor to the polymerizable liquid crystal composition.

Polymerization inhibitors include (a) phenolic antioxidants, (b) sulfur-based antioxidants, (c) phosphoric acid-based antioxidants, and (d) hindered amine-based antioxidants. Phenolic antioxidants are preferred because they are easy to prepare. A phenolic antioxidant having a t-butyl group at the ortho position of the hydroxyl group is preferable because it is easy to prepare.

In order to improve the storage stability, it is preferable to add an ultraviolet absorber to the polymerizable liquid crystal composition.

In order to improve the storage stability, it is preferable to add a light stabilizer to the polymerizable liquid crystal composition.

In order to improve the storage stability, it is preferable to add an antioxidant to the polymerizable liquid crystal composition.

In order to improve the storage stability, it is preferable to add a silane coupling agent to the polymerizable liquid crystal composition.

Since it is easy to prepare, it is preferable to add a solvent to the polymerizable liquid crystal composition which is a raw material of the liquid crystal polymerized films.

Esters, amide compounds, alcohols, ethers, glycol monoalkyl ethers, aromatic hydrocarbons, halogenated aromatic hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, alicyclic hydrocarbons, ketones, acetate solvents Etc. can be components of the solvent.

The amide-based compound refers to a compound having an amide group and which is a component of a solvent. The acetate-based solvent refers to a compound having an acetate structure and which is a component of the solvent.

Alkyl acetate, ethyl trifluoroacetate, alkyl propionate, alkyl butyrate, dialkyl malonic acid, alkyl glycolate, alkyl lactate, monoacetin, γ-butyrolactone, γ-valerolactone and the like are the esters.

Methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, 3-methoxybutyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate and the like are "alkyl acetates". Methyl propionate, methyl 3-methoxypropionate, ethyl propionate, propyl propionate, butyl propionate and the like are "alkyl propionates". Methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl butyrate, propyl butyrate and the like are "alkyl butyrate". Diethyl malonate and the like are "dialkyl malonate. Methyl glycolate, ethyl glycolate and the like are" alkyl glycolate ". Methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate, ethylhexyl lactate and the like are "alkyl lactate".

N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylacetamide dimethylacetal , N-Methylcaprolactam, dimethylimidazolidinone and the like are amide compounds.

Methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol, butanol, 2-ethylbutanol, n-hexanol, n-heptanol, n-octanol, 1 -Dodecanol, ethylhexanol, 3,5,5-trimethylhexanol, n-amyl alcohol, hexafluoro-2-propanol, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tri Propylene glycol, hexylene glycol, 1,3-butandiol, 1,4-butandiol, 2,3-butandiol, 1,5-pentanediol, 2,4-pentanediol, 2,5-hexanediol, 3 -Methyl-3-methoxybutanol, cyclohexanol, methylcyclohexanol and the like are alcohols.

Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, bis (2-propyl) ether, 1,4-dioxane, tetrahydrofuran and the like are ethers.

Ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dipropylene glycol monoalkyl ether, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, triethylene glycol monoalkyl ether Acetates, propylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ether acetates, diethylene glycol methyl ethyl ethers and the like are glycol monoalkyl ethers.

Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether and the like are ethylene glycol monoalkyl ethers. Diethylene glycol monoethyl ether and the like are diethylene glycol monoalkyl ethers. Propylene glycol monobutyl ether and the like are propylene glycol monoalkyl ethers. Dipropylene glycol monomethyl ether and the like are dipropylene glycol monoalkyl ethers. Ethylene glycol monobutyl ether acetate and the like are ethylene glycol monoalkyl ether acetates. Diethylene glycol monoethyl ether acetate and the like are diethylene glycol monoalkyl ether acetate. Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and the like are propylene glycol monoalkyl ether acetates. Dipropylene glycol monomethyl ether acetate and the like are dipropylene glycol monoalkyl ether acetate.

Benzene, toluene, xylene, mesityrene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, tetralin and the like are the aromatic hydrocarbons.

Chlorobenzene and the like are halogenated aromatic hydrocarbons. Hexane, heptane, etc. are aliphatic hydrocarbons. Chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichlorethylene, tetrachlorethylene and the like are halogenated aliphatic hydrocarbons. Cyclohexane, decalin and the like are alicyclic hydrocarbons.

Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, methyl propyl ketone and the like are ketones.

Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl acetate acetate, 1-methoxy-2-propyl acetate and the like are acetate-based solvents.

Since it is easy to prepare, the solvent in the polymerizable liquid crystal composition is preferably 30 to 96% by weight, more preferably 50 to 90% by weight, still more preferably 60 to 90% by weight, based on the total amount of the polymerizable liquid crystal composition. ..

The polymerizable liquid crystal composition may contain a compound having optical activity. The addition of an optically active compound to the liquid crystal composition induces the liquid crystal polymerized film in a twisted orientation. The liquid crystal polymer film can be used as a selective reflection film and a negative C plate in the wavelength region of 300 to 2000 nm.

Compounds having an asymmetric carbon, axial asymmetric compounds having a binaphthyl structure, a helicene structure, and the like, surface asymmetric compounds having a cyclophane structure, and the like are compounds having optical activity. In order to improve the durability, the compound having optical activity in this case is preferably a polymerizable compound.

The liquid crystal polymerized film may contain a dichroic dye. The liquid crystal polymerized films compounded with the dichroic dye can be used as an absorbent polarizing plate.

In order to improve the optical properties, the dichroic dye of the polymerizable liquid crystal composition used as a raw material for the liquid crystal polymerized films preferably has a maximum absorption wavelength in the range of 300 to 700 nm. Acridine pigments, oxazine pigments, cyanine pigments, naphthalene pigments, azo pigments, anthraquinone pigments and the like can be used. As the azo dye, a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, a stilbene azo dye and the like are dichroic dyes.

The liquid crystal polymerized film may contain a fluorescent dye. The liquid crystal polymer film composited with the fluorescent dye can be used as a polarized light emitting film and a wavelength conversion film.

≪Base material≫
Glass, plastic, metal, etc. are the materials of the base material. The surface of the glass or the metal may be slit-shaped. The plastic may be subjected to surface treatment such as stretching treatment and hydrophilization treatment and hydrophobic treatment.

In order to form a liquid crystal polymer film having a specific orientation on the base material, the base material may be surface-treated before the polymerizable liquid crystal composition is applied to the base material. As the surface treatment, (a) an alignment film is formed on the base material and rubbing, (d) an inclined vapor deposition film of silicon oxide is formed on the base material, (c) an alignment film is formed on the base material and polarized UV irradiation is performed. Method can be mentioned.

The following procedure is an example of the formation and rubbing process of the alignment film on the substrate:
(1) Apply the alignment agent solution to the substrate and apply
(2) The substrate having the obtained coating film is heat-treated.
(3) Wrap a rubbing cloth made of materials such as rayon, cotton, and polyamide around a metal roll, etc.
(4) The roll is brought into contact with the substrate.
(5) The roll is moved in parallel with the surface of the substrate while rotating the roll, or the substrate is moved while the roll is fixed.

Examples of the alignment agent include solutions containing polyimide, polyamic acid or polyvinyl alcohol.

The following procedure is an example of forming an alignment film on a substrate and irradiating polarized UV:
(1) Apply the alignment agent solution to the substrate and apply
(2) The substrate having the obtained coating film is heat-treated.
(3) The coating film on the substrate is irradiated with linearly polarized light having a wavelength of 250 to 400 nm.
(4) If necessary, heat-treat.

As the alignment agent, a solution containing polyimide having a photosensitive group, a polyamic acid, a cycloolefin polymer, a polyacrylate, or the like is used. Examples of the photosensitive group include a chalcone group, a cinnamate group, a cinnamoyl group, a stilbene group, a cyclobutane group, an azobenzene group and the like.

≪Liquid crystal polymer film with base material≫
The liquid crystal polymer film with a base material is obtained by the following steps.

(1) The polymerizable liquid crystal composition is applied onto a substrate and dried if necessary to form a coating film.

(2) In a state where the polymerizable liquid crystal composition is oriented, it is polymerized by means such as light, heat, and a catalyst to obtain a liquid crystal polymer film with a base material.

As a result, the polymerizable liquid crystal composition in the coating film is immobilized while maintaining the orientation of the liquid crystal state.

Various coating methods are used for coating the polymerizable liquid crystal composition. In order to improve the optical properties, the spin coating method, the micro gravure coating method, the gravure coating method, the wire bar coating method, the dip coating method, the spray coating method, the meniscus coating method and the die coating method are preferable.

In order to improve the production efficiency, it is preferable to heat-treat the liquid crystal polymer film with a base material during drying. The heat treatment can be performed by using a hot plate, a drying oven, and blowing hot air or hot air.

Means such as electron beam, ultraviolet light, visible light, and infrared light can be used to obtain the liquid crystal polymerized film. The wavelength range of the light irradiated to obtain the liquid crystal polymer film is 150 to 500 nm. The preferred wavelength range of light is 250-450 nm, and the more preferred range is 300-400 nm.

As a light source of the light, a low-pressure mercury lamp, a high-pressure discharge lamp, and a short arc discharge lamp can be used. Bactericidal lamps, fluorescent chemical lamps and black lights are low pressure mercury lamps. High-pressure mercury lamps, metal halide lamps, and the like are the high-pressure discharge lamps. Ultra-high pressure mercury lamps, xenon lamps, mercury xenon lamps and the like are short arc discharge lamps.

The liquid crystal polymerized films can be arranged inside and outside the liquid crystal cell of the liquid crystal display element. Since the retardation of the liquid crystal polymerized film does not fluctuate due to the thermal history and the elution of impurities from the liquid crystal polymerized film to the liquid crystal is small, the liquid crystal polymerized film can be arranged inside the liquid crystal cell.

The following method is known as a method of removing the liquid crystal polymer film from the liquid crystal polymer film with a base material and fixing the liquid crystal polymer film on another base material.

(1) The liquid crystal polymer film with a base material and the substrate having the adhesive layer are laminated so that the liquid crystal polymer film and the adhesive layer are in contact with each other.
(2) A material bonded so that the liquid crystal polymerized film and the adhesive layer are in contact with each other is peeled off between the base material portion of the liquid crystal polymerized film with a base material and the liquid crystal polymerized film.
(3) The liquid crystal polymerized film on the base material having the adhesive layer is fixed to another base material by the same method as in (1) and (2) above.

An optically anisotropic film is built in the display element. When the front contrast of the optically anisotropic film built in the display element is improved, the display quality of the display element is improved.

The disclosure is not limited to published examples.

<Definition of terms>
In the disclosed examples, "DCC" is 1,3-dicyclohexylcarbodiimide.

In the disclosed examples, "DMAP" is 4-dimethylaminopyridine.

In the disclosed examples, "pTSA" is p-toluenesulfonic acid.

<Obtaining reagents>
In the disclosed examples, "Irg-907" is Irgacure ™ 907 manufactured by BASF Japan Ltd.

In the disclosed embodiment, "NCI-930" is ADEKA CORPORATION (trademark) NCI-930 manufactured by ADEKA CORPORATION.

In the disclosed examples, "FTX-218" is Futergent ™ FTX-218 manufactured by Neos Co., Ltd.

In the disclosed embodiment, "TF370" is TEGOFlow ™ 370 of Evonik Japan Ltd.

In the disclosed examples, "polystyrene having a known molecular weight" is product number 0006476 manufactured by Tosoh Corporation.

In the disclosed embodiment, "palladium on carbon" is P1528 manufactured by Tokyo Chemical Industry Co., Ltd.

<Equipment used to determine the structure, etc.>
In the disclosed examples, NMR was measured on a Bruker DRX-500.

In the disclosed examples, the gel permeation chromatograph was measured with LC-9A manufactured by Shimadzu Corporation.

In the disclosed examples, the column of the gel permeation chromatograph is Shodex ™ GF-7M HQ.
<Equipment used for measuring optical characteristics, etc.>
In the disclosed example, the polarizing microscope is ECLIPSE E600 POL manufactured by Nikon Corporation.

In the disclosed embodiment, the polarization analyzer is an OPIPRO polarization analyzer manufactured by Shintech Co., Ltd.

In the disclosed embodiment, the luminance meter is Yokogawa 3298F.

In the disclosed examples, the wire grid polarizing plate is UVT300A manufactured by Polatechno Co., Ltd.

In the disclosed embodiment, the "receiver for measuring the illuminance at a wavelength near 313 nm" is UVD-S313 manufactured by Ushio, Inc. In the disclosed embodiment, "measures the illuminance at a wavelength near 365 nm". The "receiver for this purpose" is UVD-S365 manufactured by Ushio, Inc.
<Equipment used for other measurements>
In the disclosed embodiment, the melting point measuring device is a system including a temperature controller FP90 and a hot stage FP82 manufactured by METTLER TOLEDO Co., Ltd.
In the disclosed example, the step of the liquid crystal polymerized film portion was measured by Alpha Step IQ manufactured by KLA TENCOR Co., Ltd.
<Prototype device>
In the disclosed embodiment, the ultra-high pressure mercury lamp is a multi-light USH-250BY manufactured by Ushio, Inc.

In the disclosed embodiment, the ultraviolet illuminometer is UIT-150-A manufactured by Ushio, Inc.

In the disclosed embodiment, the receiver for measuring the illuminance at a wavelength near 313 nm is UVD-S313 manufactured by Ushio, Inc. In the disclosed embodiment, the receiver for measuring the illuminance at a wavelength near 365 nm. Is UVD-S365 manufactured by Ushio, Inc.

<Determination of structure, etc.>
The structure of the compound was determined by dissolving the compound to be measured in CDCl ₃ ^{and measuring 1} H-NMR of the solution at 500 MHz. The measured value of NMR represents the value of the shift based on TMS, excluding the unit ppm. In the notation of the measured value of NMR, s is a singlet, d is a doublet, t is a triplet, and m is a multiplet.
<Measurement of weight average molecular weight>
The weight average molecular weight was determined by gel permeation chromatograph. The temperature of the column during the development was set to 40 ° C. THF was used as the developing solvent for the gel permeation chromatograph. At this time, polystyrene having a known molecular weight was used as a standard substance for determining the weight average molecular weight.

<Measurement of optical characteristics, etc.>
<Visual observation method>
The presence or absence of orientation defects was determined by sandwiching the base material on which the retardation film was formed between two polarizing plates arranged on Cross Nicol. The base material was rotated in a horizontal plane, and the light and dark states were visually confirmed. When there is a part where light can be seen through in the dark state, or when both the bright state and the dark state cannot be confirmed, the orientation defect is regarded as "present". When the alignment defect was not "present", the alignment defect was defined as "absent".

<Measurement by ellipsometry device>
The retardation of the liquid crystal polymer film was measured with an ellipsometry apparatus with the incident angle of light set to 0 °. The wavelength of light used to measure the retardation is 550 nm.
<Judgment of homogenius orientation>
Using an ellipsometry apparatus, the angle of incidence of light on the surface of the liquid crystal polymer film was changed from −50 ° to 50 in 5 ° increments, and the retardation was measured. Here, the inclination direction of the incident angle of light is the same as the slow axis of the liquid crystal polymer film. When both of the following conditions were satisfied, the liquid crystal polymerized film was considered to have a homogeneous orientation.
The difference between the measured values of Re when (a) the retardation with respect to the incident angle of the liquid crystal polymer film is convex upward and (b) the absolute value of the incident angle is the same is 5%. If it is within.

<Evaluation of birefringence>
The birefringence was calculated by (letteration) / (film thickness).

<Measurement of brightness in cross Nicol state>
The brightness in the cross Nicol state was measured by the following procedure.

(1) A liquid crystal polymer film with a base material is sandwiched between two polarizing plates, and the two polarizing plates are arranged on a luminance meter so as to form a cross Nicol.
(2) The minimum brightness when the base material was rotated horizontally was defined as "brightness in the cross Nicol state".

<Measurement of brightness in parallel Nicole state>
The brightness in the parallel Nicole state was measured by the following procedure.

(1) A liquid crystal polymer film with a base material is sandwiched between two polarizing plates, and the two polarizing plates are arranged on a luminance meter so as to form a parallel Nicole.
(2) The maximum brightness when the base material was rotated horizontally was defined as "brightness in the parallel Nicole state".

<Measurement of phase transition temperature>
To measure the transition temperature, the sample was placed on a hot plate of a melting point measuring device, and the transition temperature was measured with a polarizing microscope. The transition temperature was measured while raising the temperature at a rate of 3 ° C./min.

<Film thickness measurement>
The film thickness of the liquid crystal polymer film having a glass substrate was measured by the following procedure.

(1) The liquid crystal polymer film is carved out from the glass substrate having the liquid crystal polymer film.
(2) Measure the step between the part with the liquid crystal polymerized film and the part excluding the liquid crystal polymerized film.
(3) The measured value was taken as the film thickness.

<Sample preparation>
<Preparation of photo-aligning agent>
The polymer represented by the formula (J) was synthesized by the same method as described in Example 9 of JP2012-087286.

In formula (J), x was 0.1 and the weight average molecular weight was 53700. A product obtained by dissolving 5% by weight of the polymer represented by the formula (J) in 95% by weight of cyclopentanone and filtering with a filter was named a photoaligning agent (1).

<Preparation of photoalignment film>
The glass substrate with the alignment film was prepared by the following procedure.

Procedure (1) The photoaligning agent (1) was spin-coated on glass to prepare a coating film.

Procedure (2) A substrate having a coating film was allowed to stand on a hot plate at 100 ° C. for 60 seconds, and the solvent was removed from the coating film.

Procedure (3) The coating film on the substrate was irradiated with linearly polarized UV having a constant output at room temperature from a direction of 90 ° to prepare a glass substrate with an alignment film.

However, the linearly polarized ultraviolet rays in the procedure (3) could transmit the light from the ultrahigh pressure mercury lamp through the wire grid polarizing plate. Further, using a receiver for measuring the illuminance at a wavelength near 313 nm nm, the exposure amount of linear ultraviolet rays to the surface of the coating film on the substrate in the procedure (3) is 200 mJ / cm ^2. In addition, the irradiation time of the procedure (3) was adjusted between 20 seconds and 40 seconds.

Compound (1-9-1) was synthesized by the following procedure.

15.0 g of 2-bromo-5-methoxybenzoic acid, 14.3 g of resorcinol, 5.2 g of sodium hydroxide and 1.6 g of copper sulfate pentahydrate were added to 50 mL of water, and the mixture was heated under a nitrogen atmosphere. It was stirred underneath for 2 hours. Then, the temperature was returned to room temperature, and the mixture was filtered to obtain a precipitate. The obtained solid was washed with water, then with methanol, and dried under reduced pressure to obtain 10.2 g of the compound (ex-1).

10.2 g of compound (ex-1) and 11.2 g of aluminum chloride were added to 100 mL of chlorobenzene, and the mixture was stirred under a nitrogen atmosphere and under heating under reflux for 6 hours. After returning the obtained liquid to room temperature, it was poured into ice water and filtered to obtain a precipitate. The obtained solid was washed with water, then with methanol, and then dried under reduced pressure to obtain 8.5 g of the compound (ex-2).

Compound (ex-3) was synthesized by the same procedure as that described in Example 5 of JP-A-2016-047813.

Add 7.5 g of compound (ex-2), 30.0 g of compound (ex-4) and 1.6 g of DMAP to 300 mL of dichloromethane and stir in a nitrogen atmosphere while cooling to 0 ° C. in an ice bath. bottom. A 50 mL dichloromethane solution in which 14.6 g of DCC was dissolved was added dropwise thereto. After the dropping, the mixture was stirred at room temperature for 16 hours. The precipitated precipitate was filtered off, the organic layer was washed with water and dried over anhydrous magnesium sulfate. Dichloromethane was distilled off under reduced pressure, the residue was purified by column chromatography, dissolved in toluene and reprecipitated in methanol to obtain 17.1 g of the compound (1-9-1). Here, the filler for column chromatography is silica gel. Here, the eluent is a mixture of toluene and ethyl acetate v / v = 9/1.

Compound (1-9-1) was in the smectic phase at room temperature, and the transition temperature to the nematic phase was 112.5 ° C. Due to thermal polymerization, the transition temperature to the isotropic liquid could not be measured. Since the viscosity increased, the freezing point could not be measured either. ^{The 1} H-NMR signal of compound (1-9-1) is as follows.
8.10-8.07 (m, 2H), 8.03 (d, 2H), 7.56 (dd, 1H), 7.14-7.09 (m, 6H), 6.83-6. 81 (m, 4H), 6.40 (dd, 2H), 6.12 (dd, 2H), 5.82 (dd, 2H), 4.80-4.75 (m, 2H), 4.17 (T, 4H), 3.94 (t, 4H), 2.89 (t, 3H), 2.63-2.56 (m, 6H), 2.21-2.19 (m, 4H), 2.09-2.07 (m, 4H), 1.82-1.66 (m, 12H), 1.54-1.42 (m, 12H).

[Example 2]
The compound (1-11-1) shown below was synthesized by the same procedure as the synthesis method described in Example 1. However, 2-methylresorcinol was used instead of resorcinol.

Compound (1-11-1) was in the smectic phase at room temperature, and the transition temperature to the nematic phase was 107.2 ° C. The transition temperature to the isotropic liquid could not be measured due to thermal polymerization. The freezing point could not be measured due to the increase in viscosity. The obtained compound (1-11-1) ^{1 1} H-NMR signal is as follows.
8.11-8.08 (m, 2H), 7.89 (d, 2H), 7.55 (dd, 1H), 7.12-7.11 (m, 4H), 7.04 (d, 2H), 6.84-6.81 (m, 4H), 6.40 (dd, 2H), 6.12 (dd, 2H), 5.82 (dd, 2H), 4.80-4.76 (M, 2H), 4.17 (t, 4H), 3.94 (t, 4H), 2.90 (t, 4H), 2.63-2.58 (m, 6H), 2.30 ( s, 3H), 2.25-2.17 (m, 4H), 2.10-2.07 (m, 4H), 1.82-1.68 (m, 12H), 1.54-1. 42 (m, 12H).

[Example 3]
The compound (1-10-1) shown below was synthesized by the same procedure as the synthesis method described in Example 1. However, 6-bromo-3-methoxy-2-methylbenzoic acid was used instead of 2-bromo-5-methoxybenzoic acid.

Compound (1-10-1) was in the smectic phase at room temperature, and the transition temperature to the nematic phase was 102.0 ° C. The transition temperature to the isotropic liquid could not be measured due to thermal polymerization. The freezing point could not be measured due to the increase in viscosity. The NMR analysis values of the obtained compound (1-10-1) are as follows.
8.00 (d, 1H), 7.96 (d, 1H), 7.43 (d, 1H), 7.26-7.04 (m, 6H), 6.83-6.81 (m, 1H) 4H), 6.40 (dd, 2H), 6.12 (dd, 2H), 5.82 (dd, 2H), 4.81-4.74 (m, 2H), 4.17 (t, 4H) ), 3.94 (t, 4H), 2.89 (t, 4H), 2.67-2.55 (m, 9H), 2.26-2.19 (m, 4H), 2.11- 2.06 (m, 4H), 1.82-1.68 (m, 12H), 1.54-1.42 (m, 12H).

[Comparative Example 1]
The structure of compound (C-1) is shown below. Compound (C-1) is a polymerizable liquid crystal compound.

Compound (C-1) was synthesized by the procedure described in Example 2 of WO 2018/030190.

<Preparation of polymerizable liquid crystal composition>
The compound (M1-1-1) was synthesized in the same procedure as in Example 3 of JP-A-2003-238491. However, 2,7-dihydroxy-9-methylfluorene was used instead of 2,7-dihydroxyfluorene.
Compound (M2-1-1) was synthesized in the same manner as described in Makromolekclare Chemie (1991), 192 (1), 59-74.

Compound (M1-1-1) and compound (M2-1-1) are polymerizable liquid crystal compounds.
<Preparation of polymerizable liquid crystal composition>
<Polymerizable liquid crystal composition (S-1)>
The compounds listed in Table 1 were mixed with cyclohexanone in the amounts shown in Table 1 to prepare (S-6) from the polymerizable liquid crystal composition (S-1). 0 in Table 1 indicates that the corresponding compound was not mixed.

The polymerizable liquid crystal compositions (S-1) to (S-6) contain the compound (1).

Table 1

The compounds listed in Table 2 were mixed with cyclohexanone in the amounts shown in Table 2 to prepare (SC-3) from the polymerizable liquid crystal composition (SC-1). 0 in Table 2 indicates that the corresponding compound was not mixed.

Table 2

<Preparation of liquid crystal polymer film with base material>
[Example 4]
A liquid crystal polymer film with a base material was prepared by the following procedure.

Procedure (1) The polymerizable liquid crystal composition is applied onto a glass substrate with a polarizing UV-treated alignment film by spin coating.
Procedure (2) The base material is heated on a hot plate at 80 ° C. for 3 minutes.
Step (3) Subsequently, the substrate is cooled at room temperature for 3 minutes.
Procedure (4) The polymerizable liquid crystal composition on the base material is irradiated with light from an ultra-high pressure mercury lamp having a constant output at room temperature from a direction of 90 ° to polymerize the polymerizable liquid crystal composition on the base material. I let you.

However, using a receiver for measuring the illuminance at a wavelength near 365 nm, the exposure amount of the light of the ultrahigh pressure mercury lamp to the surface of the polymerizable liquid crystal composition in the procedure (4) is 500 mJ / cm ^2. , The irradiation time of the procedure (4) was adjusted between 5 seconds and 10 seconds.

[Example 5]
A liquid crystal polymer film with a base material was prepared for each polymerizable liquid crystal composition. The evaluation of the liquid crystal polymer film with a base material prepared from the polymerizable liquid crystal composition was shown in Table 3.

Table 3

The front contrast of the liquid crystal polymer film with a base material prepared from the polymerizable liquid crystal compositions (S-1) to (S-6) is prepared from the polymerizable liquid crystal compositions (SC-1) to (SC-3). It was significantly higher than the frontal contrast of the liquid crystal polymer film with a base material.

From this, it was clarified that a liquid crystal polymer film with a base material having a high front contrast can be obtained by using a polymerizable liquid crystal composition containing the disclosed polymerizable liquid crystal compound as a part of the raw material.

1 Liquid crystal polymer film 2 base material

Claims (9)

A polymerizable compound represented by the formula (1).

In equation (1),
A ¹ and A ² are independently 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenylene, pyridine-2,5-diyl, or naphthalene-2,6-diyl. , In this 1,4-phenylene or naphthalene-2,6-diyl, at least one hydrogen is fluorine, chlorine, trifluoromethyl, alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, carbon number 1 May be replaced with ~ 5 alkoxycarbonyl, or 1-5 carbon alkanoyl;
X ¹ , X ² , X ³ , X ⁴ , X ⁵ and X ⁶ are independently hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, alkyl with 1 to 12 carbon atoms, and 1 to 12 carbon atoms. Alkoxy, an alkoxycarbonyl having 1 to 12 carbon atoms, or an alkanoyl having 1 to 12 carbon atoms, and in these alkyl, alkoxy, alkoxycarbonyl, and alkanoyls, at least one -CH ₂ − is -O-, -CO. May be replaced with − or −S−;
Z ¹ and Z ² are independently single-bonded, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -CF ₂ CF _2- , -OCH ₂ CH ₂ O-, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, -COOCH ₂ CH _2- , -CH = CH-, -N = CH-, -CH = N-, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, -N = N- , Or -C≡C-;
m and n are independently integers from 0 to 3;
R ¹ and R ² are independently hydrogen, fluorine, chlorine, trifluoromethyl, trifluoromethoxy, cyano, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 1 to 12 carbon atoms, A hydrocarbylene ester having 1 to 12 carbon atoms, or a group represented by the formula (2), wherein at ^{least one of R 1} and R ² is a group represented by the formula (2).

In equation (2),
Y ¹ is a single bond, -O-, -COO-, -OCO-, or -OCOO-;
Q ¹ is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one −CH ₂ − is −O−, −COO−, −OCO−, −CH = CH−, or −CH≡ May be replaced by CH-;
P is a polymerizable functional group represented by any one of the formulas (P-1) to (P-9). )

In equations (P-1) to (P-9),
R ³ is independently hydrogen, halogen, methyl, ethyl or trifluoromethyl. A ¹ and A ² are independently 1,4-phenylene or 1,4-cyclohexylene, in which at least one hydrogen is fluorine, trifluoromethyl, carbon 21-5. May be replaced with alkyl;
X ¹ , X ² , X ³ , X ⁴ , X ⁵ , and X ⁶ are independently hydrogen or alkyl with 1 to 5 carbon atoms;
The sum of m and n is 1 or more;
Z ¹ and Z ² are independently single-bonded, -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , -OCH ₂ CH ₂ O-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO-, or -COOCH ₂ CH _2- ;
The polymerizable liquid crystal compound according to claim 1, wherein R ¹ and R ² are independently one of an alkyl having 1 to 12 carbon atoms and a group represented by the formula (2). The polymerizable liquid crystal compound according to claim 1 or 2, wherein both R ¹ and R ^{2 are groups represented by the formula (2).} The invention according to any one of claims 1 to 3, wherein P is a polymerizable functional group represented by the formula (P-1), and R ^{3 is hydrogen or methyl in the formula (P-1).} Polymerizable liquid crystal compound. A polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound according to any one of claims 1 to 4. A polymerizable liquid crystal composition in which the total amount of the polymerizable liquid crystal compound according to any one of claims 1 to 4 is 1 to 50% by weight. Liquid crystal polymer films obtained by polymerizing the polymerizable liquid crystal composition according to claim 5 or 6. The polarizing plate having the liquid crystal polymerized film according to claim 7. A display device having the liquid crystal polymerized film according to claim 7.

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