JP2022043618A - Polymerizable liquid crystal composition and liquid crystal polymers - Google Patents

Abstract

To provide a polymerizable liquid crystal composition that gives a retardation film having improved front contrast and having less tendency to decrease Re even with treatment at 230°C.SOLUTION: A polymerizable liquid crystal composition has a polymerizable liquid crystal compound represented by formula (1), and a polymerizable liquid crystal compound represented by formula (2) or formula (3).SELECTED DRAWING: None

Description

The present disclosure relates to polymerizable liquid crystal compositions and liquid crystal polymers.

The liquid crystal polymer obtained by curing the polymerizable liquid crystal composition becomes an optical element. The display element incorporates the optical element with the intention of improving the quality of the image display.

Patent Document 1 refers to a retardation film made of a liquid crystal polymer.
Patent Document 2 refers to a liquid crystal polymer obtained by curing a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound.
Patent Document 3 refers to a retardation film obtained by curing a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a silsesquioxane structure.

In order to achieve high image quality, improvement of front contrast is required.

There is a liquid crystal display element that arranges a retardation film inside the liquid crystal cell. In a typical manufacturing process of the display element, there is a heat treatment step for the display element at around 230 ° C. Therefore, if the heat resistance of the retardation film is low, the display element maintains high image quality and is difficult to mass-produce.

Japanese Unexamined Patent Publication No. 2016-051178 International release 2018/030190 JP-A-2015-105986

It is to improve the optical performance and heat resistance of the retardation film made of a liquid crystal polymer. Specifically, it is to improve the front contrast and reduce Re even in the treatment at 230 ° C. Is the subject of this aspect. It is also an issue of this aspect to facilitate mass production of high-quality display elements manufactured by the heat treatment process using the retardation film.

Aspects of the present disclosure are the following [1] to [11].

式（１）中、
Ａ^１は、独立して、１，４－フェニレン、１，４－シクロヘキシレンまたはナフタレン－２,６－ジイルであり、この１，４－フェニレンまたはナフタレン－２,６－ジイルにおいて少なくとも１つの水素はフッ素、塩素、シアノ、ホルミル、炭素数１～５のアルキル、炭素数１～５のアルコキシ、炭素数１～５のアルケニル、炭素数１～５のアルコキシカルボニル、炭素数１～５のアルカノイル、炭素数１～５のアルカノイルオキシ、炭素数１～５のフルオロアルキルまたは式（Ｐ－１）で表される基で置き換えられてもよく、
Ｚ^１は、独立して、単結合、－ＣＨ_２ＣＨ_２－、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ_２Ｏ－、－ＯＣＨ_２－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ_２ＣＨ_２ＣＯＯ－または－ＯＣＯＣＨ_２ＣＨ_２－であり、
ｎおよびｍは、０、１または２であり、かつｎおよびｍのうち少なくとも一つは１であり、
Ｐ^１は、独立して、式（Ｐ－１）で表される基であり、

式（Ｐ－１）中、
Ｙ^１は、単結合、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－または－ＯＣＯＯ－であり、
Ｑ^１は、単結合または炭素数１～２０のアルキレンであり、該アルキレンにおいて少なくとも一つの－ＣＨ_２－は－Ｏ－、－ＣＯＯ－または－ＯＣＯ－で置き換えられてもよく、
ＰＧは、アクリロイルオキシまたはメタクリロイルオキシである。

式（２）中、
Ｗ^２は、炭素数１～５のアルキル、炭素数１～５のアルコキシ、炭素数２～５のアルケニル、炭素数１～５のアルコキシカルボニル、炭素数１～５のアルカノイル、炭素数１～５のアルカノイルオキシ、炭素数１～５のフルオロアルキルまたは式（Ｐ－２）で表される基であり、これらの基において少なくとも一つの－ＣＨ_２－は－Ｏ－で置き換えられてもよく、
Ａ_２は、独立して、１，４－フェニレン、１，４－シクロヘキシレンまたはナフタレン－２，６－ジイルであり、この１，４－フェニレンまたはナフタレン－２，６－ジイルにおいて少なくとも１つの水素はフッ素、塩素、シアノ、ホルミル、炭素数１～５のアルキル、炭素数１～５のアルコキシ、炭素数１～５のアルケニル、炭素数１～５のアルコキシカルボニル、炭素数１～５のアルカノイル、炭素数１～５のアルカノイルオキシ、炭素数１～５のフルオロアルキルまたは式（Ｐ－２）で表される基で置き換えられてもよく、
Ｚ^２は、独立して、単結合、－ＣＨ_２ＣＨ_２－、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ_２Ｏ－、－ＯＣＨ_２－、－ＯＣＨ_２ＣＨ_２Ｏ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ_２ＣＨ_２ＣＯＯ－または－ＯＣＯＣＨ_２ＣＨ_２－であり、かつＺ^２のうち少なくとも一つは－ＣＨ_２ＣＨ_２ＣＯＯ－または－ＯＣＯＣＨ_２ＣＨ_２－であり、
ｒおよびｓは、それぞれ独立して、１または２であり、かつｒおよびｓのうち少なくとも一つは２であり、
Ｐ^２は、独立して、式（Ｐ－２）で表される基であり、

式（Ｐ－２）中、
Ｙ^２は、単結合、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－または－ＯＣＯＯ－であり、
Ｑ^２は、単結合または炭素数１～２０のアルキレンであり、該アルキレンにおいて少なくとも一つの－ＣＨ_２－は－Ｏ－、－ＣＯＯ－または－ＯＣＯ－で置き換えられてもよく、
ＰＧは、アクリロイルオキシまたはメタクリロイルオキシである。

式（３）中、
Ｗ^３は、独立して、水素、フッ素、炭素数１～５のアルキル、炭素数２～５のアルケニルまたは炭素数１～５のフルオロアルキルであり、
Ａ^３は、独立して、１，４－フェニレン、１，４－シクロヘキシレンまたはナフタレン－２，６－ジイルであり、この１，４－フェニレンまたはナフタレン－２,６－ジイルにおいて、少なくとも一つの水素はフッ素、塩素、シアノ、ホルミル、炭素数１～５のアルキル、炭素数１～５のアルコキシ、炭素数１～５のアルケニル、炭素数１～５のアルコキシカルボニル基、炭素数１～５のアルカノイル、炭素数１～５のフルオロアルキルまたは式（Ｐ－３）で表される基で置き換えられてもよく、
Ｚ^３は、独立して、単結合、－ＣＨ_２ＣＨ_２－、－ＣＯＯ－、－ＯＣＯ－、－ＣＨ_２Ｏ－、－ＯＣＨ_２－、－ＯＣＨ_２ＣＨ_２Ｏ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨＣＯＯ－、－ＯＣＯＣＨ＝ＣＨ－、－ＣＨ_２ＣＨ_２ＣＯＯ－、－ＯＣＯＣＨ_２ＣＨ_２－、－ＣＨ_２ＣＨ_２ＯＣＯ－または－ＣＯＯＣＨ_２ＣＨ_２－であり、
ｔおよびｕは、独立して、０、１または２であり、
Ｐ^３は独立して式（Ｐ－３）で表される基である。

式（Ｐ－３）中、
Ｙ^３は、単結合、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－または－ＯＣＯＯ－であり、
Ｑ^３は、単結合または炭素数１～２０のアルキレンであり、該アルキレンにおいて少なくとも一つの－ＣＨ_２－は－Ｏ－、－ＣＯＯ－または－ＯＣＯ－で置き換えられてもよく、
ＰＧは、アクリロイルオキシまたはメタクリロイルオキシである。 [1]
The polymerizable liquid crystal compound represented by the formula (1) and
A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound represented by the formula (2) or the formula (3).

In equation (1),
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl, and at least one hydrogen in this 1,4-phenylene or naphthalene-2,6-diyl. Fluorine, chlorine, cyano, formyl, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkenyl with 1 to 5 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms, alkanoyl with 1 to 5 carbon atoms, It may be replaced with an alkanoyloxy having 1 to 5 carbon atoms, a fluoroalkyl having 1 to 5 carbon atoms or a group represented by the formula (P-1).
Z ¹ is independently single-bonded, -CH ₂ CH _2- , -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -C≡C-, -CH = CHCOO-,- OCOCH = CH-, -CH ₂ CH ₂ COO- or -OCOCH ₂ CH _2- ,
n and m are 0, 1 or 2, and at least one of n and m is 1.
P ¹ is an independent group represented by the formula (P-1).

In equation (P-1),
Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-,
^Q1 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-.
PG is acryloyloxy or methacryloyloxy.

In equation (2),
W ² has an alkyl having 1 to 5 carbon atoms, an alkoxy having 1 to 5 carbon atoms, an alkenyl having 2 to 5 carbon atoms, an alkoxycarbonyl having 1 to 5 carbon atoms, an alkanoyl having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. Alkoxyyloxy, fluoroalkyl having 1 to 5 carbon atoms or a group represented by the formula (P-2), in which at least one -CH _2- may be replaced with -O-.
A ₂ is independently 1,4-phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl, and at least one hydrogen in this 1,4-phenylene or naphthalene-2,6-diyl. Fluorine, chlorine, cyano, formyl, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkenyl with 1 to 5 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms, alkanoyl with 1 to 5 carbon atoms, It may be replaced with an alkanoyloxy having 1 to 5 carbon atoms, a fluoroalkyl having 1 to 5 carbon atoms or a group represented by the formula (P-2).
Z ² is independently single-bonded, -CH ₂ CH _2- , -COO-, -OCO-, -CH ₂ O-, -OCH _{2-, -OCH 2 CH 2} O-, -C≡C- , -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO- or -OCOCH ₂ CH _2- , and at least one of Z ² is -CH ₂ CH ₂ COO- or -OCOCH ₂ CH ₂ -and
r and s are independently 1 or 2, and at least one of r and s is 2.
P ² is an independent group represented by the formula (P-2).

In equation (P-2),
Y ² is a single bond, -O-, -COO-, -OCO- or -OCOO-,
^Q2 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-.
PG is acryloyloxy or methacryloyloxy.

In equation (3),
W ³ is independently hydrogen, fluorine, an alkyl having 1 to 5 carbon atoms, an alkenyl having 2 to 5 carbon atoms or a fluoroalkyl having 1 to 5 carbon atoms.
A3 is independently 1,4 ^- phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl, and at least one of the 1,4-phenylene or naphthalene-2,6-diyl. Hydrogen is fluorine, chlorine, cyano, formyl, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkenyl with 1 to 5 carbon atoms, alkoxycarbonyl group with 1 to 5 carbon atoms, and 1 to 5 carbon atoms. It may be replaced with an alkanoyl, a fluoroalkyl having 1 to 5 carbon atoms or a group represented by the formula (P-3).
Z ³ is independently single-bonded, -CH ₂ CH _2- , -COO-, -OCO-, -CH ₂ O-, -OCH _{2-, -OCH 2 CH 2} O-, -C≡C- , -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO- or -COOCH ₂ CH _2- , and
t and u are independently 0, 1 or 2,
P ³ is a group independently represented by the formula (P-3).

In equation (P-3),
^Y3 is a single bond, -O-, -COO-, -OCO- or -OCOO-,
^Q3 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-.
PG is acryloyloxy or methacryloyloxy.

[2] The total amount of the polymerizable liquid crystal compound represented by the formula (1) is 5 to 50% by weight, and the total amount of the polymerizable liquid crystal compound represented by the formulas (2) and (3) is 5 to 50%. The polymerizable liquid crystal composition of [1], which is 80% by weight.

[3] The polymerizable liquid crystal compound represented by the formula (1) and
The polymerizable liquid crystal compound represented by the formula (2) and
The polymerizable liquid crystal composition according to [1], which comprises a polymerizable liquid crystal compound represented by the formula (3).

[4] The total amount of the polymerizable liquid crystal compound represented by the formula (1) is 5 to 50% by weight.
The total amount of the polymerizable liquid crystal compound represented by the formula (2) is 5 to 80% by weight, and
The polymerizable liquid crystal composition according to [1], wherein the total amount of the polymerizable liquid crystal compound represented by the formula (3) is 5 to 80% by weight.

[5] The polymerizable liquid crystal composition according to [1] to [4], which contains at least one of a polymerization initiator, a surfactant and an antioxidant.

[6] A solution containing the polymerizable liquid crystal composition according to any one of [1] to [5].

[7] Liquid crystal polymers comprising a cured product of the polymerizable liquid crystal composition according to any one of [1] to [5].

[8] A retardation film made of the liquid crystal polymer according to [7].

[9] A polarizing plate including the retardation film according to [8].

[10] A display element including the retardation film according to [8].

The retardation film made of the cured product of the polymerizable liquid crystal composition according to [1] to [5] has high optical performance and heat resistance.
The retardation film made of a cured product of the solution according to [6] has high optical performance and heat resistance.
The retardation film made of the liquid crystal polymers of [7] has high optical performance and heat resistance.
The retardation film of [8] has high optical performance and heat resistance.
The polarizing plate of [9] has high optical performance and heat resistance.
The display element of [10] has high image quality, and the display element is likely to be mass-produced even when it is manufactured by a heat treatment step.

In the present disclosure, "easy designability" refers to properties for a polymerizable liquid crystal composition.
In the present disclosure, "preservability" refers to properties for a polymerizable liquid crystal composition.

In the present disclosure, "heat resistance" refers to properties for liquid crystal polymers.
In the present disclosure, "optical properties" refers to properties for liquid crystal polymers.
In the present disclosure, "mechanical properties" refers to properties for liquid crystal polymers.
In the present disclosure, "durability" refers to properties with respect to liquid crystal polymers.

In the present disclosure, "mass production" includes low cost, short time and / or mass production.

In the present disclosure, the "front contrast" is a value of (luminance in the parallel Nicol state) / (luminance in the cross Nicol state) when an object is placed between two polarizing plates.
In the present disclosure, the "parallel Nicol state" is a state in which the polarization axes of the polarizing plates arranged opposite to each other coincide with each other.
In the present disclosure, the "cross Nicol state" is a state in which the polarization axes of the polarizing plates arranged opposite to each other are orthogonal to each other.

In the present disclosure, "Δn" is the birefringence of the liquid crystal polymer.
In the present disclosure, "d" is the thickness of the liquid crystal polymer.
In the present disclosure, "Re" is a phase delay or retardation of anomalous light with respect to normal light.
There is a relationship of Re = Δn · d.

In the present disclosure, the "compound (X)" is a compound represented by the formula (X). Here, X in "compound (X)" is a character string, a number, a symbol, or the like.
When a plurality of compounds represented by the formula (X) are present, the description "containing the compound (X)" may contain a plurality of the compounds represented by the formula (X).

In the present disclosure, the "liquid crystal composition" is a mixture having a liquid crystal phase.
In the present disclosure, the "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.

In the present disclosure, the "polymerizable 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.
In the present disclosure, the "monofunctional compound" is a compound having one polymerizable group.

In the present disclosure, the "polymerizable compound" is a compound having at least one polymerizable group.
In the present disclosure, the "polymerizable liquid crystal compound" means a liquid crystal compound which is a polymerizable compound.
In the present disclosure, the "non-liquid crystal polymerizable compound" is a polymerizable compound which is a compound having no liquid crystal phase in a pure substance.

In the present disclosure, the "polymerizable liquid crystal composition" is a composition containing a polymerizable compound and a liquid crystal compound or a composition containing a "polymerizable liquid crystal compound" and having a liquid crystal phase.
In the present disclosure, the "polymerizable liquid crystal composition solution" is a mixture containing a polymerizable liquid crystal composition and a solvent.

In the present disclosure, the "liquid crystal polymer" is a cured product of a polymerizable liquid crystal composition.
In the present disclosure, the "liquid crystal polymer with a base material" is a product composed of a base material and a liquid crystal polymer prepared by curing a polymerizable liquid crystal composition on the base material.
In the present disclosure, "liquid crystal polymers" is a general term for "liquid crystal polymers" and "liquid crystal polymers with a substrate".
The liquid crystal polymer can be separated from the base material by removing the base material from the liquid crystal polymer with a base material.
In the present disclosure, the "phase difference film" is an element having optical anisotropy and is in the form of a film or a plate.

In the present disclosure, the "pre-tilt angle" is an angle between the orientation direction of the liquid crystal molecules and the surface of the supporting base material.
In the present disclosure, "tilt orientation" refers to a pretilt angle of 5 to 85 degrees.
In the present disclosure, "homogeneous orientation" refers to a pretilt angle of 0 to 5 degrees.
In the present disclosure, "homeotropic orientation" refers to a pretilt angle of 85 to 90 degrees.
In the present disclosure, "twist orientation" is a state in which the orientation direction of the liquid crystal molecules in the long axis direction is parallel to the base material and is twisted stepwise around the spiral axis as the distance from the base material increases. Is.

In the present disclosure, "room temperature" is in the range of 15 ° C to 35 ° C.

When the following group is described in the chemical formula, the wavy line portion is the bonding position of the group. Here, the Arbitrary below is any atom or group.

<< Polymerizable Liquid Crystal Composition >> The polymerizable liquid crystal composition of the present disclosure comprises a polymerizable liquid crystal compound represented by the formula (1) and a polymerizable liquid crystal compound represented by the formula (2) or the formula (3). contains. The compound (1), the compound (2), or the compound (3), respectively, in the polymerizable liquid crystal composition may be one or more. A liquid crystal polymer using a polymerizable liquid crystal composition containing the polymerizable liquid crystal compound represented by the formula (1) and the formula (2) or the formula (3) as a raw material has improved front contrast and improved heat resistance. ..

In the polymerizable liquid crystal composition of the present disclosure, even if a large amount of the polymerizable liquid crystal compound is contained, crystals are recognized in the polymerizable liquid crystal composition even after the solvent is removed by ultraviolet rays having a wavelength of 100 nm or more and visible light. Can not. From this polymerizable liquid crystal composition, a cured product having no optical defects can be obtained.

In equation (1),
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl, and at least one hydrogen in this 1,4-phenylene or naphthalene-2,6-diyl. Fluorine, chlorine, cyano, formyl, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkenyl with 1 to 5 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms, alkanoyl with 1 to 5 carbon atoms, It may be replaced with an alkanoyloxy having 1 to 5 carbon atoms, a fluoroalkyl having 1 to 5 carbon atoms or a group represented by the formula (P-2).

Z ¹ is independently single-bonded, -CH ₂ CH _2- , -COO-, -OCO-, -C≡C-, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ . COO- or -OCOCH ₂ CH _2- .

n and m are independently 0, 1 or 2, respectively, and at least one of n and m is 1.

式（Ｐ－１）中、
Ｙ^１は、単結合、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－または－ＯＣＯＯ－であり、
Ｑ^１は、単結合または炭素数１～２０のアルキレンであり、該アルキレンにおいて少なくとも一つの－ＣＨ_２－は－Ｏ－、－ＣＯＯ－または－ＯＣＯ－で置き換えられてもよく、
ＰＧは、アクリロイルオキシ基またはメタクリロイルオキシ基である。
耐久性のため、アクリロイルオキシ基またはメタクリロイルオキシ基が、好ましい。 P ¹ is an independent group represented by the formula (P-1).

In equation (P-1),
Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-,
^Q1 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-.
PG is an acryloyloxy group or a methacryloyloxy group.
Acryloyloxy groups or methacryloyloxy groups are preferred for durability.

The compounds represented by the formulas (1-1) to (1-3) are examples of polymerizable liquid crystal compounds represented by the formula (1).

In equations (1-1) to (1-3),
Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-,
^Q1 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-.
PG is an acryloyloxy group or a methacryloyloxy group.

In equation (2),
W ² has an alkyl having 1 to 5 carbon atoms, an alkoxy having 1 to 5 carbon atoms, an alkenyl having 2 to 5 carbon atoms, an alkoxycarbonyl having 1 to 5 carbon atoms, an alkanoyl having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. Alkoxyyloxy, fluoroalkyl having 1 to 5 carbon atoms or a group represented by the formula (P-2), in which at least one -CH _2- may be replaced with -O-.
For easy design, W ¹ is preferably alkoxy having 1 to 5 carbon atoms, alkoxycarbonyl having 1 to 5 carbon atoms, alkanoyl having 1 to 5 carbon atoms, or alkanoyloxy having 1 to 5 carbon atoms.

In equation (2),
A ² is independently 1,4-phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl. In this case, in 1,4-phenylene or naphthalene-2,6-diyl, at least one hydrogen is fluorine, chlorine, cyano, formyl, an alkyl having 1 to 5 carbon atoms, an alkoxy having 1 to 5 carbon atoms, and a carbon number of carbon atoms. It is represented by an alkenyl of 1 to 5, an alkoxycarbonyl having 1 to 5 carbon atoms, an alkanoyl having 1 to 5 carbon atoms, an alkanoyloxy having 1 to 5 carbon atoms, a fluoroalkyl having 1 to 5 carbon atoms or the formula (P-2). It may be replaced with a carbonyl group.

In equation (2),
Z ² is independently single-bonded, -CH ₂ CH _2- , -COO-, -OCO-, -C≡C-, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO- or -OCOCH ₂ CH _2- , and at least one of Z ² is -CH ₂ CH ₂ COO- or -OCOCH ₂ CH _2- . For ease of design, at least one of Z ² is preferably -CH ₂ CH ₂ COO- or -OCOCH ₂ CH _2- .

r and s are independently 1 or 2, respectively, and at least one of r and s is 2.

式（Ｐ－２）中、
Ｙ^２は、単結合、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－または－ＯＣＯＯ－である。
Ｑ^２は、単結合または炭素数１～２０のアルキレンであり、該アルキレンにおいて少なくとも一つの－ＣＨ_２－は、－Ｏ－、－ＣＯＯ－または－ＯＣＯ－で置き換えられてもよい。
ＰＧは、アクリロイルオキシ基またはメタクリロイルオキシ基である。 P ² is a group independently represented by the formula (P-2).

In equation (P-2),
Y ² is a single bond, -O-, -COO-, -OCO- or -OCOO-.
^Q2 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-.
PG is an acryloyloxy group or a methacryloyloxy group.

The compounds represented by the formulas (2-1) to (2-9) are examples of the polymerizable liquid crystal compound represented by the formula (2).

In equations (2-1) to (2-9)
Y ² is a single bond, -O-, -COO-, -OCO- or -OCOO-,
^Q2 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-.
PG is an acryloyloxy group or a methacryloyloxy group.

In equation (3),
W ³ is independently hydrogen, fluorine, an alkyl having 1 to 5 carbon atoms, an alkenyl having 2 to 5 carbon atoms, or a fluoroalkyl having 1 to 5 carbon atoms.

A3 is independently 1,4 ^- phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl. In this case, in 1,4-phenylene or naphthalene-2,6-diyl, at least one hydrogen is fluorine, chlorine, a cyano group, a formyl group, an alkyl group having 1 to 5 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. , An alkenyl group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, an alkanoyl group having 1 to 5 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms or a group represented by the formula (P-3). May be replaced with.

Z ³ are independently single-bonded, -CH ₂ CH _2- , -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -OCH ₂ CH ₂ O-, -C≡C. -, -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO- or -COOCH ₂ CH _2- .

t and u are 0, 1 or 2, respectively.

式（Ｐ－３）中、
Ｙ^３は、単結合、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－または－ＯＣＯＯ－であり、
Ｑ^３は、単結合または炭素数１～２０のアルキレンであり、該アルキレンにおいて少なくとも一つの－ＣＨ_２－は－Ｏ－、－ＣＯＯ－または－ＯＣＯ－で置き換えられてもよく、
ＰＧは、アクリロイルオキシ基またはメタクリロイルオキシ基である。 P ³ is an independent group represented by the formula (P-3).

In equation (P-3),
^Y3 is a single bond, -O-, -COO-, -OCO- or -OCOO-,
^Q3 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-.
PG is an acryloyloxy group or a methacryloyloxy group.

The compounds represented by the formulas (3-1) to (3-6) are examples of the polymerizable liquid crystal compound represented by the formula (3).

In equations (3-1) to (3-6)
^Y3 is a single bond, -O-, -COO-, -OCO- or -OCOO-,
^Q3 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-, and PG is acryloyl. It is an oxy group or a methacryloyloxy group.

Due to its optical properties and heat resistance, the polymerizable liquid crystal compositions of the present disclosure are more likely to contain at least one compound (1), at least one compound (2), and at least one compound (3). preferable. The total weight of the polymerizable liquid crystal compound (1) in the polymerizable liquid crystal composition is preferably 5 to 50% by weight because of optical properties and / or easy design. The total weight of the polymerizable liquid crystal compound (2) in the polymerizable liquid crystal composition is preferably 5 to 80% by weight because of optical properties and / or easy design. The total weight of the polymerizable liquid crystal compound (3) in the polymerizable liquid crystal composition is preferably 5 to 80% by weight because of optical properties and / or easy design.

The polymerizable liquid crystal composition of the present disclosure may contain a polymerizable liquid crystal compound represented by the formula (4).

In equation (4),
A4 is independently 1,4 ^- phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl. In this case, in 1,4-phenylene or naphthalene-2,6-diyl, at least one hydrogen is fluorine, chlorine, cyano group, formyl group, alkyl group having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms. It is represented by a group, an alkenyl group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, an alkanoyl group having 1 to 5 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms or a formula (P-4). It may be replaced with a group.

Z ⁴ is independently single-bonded, -CH ₂ CH _2- , -COO-, -OCO-, -CH ₂ O-, -OCH _{2-, -OCH 2 CH 2} O-, -C≡C- , -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO- or -COOCH ₂ CH _2- .

q is 1 or 2 independently.

t and u are 0, 1 or 2, respectively.

式（Ｐ－４）中、
Ｙ^４は、単結合、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－または－ＯＣＯＯ－であり、
Ｑ^４は、単結合または炭素数１～２０のアルキレンである。この場合、該アルキレンにおいて、少なくとも一つの－ＣＨ_２－は、－Ｏ－、－ＣＯＯ－または－ＯＣＯ－で置き換えられてもよく、
ＰＧは、アクリロイルオキシ基またはメタクリロイルオキシ基である。 R is hydrogen, fluorine, chlorine, a cyano group, a formyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, and an alkoxycarbonyl having 1 to 10 carbon atoms. A group, an alkanoyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 5 carbon atoms, or a group represented by the formula (P-4).

In equation (P-4),
Y4 is a single bond, -O-, -COO-, ^-OCO- or -OCOO-,
^Q4 is a single bond or an alkylene having 1 to 20 carbon atoms. In this case, in the alkylene, at least one -CH _2- may be replaced by -O-, -COO- or -OCO-.
PG is an acryloyloxy group or a methacryloyloxy group.

<< Additives for polymerizable liquid crystal composition >>
The polymerizable liquid crystal composition of the present disclosure may contain an additive other than the polymerizable liquid crystal compound as long as the expression of the liquid crystal phase of the polymerizable liquid crystal composition is not impaired.

Due to the optical properties, it is preferable to add a surfactant to the polymerizable liquid crystal composition, and it is more preferable to add a nonionic surfactant.

Due to its optical properties, nonionic surfactants are preferable because they have the effect of suppressing the tilt orientation of the liquid crystal polymer on the air interface side, and the surfactants are more preferably surfactants that initiate a polymerization reaction with ultraviolet rays. ,preferable. Silicone-based nonionic surfactants, fluorine-based nonionic surfactants, vinyl-based nonionic surfactants, hydrocarbon-based nonionic surfactants, and the like are nonionic surfactants.

For optical properties and easy design, the total amount of the surfactant in the polymerizable liquid crystal composition is preferably 0.01 to 5% by weight, more preferably 0.05 to 1% by weight, based on the total amount of the polymerizable liquid crystal composition. preferable.

Silicone-based nonionic surfactants are linear polymers composed of siloxane bonds, such as compounds 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 the vinyl-based nonionic surfactant include (meth) acrylic polymers having a weight average molecular weight of 1000 to 1000000.

The polymerizable liquid crystal composition of the present disclosure may contain a non-liquid crystal polymerizable compound. For easy design, the total amount of the non-liquid crystal polymerizable compound in the polymerizable liquid crystal composition is preferably 30% by weight or less based on the total weight ratio of the polymerizable compounds in the polymerizable liquid crystal composition.

Due to its mechanical properties and / or durability, the polymerizable liquid crystal composition preferably contains a polyfunctional non-liquid crystal polymerizable compound.
The non-liquid crystal polymerizable compound is typically a compound having one or more vinyl-based polymerizable groups.

Addition of a non-liquid crystal polymerizable compound having a polar group at the side chain and / or the terminal to the polymerizable liquid crystal composition can be expected to improve the adhesion between the liquid crystal polymer and the photoalignment film.
The carbon number of styrene, nuclear-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylpyrrolidone, vinylsulfonic acid, fatty acid vinyl, α, β-ethylenically 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-butanoate, vinyl propionate, vinyl stearate, 2-ethyl-2- Vinyl methylbutanoate, dicyclopentanyloxylethyl (meth) acrylate, isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclopentanyl (meth) ) Acrylate, dicyclopentenyl (meth) acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxy Polyalkylyl such as ethylphthalic acid, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, polyethylene glycol with a degree of polymerization of 2 to 100, polypropylene glycol, a copolymer of ethylene oxide and propylene oxide. Mono (meth) acrylic acid ester of len glycol or di (meth) acrylic acid ester or polyethylene glycol, polypropylene glycol, ethylene oxide and propylene oxide having a degree of polymerization of 2 to 100 capped with an alkyl having 1 to 6 carbon atoms at the end. The mono (meth) acrylic acid ester of polyalkylene glycol which is a copolymer is a non-liquidaceous polymerizable compound which is a monofunctional compound. Vinyl acetate and the like are "vinyl acetate". 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, methylcarbyl ester, ethylcarbyl ester, butylcarbyl ester, etc. are described as "ether oxygen-containing alkyl of (meth) acrylic acid having 3 to 18 carbon atoms of ether oxygen-containing alkyl. 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 non-liquidaceous polymerizable compounds. Is.

Pentaeristol Triacrylate, Trimethylol Propane Triacrylate, Trimethylol EO-Addition Triacrylate, Trisacryloyloxyethyl Phosphate, Tris (Acryloyloxyethyl) Isocyanurate, Alkyl-modified Dipentaerythritol Triacrylate, EO-Modified Trimethylol Propanetricyl Rate, PO-modified trimethylol propanetriacrylate, pentaerythritol tetraacrylate, alkyl-modified dipentaerythritol tetraacrylate, ditrimethylol propanetetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, alkyl-modified dipentaerythritol pentaacrylate , Pentaeristol trimetaacrylate, trimethylolpropane trimetaacrylate, trimethylol EO-added trimetaacrylate, trimethacryloyloxyethyl phosphate, trismethacryloyloxyethyl 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 trifunctional or higher functional polyfunctional non-liquidaceous polymerizable compounds.

Addition of a polymerizable compound having a bisphenol structure or a cardo structure to a polymerizable liquid crystal composition induces an improvement in the degree of curing of the polymer and a homeotropic orientation of the liquid crystal polymer.

Examples of the polymerizable fluorene derivative having a cardo structure include compounds (α-1) to (α-3).

In the formulas (α-1) to (α-3), Rα is independently hydrogen or methyl, and s is independently an integer of 0 to 4.

The addition of the polymerization initiator optimizes the polymerization rate of the polymerizable liquid crystal composition. A photoradical initiator is preferable as the polymerization initiator because of the ease of the curing process.

As the photoradical initiator, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-1,2 -Diphenylethan-1-one, p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystylyl) -5-trichloromethyl-1,3,4-oxadiazole, 9- Phenylaclysin, 9,10-benzphenazine, benzophenone / Michelersketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, benzyldimethylketal , 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one, 2,4-diethylxanthone / p-dimethylaminomethyl benzoate mixture, benzophenone / methyltriethanolamine mixture, Adeca Arcles N-1919, Adeca Arkles NCI-831, Adeca Arkles NCI-930, Adeca Arkles NCI-730, Omnirad 127, Omnirad 184, Omnirad 369, Omnirad 379, Omnirad 500, Omnirad 651, Omnirad 651, Omnirad 651 , Omnirad 907, Omnirad 1173, Omnirad 2022, Omnirad 2100, Omnirad 2959, Omnirad 4265, IrgaCure OXE01, IrgaCure OXE02, Omnirad MBF, Omnirad TPO and the like. Here, Adeka Arcurus, Omnirad and Irga Cure are registered trademarks.

From the viewpoint of optical properties, mechanical properties and durability, the total weight of the photoradical polymerization initiator in the polymerizable liquid crystal composition is preferably 1 to 30% by weight based on the total amount of the polymerizable liquid crystal composition. It is more preferably from 15% by weight, still more preferably from 3 to 10% by weight.

From the viewpoint of mechanical properties and durability, it is preferable to add a sensitizer to the polymerizable liquid crystal composition containing a photoradical polymerization initiator. Sensitizers include isopropylthioxanthone, diethylthioxanthone, ethyl-4dimethylaminobenzoate, 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 length of the chain of the polymer in the liquid crystal polymer 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. From the viewpoint of mechanical properties and durability, it is preferable to adjust the reaction rate of the polymerizable liquid crystal compound and the chain length of the polymer in the liquid crystal polymer.

Monofunctional thiol derivatives, polyfunctional all derivatives, styrene dimer derivatives and the like are chain transfer agents.

Dodecanethiol, 2-ethylhexyl- (3-mercapto) propionate and the like are thiol derivatives.

Trimethylol propanetris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 1,4-bis (3-mercaptobutylyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate) , 1,3,5-Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like are polyfunctional thiol derivatives.

2,4-Diphenyl-4-methyl-1-pentene, 2,4-diphenyl-1-butene and the like are styrene dimer-based chain transfer agents.
For storage stability, it is preferable to add a polymerization inhibitor to the polymerizable composition.

Polymerization inhibitors are (a) phenol-based antioxidants, (b) sulfur-based antioxidants, (c) phosphoric acid-based antioxidants, (d) hindered amine-based antioxidants, and the like. Phenolic antioxidants are preferred from the standpoint of ease of design and optical properties. From the viewpoint of easy design, a phenolic antioxidant having a t-butyl group at the ortho position of the hydroxyl group is preferable.

The total weight of the polymerization inhibitor in the polymerizable liquid crystal composition is preferably 0.01 to 5% by weight, more preferably 0.01 to 0.5% by weight, because of storage stability, durability, and mechanical properties. ..

The addition of an ultraviolet absorber to the polymerizable liquid crystal composition improves the weather resistance of the polymerizable liquid crystal composition.
Addition of a light stabilizer to the polymerizable liquid crystal composition improves the weather resistance of the polymerizable liquid crystal composition.
Addition of an antioxidant to the polymerizable liquid crystal composition improves the weather resistance of the polymerizable liquid crystal composition.
The addition of a silane coupling agent to the polymerizable liquid crystal composition improves durability, optical properties, and mechanical properties.

<< Polymerizable liquid crystal composition solution >>
It is preferable to add a solvent to the polymerizable liquid crystal composition because of the ease of design. For easy design, the content of the polymerizable liquid crystal composition in the polymerizable liquid crystal composition solution is preferably 5 to 50% by weight, more preferably 15 to 40% by weight.

Ester-based solvent, amide-based solvent, alcohol-based solvent, ether-based solvent, cyclic ether-based solvent, aromatic hydrocarbon-based solvent, halogenated aromatic hydrocarbon-based solvent, aliphatic hydrocarbon-based solvent, halogenated aliphatic hydrocarbon A system solvent, an alicyclic hydrocarbon solvent, a ketone solvent, an acetate solvent and the like are typical components of the solvent.

The ester-based solvent refers to a compound having an ester bond 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 ester solvents.

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 malonic acid.
Methyl glycolate, ethyl glycolate and the like are alkyl glycolates.
Methyl lactate, ethyl lactate, isopropyl lactate, n-propyl lactate, butyl lactate, ethylhexyl lactate and the like are alkyl lactates.

The amide-based solvent is a compound having an amide bond and is a component of the solvent.
N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylacetamide dimethylacetamide , N-Methylcaprolactam, 1,3-dimethyl-2-imidazolidinone and the like are amide-based solvents.

The alcohol-based solvent is a compound having a hydroxyl group and is a component of the solvent.
Methanol, ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, t-butyl alcohol, sec-butyl alcohol, butanol, 3-methoxybutanol, 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, tripropylene glycol, hexylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,4-pentanediol, 2,5 -Hexanediol, 3-methyl-3-methoxybutanol, cyclohexanol, methylcyclohexanol, ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, Terpineol, dihydroterpineol, etc. are alcohols.

The ether solvent is a compound having an ether bond and is a component of the solvent.
Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, bis (2-propyl) ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, anisole, cyclopentylmethyl ether, methyl T-butyl ether and the like are ether-based solvents.

The cyclic ether solvent is a cyclic compound having an ether bond and is a component of the solvent.
1,4-dioxane, 1,3-dioxolane, tetrahydrofuran and the like are cyclic ether solvents.

The aromatic hydrocarbon-based solvent is a compound having an aromatic hydrocarbon and is a component of the solvent.
Benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, i-propylbenzene, n-propylbenzene, t-butylbenzene, s-butylbenzene, n-butylbenzene, tetraline and the like are aromatic hydrocarbon solvents.

Chlorobenzene, 1,2-dichlorobenzene and the like are halogenated aromatic hydrocarbon solvents.
Hexane, heptane, myrcene and the like are aliphatic hydrocarbon solvents.

Chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichlorethylene, tetrachlorethylene and the like are halogenated aliphatic hydrocarbon solvents.
Cyclohexane, cycloheptane, decalin, α-pinene, β-pinene, D-limonene and the like are alicyclic hydrocarbons.

The ketone solvent is a compound having a ketone structure and is a component of the solvent.
Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, methyl propyl ketone and the like are ketone solvents.

The acetate-based solvent is a compound having an acetoxy group and is a component of the solvent.
Ethylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, methyl acetate acetate, 1-methoxy-2-propyl acetate, etc. However, it is an acetate-based solvent.

The polymerizable liquid crystal composition of the present disclosure may contain a compound having optical activity. Addition of an optically active compound to the liquid crystal composition induces the liquid crystal polymer in a twisted orientation. The liquid crystal polymer can be used as a selective reflection film and a negative C plate in the wavelength region of 300 to 2000 nm.
By adjusting the content of the optically active compound, it can be used as a reflective film that selectively reflects a specific circularly polarized light in a specific wavelength region. Adjusting the selectivity of the reflection by adjusting the content of the optically active compound is a matter of design by those skilled in the art.

Examples of the optically active compound include compounds having an asymmetric carbon such as isosorbide and isomannide, axial asymmetric compounds having a binaphthyl structure and a helicene structure, and surface asymmetric compounds having a cyclophane structure and the like. For durability, the optically active compound in this case is preferably a polymerizable compound.

The liquid crystal polymer of the present disclosure may contain a dichroic dye. The liquid crystal polymer complexed with the dichroic dye can be used as a polarizing plate.

The dichroic dye preferably has a maximum absorption wavelength in the range of 300 to 700 nm in order to exhibit polarization performance in the visible region. As the dichroic dye, an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye, an anthraquinone dye and the like can be used. Examples of the azo dye include a monoazo dye, a bisazo dye, a trisazo dye, a tetrakisazo dye, and a stilbene azo dye.

The liquid crystal polymer of the present disclosure may contain a fluorescent dye. The liquid crystal polymer complexed with the fluorescent dye can be used as a polarized light emitting film and a wavelength conversion film.

≪Base material≫
Glass, plastic, metal and the like can be used as substrates. 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.

When forming a homogenius-oriented and tilt-oriented liquid crystal polymer on a substrate, the substrate is surface-treated to induce the orientation of the liquid crystal polymer before the polymerizable liquid crystal composition is applied to the substrate. do. The surface treatment is a method such as (a) rubbing on a base material, (d) inclined vapor deposition of silicon oxide on a base material, and (c) polarized UV irradiation.

Due to the optical properties, it is preferable to form an alignment film on the substrate.

The following procedure is an example of the rubbing.
(1) Wrap a rubbing cloth made of materials such as rayon, cotton, and polyamide around a metal roll, etc.
(2) The roll is brought into contact with the base material, and the roll is brought into contact with the base material.
(3) The roll is moved in parallel with the surface of the base material while rotating the roll, or the base material is moved while the roll is fixed.
Prior to rubbing, the substrate may be provided with a polymer coating on the substrate and rubbed on the coating. As the film, what is called a rubbing alignment film such as polyimide, polyamic acid or polyvinyl alcohol is used.
Rubbing is preferred because of its optical properties.

The following procedure is an example of the polarized UV irradiation.
(1) A polymer film called a photo-alignment film is provided on the substrate.
(2) The substrate is irradiated with linearly polarized light having a wavelength of 250 to 400 nm.
Due to optical and / or mechanical properties, the substrate may be heat treated.
The photoalignment film may be a polyimide containing a photosensitive group, a polyamic acid, a polyacrylate, or the like. The photosensitive group is preferably a chalcone, cinnamate, cinnamoyl or azo group.
Polarized UV irradiation is preferred because of its optical and / or mechanical properties.

≪Liquid crystal polymer≫
The liquid crystal polymer of the present disclosure 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) The polymerizable liquid crystal composition is polymerized by means such as light, heat, and a catalyst to obtain a liquid crystal polymer.
As a result, the polymerizable liquid crystal composition in the coating film is cured in the state of a liquid crystal.

Due to its mechanical properties, the polymerizable liquid crystal composition can be applied to a substrate by spin coating, micro gravure coating, gravure coating, wire bar coating, dip coating, spray coating, meniscus coating and die coating. The method is preferred.

For mass production, it is preferable to heat-treat during drying when forming a coating film composed of a polymerizable liquid crystal composition. The heat treatment includes the use of a hot plate or drying oven and the blowing of warm or hot air.

An electron beam, light, or the like can be used to cure the polymerizable liquid crystal composition. In this case, the wavelength range of light is preferably 150 to 500 nm, more preferably 250 to 450 nm, and most preferably 300 to 400 nm.

As the light source of the light, a low pressure mercury lamp, a high pressure discharge lamp, and a short arc discharge lamp can be used. The sterilization lamp, fluorescent chemical lamp, rack light and the like are the 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 the short arc discharge lamps.

By applying the polymerizable liquid crystal composition on the polarizing plate and curing it, a polarizing plate having a function such as optical compensation can be manufactured. A circular polarizing plate can be manufactured by combining a liquid crystal polymer having Re of a 1/4 wave plate and a polarizing plate. In this case, an absorption-type polarizing plate doped with iodine or a dichroic dye, a reflection-type polarizing plate such as a wire grid polarizing plate, or the like is the polarizing plate.

This disclosure is not limited to published examples.

化合物（１－２－１）および化合物（１－３－１）は特開２０１３－２５３０４１に従い合成できる。化合物（２－５－１）は国際公開２０１８／０３０１９０に従い合成できる。化合物（２－６－１）は特開２０１８－０７６４９１に従い合成できる。化合物（３－１－１）特開２００３－２３８４９１に従い合成できる。化合物（３－４－１）は特開２０１８－３９９９０に従い合成できる。化合物（４－１）はＭａｋｒｏｍｏｌｅｋｕｌａｒｅ Ｃｈｅｍｉｅ，（１９９１），１９２（１），５９－７４に従い合成できる。化合物（４－２）は特開２０００－３１０７１５に従い合成できる。化合物（Ｍ－１）は特願２０１７－１２５００９に従い合成できる。 1. 1. Definition of Term In the examples, "NCI-730" is an initiator manufactured by ADEKA Corporation, ADEKA ARCRUSE ™ NCI-730.
In the examples, "NCI-930" is an initiator manufactured by ADEKA Corporation, ADEKA A-CRUSE ™ NCI-930.
In the examples, "FTX-218" is a surfactant manufactured by Neos Co., Ltd., FTX-218 (trademark).
In the examples, "Polyflow No. 75" is an acrylic surfactant of Kyoeisha Chemical Co., Ltd., Polyflow No. 75. 75.
In the examples, "F-556" is DIC Corporation's fluorine-based surfactant, Megafuck ™ F-556.
In the examples, "AO-60" is a polymerization inhibitor manufactured by ADEKA Corporation, ADEKA STAB ™ AO-60.
In the examples, "CHN" is cyclohexanone.
In the examples, "CPN" is cyclopentanone.
Compound (1-2-1), compound (1-3-1), compound (2-5-1), compound (2-6-1), compound (3-1-1), compound (3-4) -1), compound (4-1), compound (4-2) and the structure of compound (M-1) are as follows.

Compound (1-2-1) and compound (1-3-1) can be synthesized according to Japanese Patent Application Laid-Open No. 2013-253041. Compound (2-5-1) can be synthesized according to International Publication 2018/030190. Compound (2-6-1) can be synthesized according to JP-A-2018-076491. Compound (3-1-1) can be synthesized according to JP-A-2003-238491. Compound (3-4-1) can be synthesized according to JP-A-2018-39990. Compound (4-1) can be synthesized according to Machromolekulare Chemie, (1991), 192 (1), 59-74. Compound (4-2) can be synthesized according to JP-A-2000-310715. Compound (M-1) can be synthesized according to Japanese Patent Application No. 2017-125009.

In the embodiment of the present disclosure, the "wire grid polarizing plate" is UVT300A manufactured by Polatechno Co., Ltd.
In the embodiment of the present disclosure, the "ultra-high pressure mercury lamp" is a multi-light USH-250BY manufactured by Ushio, Inc.
In the embodiment of the present disclosure, the "365 receiver" is a UVD-S365 manufactured by Ushio, Inc. connected to a UIT-150-A manufactured by Ushio, Inc.

2. 2. Preparation of a glass substrate with a photo-alignment-treated alignment film A glass substrate with a photo-alignment-treated alignment film is prepared by the following procedure.
(1) Spin-coat the glass with a photo-aligning agent.
(2) The obtained glass was placed on a hot plate at 60 ° C. with the spin-coated side facing up, and the solvent in the photoaligning agent was removed to prepare a coating film.
(3) The coating film was irradiated with linear polarization having a wavelength of 365 nm from the normal of the coated surface at room temperature in an air atmosphere until the wavelength reached 2000 mJ / cm ² using an ultrahigh pressure mercury lamp.
(4) After that, it is allowed to stand for 30 minutes in an oven set at 230 ° C. to obtain a glass substrate with a photoalignment-treated alignment film.
Here, as the photo-aligning agent, PIA-105C-03X is a polymer for photo-alignment treatment manufactured by JNC Co., Ltd. The photo-alignment process induces a horizontal alignment mode. The spin coating is adjusted so that the film thickness after the spin coating is 100 nm.
The linearly polarized ultraviolet rays are obtained by transmitting the light from the ultrahigh pressure mercury lamp through the wire grid polarizing plate.
The linearly polarized ultraviolet light confirms the energy per area with a 365 receiver.

3. 3. Preparation of Polymerizable Liquid Crystal Composition Solution The polymerizable liquid crystal composition solution is prepared by the following procedure:
(1) A polymerizable liquid crystal compound, a photopolymerization initiator, a surfactant and a polymerization inhibitor were mixed at the weight ratios shown in Table 1 to obtain a polymerizable liquid crystal composition.
(2) The polymerizable liquid crystal composition and the solvent are mixed at the weight ratios shown in Table 1 to obtain a mixture.
(3) Filter with a 0.2 μm membrane filter and name the solution of the polymerizable liquid crystal composition shown in Table 1.

Table 1

4. Preparation of liquid crystal polymer A liquid crystal polymer is prepared by the following procedure:
(1) The polymerizable liquid crystal composition solution is spin-coated on a glass substrate with a photo-alignment-treated alignment film at room temperature.
(2) The glass substrate was spin-coated on a hot plate at 80 ° C. with the portion facing up, and the glass substrate was allowed to stand for 2 minutes.
(3) Allow the glass substrate to stand at room temperature for 1 minute.
(4) The glass substrate is irradiated with UV of 500 mJ / cm ² from the normal direction of the substrate to prepare a liquid crystal polymer, and the names of the liquid crystal polymers shown in Table 2 are named.

Table 2

5. Evaluation Method of Liquid Crystal Polymer In the examples, the "polarization analyzer" is an OPIPRO polarization analyzer manufactured by Shintech Co., Ltd.
In the embodiment, the "polarizing microscope" is an ECLIPSE E600 POL manufactured by Nikon Corporation.
In the embodiment, the "luminance meter" is Yokogawa 3298F.
In the embodiment, the "fine shape measuring device" is an Alpha Step IQ manufactured by KLA TECOR Co., Ltd.

<Measurement by ellipsometry device>
Re of the liquid crystal polymer is measured by an ellipsometry device with the incident angle of light set to 0 °. The wavelength of the light used for the measurement is 550 nm.

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

<Measurement of brightness in cross Nicol state>
Measure the brightness in the cross Nicol state by the following procedure.
(1) A retardation film is sandwiched between two polarizing plates, and both polarizing plates are arranged on a luminance meter so as to form a cross Nicol.
(2) The minimum luminance when the retardation film is rotated horizontally is defined as "luminance in the cross Nicol state".

<Measurement of brightness in parallel Nicol state>
The brightness in the parallel Nicol state was measured by the following procedure.
(1) A retardation film is sandwiched between two polarizing plates, and both polarizing plates are arranged on a luminance meter so as to form a parallel Nicol.
(2) The maximum brightness when the retardation film is rotated horizontally is defined as "brightness in the parallel Nicol state".

<Measurement of frontal contrast of liquid crystal polymer>
The front contrast of the liquid crystal polymer is calculated by "brightness in the parallel Nicol state" / "brightness in the cross Nicol state".

6. Evaluation Results of Liquid Crystal Polymers From the obtained liquid crystal polymer (F-1), the liquid crystal polymer (F-7), the liquid crystal polymer (SF-7) and the liquid crystal polymer (SF-7) are homogenically oriented. ..

From the obtained liquid crystal polymer (F-1), the liquid crystal polymer (F-7), the liquid crystal polymer (SF-7) and the liquid crystal polymer (SF-7) were found to have orientation defects by a polarizing microscope and a polarization analyzer. Cannot be found.

The heat resistance of the liquid crystal polymer was evaluated by the following procedure.
(1) Re of the liquid crystal polymer of the liquid crystal polymer with a base material was obtained and set as Re_a.
(2) The liquid crystal polymer with a substrate was allowed to stand in an oven at 230 ° C. for 30 minutes.
(3) The liquid crystal polymer with a base material is air-cooled and then air-cooled.
(4) Re of the liquid crystal polymer of the liquid crystal polymer with a base material was obtained and set as Re_b.
(5) Re_a / (Re_a / Re_b) is calculated and heat resistance is evaluated.

From the obtained liquid crystal polymer (F-1), the front contrast of the liquid crystal polymer (F-7), the liquid crystal polymer (SF-7) and the liquid crystal polymer (SF-7), Re_a, Re_b and Re_a / ( Re_a / Re_b) are shown in Table 3.

In Table 2, the liquid crystal polymers (F-1) to (F-7) of the present disclosure have higher frontal contrast and maintain heat resistant phase difference as compared with the liquid crystal polymers (CF-1) and (CF-2). It is shown that a liquid crystal polymer having a high ratio can be obtained.

Claims (10)

The polymerizable liquid crystal compound represented by the formula (1) and
A polymerizable liquid crystal composition containing a polymerizable liquid crystal compound represented by the formula (2) or the formula (3).

In equation (1),
A ¹ is independently 1,4-phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl, and at least one hydrogen in this 1,4-phenylene or naphthalene-2,6-diyl. Is fluorine, chlorine, cyano, formyl, an alkyl group having 1 to 5 carbon atoms, an alkoxy having 1 to 5 carbon atoms, an alkenyl having 1 to 5 carbon atoms, an alkoxycarbonyl having 1 to 5 carbon atoms, and an alkanoyl having 1 to 5 carbon atoms. , Alcanoyloxy having 1 to 5 carbon atoms, fluoroalkyl having 1 to 5 carbon atoms or a group represented by the formula (P-1) may be replaced.
Z ¹ is independently single-bonded, -CH ₂ CH _2- , -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -C≡C-, -CH = CHCOO-,- OCOCH = CH-, -CH ₂ CH ₂ COO- or -OCOCH ₂ CH _2- ,
n and m are 0, 1 or 2, and at least one of n and m is 1.
P ¹ is an independent group represented by the formula (P-1).

In equation (P-1),
Y ¹ is a single bond, -O-, -COO-, -OCO- or -OCOO-,
^Q1 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-.
PG is acryloyloxy or methacryloyloxy.

In equation (2),
W ² has an alkyl having 1 to 5 carbon atoms, an alkoxy having 1 to 5 carbon atoms, an alkenyl having 2 to 5 carbon atoms, an alkoxycarbonyl having 1 to 5 carbon atoms, an alkanoyl having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. Alkoxyyloxy, fluoroalkyl having 1 to 5 carbon atoms or a group represented by the formula (P-2), in which at least one -CH _2- may be replaced with -O-.
A ² is independently 1,4-phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl, and at least one hydrogen in this 1,4-phenylene or naphthalene-2,6-diyl. Fluorine, chlorine, cyano, formyl, alkyl with 1 to 5 carbon atoms, alkoxy with 1 to 5 carbon atoms, alkenyl with 1 to 5 carbon atoms, alkoxycarbonyl with 1 to 5 carbon atoms, alkanoyl with 1 to 5 carbon atoms, It may be replaced with an alkanoyloxy having 1 to 5 carbon atoms, a fluoroalkyl having 1 to 5 carbon atoms or a group represented by the formula (P-2).
Z ² is independently single-bonded, -CH ₂ CH _2- , -COO-, -OCO-, -CH ₂ O-, -OCH _{2-, -OCH 2 CH 2} O-, -C≡C- , -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO- or -OCOCH ₂ CH _2- , and at least one of Z ² is -CH ₂ CH ₂ COO- or -OCOCH ₂ CH ₂ -and
r and s are independently 1 or 2, and at least one of r and s is 2.
P ² is an independent group represented by the formula (P-2).

In equation (P-2),
Y ² is a single bond, -O-, -COO-, -OCO- or -OCOO-,
^Q2 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-.
PG is acryloyloxy or methacryloyloxy.

In equation (3),
W ³ is independently hydrogen, fluorine, an alkyl having 1 to 5 carbon atoms, an alkenyl having 2 to 5 carbon atoms or a fluoroalkyl having 1 to 5 carbon atoms.
A3 is independently 1,4 ^- phenylene, 1,4-cyclohexylene or naphthalene-2,6-diyl, and at least one of the 1,4-phenylene or naphthalene-2,6-diyl. Hydrogen is fluorine, chlorine, cyano, formyl, an alkyl group having 1 to 5 carbon atoms, an alkoxy having 1 to 5 carbon atoms, an alkenyl having 1 to 5 carbon atoms, an alkoxycarbonyl having 1 to 5 carbon atoms, and 1 to 5 carbon atoms. It may be replaced with an alkanoyl, a fluoroalkyl having 1 to 5 carbon atoms or a group represented by the formula (P-3).
Z ³ is independently single-bonded, -CH ₂ CH _2- , -COO-, -OCO-, -CH ₂ O-, -OCH _{2-, -OCH 2 CH 2} O-, -C≡C- , -CH = CHCOO-, -OCOCH = CH-, -CH ₂ CH ₂ COO-, -OCOCH ₂ CH _2- , -CH ₂ CH ₂ OCO- or -COOCH ₂ CH _2- , and
t and u are independently 0, 1 or 2,
P ³ is a group independently represented by the formula (P-3).

In equation (P-3),
^Y3 is a single bond, -O-, -COO-, -OCO- or -OCOO-,
^Q3 is a single bond or an alkylene having 1 to 20 carbon atoms, in which at least one -CH _2- may be replaced with -O-, -COO- or -OCO-.
PG is acryloyloxy or methacryloyloxy. Based on the total amount of the polymerizable liquid crystal composition, the total amount of the polymerizable liquid crystal compound represented by the formula (1) is 5 to 50% by weight, and the polymerizable liquid crystal compounds represented by the formulas (2) and (3) are polymerizable. The polymerizable liquid crystal composition according to claim 1, wherein the total amount of the liquid crystal compound is 5 to 80% by weight. The polymerizable liquid crystal compound represented by the formula (1) and
The polymerizable liquid crystal compound represented by the formula (2) and
The polymerizable liquid crystal composition according to claim 1, which comprises a polymerizable liquid crystal compound represented by the formula (3). The total amount of the polymerizable liquid crystal compound represented by the formula (1) is 5 to 50% by weight.
The total amount of the polymerizable liquid crystal compound represented by the formula (2) is 5 to 80% by weight, and
The polymerizable liquid crystal composition according to claim 1 or 3, wherein the total amount of the polymerizable liquid crystal compound represented by the formula (3) is 5 to 80% by weight. The polymerizable liquid crystal composition according to any one of claims 1 to 4, which contains at least one of a polymerization initiator, a surfactant and an antioxidant. A solution containing the polymerizable liquid crystal composition according to any one of claims 1 to 5. A liquid crystal polymer comprising a cured product of the polymerizable liquid crystal composition according to any one of claims 1 to 5. A retardation film made of the liquid crystal polymers of claim 7. A polarizing plate including the retardation film according to claim 8. A display element including the retardation film according to claim 8.