JP6922205B2 - Side chain type liquid crystal polymer, liquid crystal composition, retardation film and its manufacturing method, transfer laminate, optical member, and display device. - Google Patents

Description

The present disclosure relates to side chain liquid crystal polymers, liquid crystal compositions, retardation films and methods for producing them, transfer laminates, optical members, and display devices.

Conventionally, with respect to display devices such as a liquid crystal display device and a light emitting display device, a configuration in which various optical members are arranged on a panel surface has been proposed. Further, it has been proposed that such an optical member has a configuration in which a phase difference is provided by a liquid crystal material.

For example, in a light emitting display device such as an organic light emitting display device, a metal electrode having excellent reflectivity is provided in order to efficiently use the light of the light emitting layer. On the other hand, since the reflection of external light is increased by using the metal electrode, the light emission display device has a circular polarizing plate or the like for suppressing the reflection of external light.

The light transmitted through the polarizing plate has optical anisotropy, and in the display device, the anisotropy causes a decrease in contrast due to the viewing angle and the like. On the other hand, a method of improving the viewing angle by using a retardation film, particularly a positive C-type retardation film (positive C plate) is known.

The positive C plate can be obtained, for example, by orienting the rod-shaped liquid crystal molecules in the plate perpendicularly to the plate surface.
For example, Patent Document 1 has a phase difference having a homeotropic-oriented liquid crystal film formed of a homeotropic-oriented liquid crystal composition containing a specific homeotropic-oriented side-chain liquid crystal polymer and a photopolymerizable liquid crystal compound. The board is disclosed.

Japanese Unexamined Patent Publication No. 2003-149441

The embodiment of the present disclosure has a side-chain type liquid crystal polymer and a liquid crystal composition capable of suppressing the precipitation of liquid crystals and widening the temperature range in which the liquid crystals are oriented, and a retardation layer in which precipitation of liquid crystals is suppressed and mass productivity is improved. It is an object of the present invention to provide a retardation film, a transfer laminate capable of transferring the retardation layer, an optical member having the retardation film, and a display device.

One embodiment of the present disclosure provides a side chain type liquid crystal polymer containing a copolymer having a structural unit represented by the following general formula (I) and a liquid crystal structural unit.

（一般式（Ｉ）中、Ｒ^１は、水素原子又はメチル基を、Ｒ^２は、−（ＣＨ_２）_ｎ−Ｌ^１−Ａｒ^１−Ｒ^３、又は−（Ｃ_２Ｈ_４Ｏ）_ｎ’−Ａｒ^１−Ｒ^３で表される基を、Ｌ^１は、直接結合、又は、−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、若しくは−Ｃ（＝Ｏ）−Ｏ−で表される連結基を、Ａｒ^１は、置換基を有していてもよい炭素原子数６以上１２以下のアリーレン基を、Ｒ^３は、置換基を有していてもよい炭素原子数２以上１０以下の直鎖又は分岐のアルキル基又はアルコキシ基を表し、ｎ及びｎ’はそれぞれ独立に２以上１０以下の整数である。）

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is − (CH ₂ ) _n −L ¹ −Ar ¹ −R ³ or − (C ₂ H ₄ O) _{n ′.} The group represented by ^{−Ar 1} −R ^{3 is directly bonded to L 1} , or is represented by −O−, −OC (= O) −, or −C (= O) −O−. As the linking group, Ar ¹ is an arylene group having 6 or more and 12 or less ^{carbon atoms which may have a substituent, and R 3} is an arylene group which may have a substituent and has 2 or more and 10 or less carbon atoms. Represents a linear or branched alkyl group or alkoxy group, and n and n'are independently integers of 2 or more and 10 or less.)

One embodiment of the present disclosure provides a side chain liquid crystal polymer in which the liquid crystal structural unit contains a structural unit represented by the following general formula (II).

（一般式（ＩＩ）中、Ｒ^１１は、水素原子又はメチル基を、Ｒ^１２は、−（ＣＨ_２）_ｍ−、又は−（Ｃ_２Ｈ_４Ｏ）_ｍ’−で表される基を表す。Ｌ^２は、直接結合、又は、−Ｏ−、−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｎ（−Ｒ^１４ ）−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｎ（−Ｒ^１４）−、−Ｏ−Ｃ（＝Ｏ）−Ｎ（−Ｒ^１４）−、−Ｎ（−Ｒ^１４）−Ｃ（＝Ｏ）−Ｏ−、−Ｎ（−Ｒ^１４）−Ｃ（＝Ｏ）−Ｎ（−Ｒ^１４）−、−Ｏ−Ｎ（−Ｒ^１４）−、若しくは−Ｎ（−Ｒ^１４）−Ｏ−で表される連結基を、Ｒ^１４は、水素原子又は炭素原子数１以上６以下のアルキル基を表す。Ａｒ^２は、置換基を有していてもよい炭素原子数６以上１０以下のアリーレン基を表し、複数あるＬ^２及びＡｒ^２はそれぞれ同一であっても異なっていても良い。Ｒ^１３は、−Ｆ、−Ｃｌ、−ＣＮ、−ＯＣＦ_３、−ＯＣＦ_２Ｈ、−ＮＣＯ、−ＮＣＳ、−ＮＯ_２、−ＮＨＣ（＝Ｏ）−Ｒ^１５、−Ｃ（＝Ｏ）−ＯＲ^１５、−ＯＨ、−ＳＨ、−ＣＨＯ、−ＳＯ_３Ｈ、−ＮＲ^１５ _２、−Ｒ^１６、又は−ＯＲ^１６を、Ｒ^１５は、水素原子又は炭素原子数１以上６以下のアルキル基を表し、Ｒ^１６は、炭素原子数１以上６以下のアルキル基を表す。ａは２以上４以下の整数、ｍ及びｍ’はそれぞれ独立に２以上１０以下の整数である。）

(In the general formula (II), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a group represented by − (CH ₂ ) _m − or − (C ₂ H ₄ O) _{m ′ −.} . L ² is a direct bond or -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -N (-R ¹⁴ ) -C (= O)-, -C (= O) -N (-R ¹⁴ )-, -OC (= O) -N (-R ¹⁴ )-, -N ( -R ¹⁴ ) -C (= O) -O-, -N (-R ¹⁴ ) -C (= O) -N (-R ¹⁴ )-, -ON (-R ¹⁴ )-, or -N (-R ¹⁴ ) The linking group represented by -O-, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms. Ar ² is a carbon which may have a substituent. It represents an arylene group having 6 or more and 10 or less atoms, and a plurality of L ² and Ar ² may be the same or different, respectively. R ¹³ is -F, -Cl, -CN, -OCF ₃ , -. OCF ₂ H, -NCO, -NCS, -NO ₂ , -NHC (= O) -R ¹⁵ , -C (= O) -OR ¹⁵ , -OH, -SH, -CHO, -SO ₃ H, -NR ¹⁵ _2, ^{-R 16,} or ^{-OR 16, R 15} represents a hydrogen atom or a carbon atoms of 1 to 6. the alkyl ^{group, R 16} represents 1 to 6 alkyl group carbon atoms. a is an integer of 2 or more and 4 or less, and m and m'are independently integers of 2 or more and 10 or less.)

One embodiment of the present disclosure contains a side-chain type liquid crystal polymer, a polymerizable liquid crystal compound, and a photopolymerization initiator, and the side-chain type liquid crystal polymer is a structural unit represented by the general formula (I). And a liquid crystal composition containing a copolymer having a liquid crystal constituent unit.

One embodiment of the present disclosure provides a liquid crystal composition in which the liquid crystalline structural unit contains a structural unit represented by the general formula (II).

One embodiment of the present disclosure is a retardation film having a retardation layer, wherein the retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, and the side chain type liquid crystal polymer comprises a side chain type liquid crystal polymer. Provided is a retardation film composed of a cured product of a liquid crystal composition containing a copolymer having a structural unit represented by the general formula (I) and a liquid crystal structural unit.

One embodiment of the present disclosure provides a retardation film in which the liquid crystalline structural unit includes the structural unit represented by the general formula (II).

One embodiment of the present disclosure includes a step of forming a film of the liquid crystal composition of the first embodiment of the present disclosure.
A step of orienting the liquid crystal constituent unit of the side chain type liquid crystal polymer in the film-formed liquid crystal composition and the polymerizable liquid crystal compound.
Provided is a method for producing a retardation film, which forms a retardation layer by having a step of polymerizing the polymerizable liquid crystal compound after the alignment step.

One embodiment of the present disclosure comprises a retardation layer and a support that detachably supports the retardation layer.
The retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, and the side chain type liquid crystal polymer has a structural unit represented by the general formula (I) and a liquid crystal structural unit. Consists of a cured product of the liquid crystal composition containing the copolymer having
Provided is a transfer laminate to be used for transfer of a retardation layer.

One embodiment of the present disclosure provides a transfer laminate in which the liquid crystalline structural unit contains the structural unit represented by the general formula (II).

One embodiment of the present disclosure provides an optical member including a polarizing plate on the retardation film of the first embodiment of the present disclosure.

Further, one embodiment of the present disclosure provides a display device including the retardation film of the one embodiment of the present disclosure or the optical member of the one embodiment of the present disclosure.

According to the embodiment of the present disclosure, the precipitation of the liquid crystal is suppressed, the side chain type liquid crystal polymer and the liquid crystal composition capable of widening the temperature range in which the liquid crystal is oriented, and the precipitation of the liquid crystal are suppressed, and the retardation layer with improved mass productivity. A transfer film capable of transferring the retardation layer, an optical member having the retardation film, and a display device can be provided.

FIG. 1 is a schematic cross-sectional view showing one embodiment of a retardation film. FIG. 2 is a schematic cross-sectional view showing one embodiment of the retardation film. FIG. 3 is a schematic cross-sectional view showing one embodiment of the retardation film. FIG. 4 is a schematic cross-sectional view showing one embodiment of the transfer laminate. FIG. 5 is a schematic cross-sectional view showing one embodiment of the transfer laminate. FIG. 6 is a schematic cross-sectional view showing one embodiment of the transfer laminate. FIG. 7 is a schematic cross-sectional view showing one embodiment of the optical member. FIG. 8 is a schematic cross-sectional view showing one embodiment of the display device.

Hereinafter, embodiments and examples of the present disclosure will be described with reference to drawings and the like. However, the present disclosure can be implemented in many different modes, and is not construed as being limited to the description contents of the embodiments and examples illustrated below. In addition, in order to clarify the explanation, the drawings may schematically represent the width, thickness, shape, etc. of each part as compared with the actual embodiment, but this is just an example, and the interpretation of the present disclosure is used. It is not limited. Further, in the present specification and each figure, the same elements as those described above with respect to the above-mentioned figures may be designated by the same reference numerals, and detailed description thereof may be omitted as appropriate. Further, for convenience of explanation, the phrase "upper" or "lower" may be used for explanation, but the vertical direction may be reversed.
"In the present specification, when a certain structure such as a member or a certain area is" above (or below) "an other structure such as another member or another area, unless otherwise specified. , This includes not only the case of being directly above (or directly below) the other configuration, but also the case of being above (or below) the other configuration, i.e., another in between above (or below) the other configuration. Including the case where the component is included.

In the present disclosure, the orientation regulating force means an action of arranging liquid crystal compounds in a retardation layer in a specific direction.
In the present disclosure, (meth) acrylic represents each of acrylic or methacrylic, and (meth) acrylate represents each of acrylate or methacrylate.
Further, in the present specification, the terms "board", "sheet", and "film" are not distinguished from each other based only on the difference in names, but are referred to as "film surface (plate surface, sheet surface)". Is a surface that coincides with the plane direction of the target film-shaped member (plate-shaped member, sheet-shaped member) when the target film-shaped member (plate-shaped, sheet-shaped) is viewed as a whole and globally. Point to that.

A. Side-chain type liquid crystal polymer The side-chain type liquid crystal polymer of the present disclosure is a side-chain type liquid crystal polymer containing a copolymer having a structural unit represented by the following general formula (I) and a liquid crystal structural unit.

（一般式（Ｉ）中、Ｒ^１は、水素原子又はメチル基を、Ｒ^２は、−（ＣＨ_２）_ｎ−Ｌ^１−Ａｒ^１−Ｒ^３、又は−（Ｃ_２Ｈ_４Ｏ）_ｎ’−Ａｒ^１−Ｒ^３で表される基を、Ｌ^１は、直接結合、又は、−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、若しくは−Ｃ（＝Ｏ）−Ｏ−で表される連結基を、Ａｒ^１は、置換基を有していてもよい炭素原子数６以上１２以下のアリーレン基を、Ｒ^３は、置換基を有していてもよい炭素原子数２以上１０以下の直鎖又は分岐のアルキル基又はアルコキシ基を表し、ｎ及びｎ’はそれぞれ独立に２以上１０以下の整数である。）

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is − (CH ₂ ) _n −L ¹ −Ar ¹ −R ³ or − (C ₂ H ₄ O) _{n ′.} The group represented by ^{−Ar 1} −R ^{3 is directly bonded to L 1} , or is represented by −O−, −OC (= O) −, or −C (= O) −O−. As the linking group, Ar ¹ is an arylene group having 6 or more and 12 or less ^{carbon atoms which may have a substituent, and R 3} is an arylene group which may have a substituent and has 2 or more and 10 or less carbon atoms. Represents a linear or branched alkyl group or alkoxy group, and n and n'are independently integers of 2 or more and 10 or less.)

Side chain type liquid crystal polymer of the present disclosure, in addition to the liquid crystalline structural units, the alkylene chain _{{- (CH 2) n -} }, or oligoethylene oxide chain _{{- (C 2 H 4 O} ) n '-} and, substituted It has a structural unit represented by the general formula (I) having the specific arylene group between the linear or branched alkyl group or alkoxy group which may have a group.
In the embodiment of the present disclosure, the side chain type liquid crystal polymer has the structural unit represented by the general formula (I), so that the side chain of the liquid crystal structural unit in the side chain type liquid crystal polymer is formed. In addition to facilitating vertical orientation, it enhances compatibility with other liquid crystal compounds such as the polymerizable liquid crystal compound described later, and facilitates vertical orientation of the polymerizable liquid crystal compound. As a result, it is presumed that the temperature range in which the liquid crystal is oriented is widened, and the precipitation of the polymerizable liquid crystal compound described later is suppressed.
Hereinafter, each structural unit in the copolymer will be described.

1. 1. _{The n} and n'of the structural unit alkylene chain {-(CH ₂ ) n-} represented by the general formula (I) or the oligoethylene oxide chain {-(C ₂ H ₄ O) _n'- } are 2 independently of each other. It is an integer of 10 or more. Above all, n is preferably an integer of 2 or more and 8 or less from the viewpoint of exerting the above effect. In addition, among them, n'is preferably an integer of 2 or more and 4 or less from the viewpoint of exerting the above effect.

L ¹ is a direct bond or a linking group represented by -O-, -OC (= O)-, or -C (= O) -O-, and among them, the above-mentioned effect is exhibited. From the point of view, it is preferably −O−.

Ar ¹ represents an arylene group having 6 to 12 carbon atoms which may have a substituent, and examples thereof include a phenylene group, a naphthylene group, and a biphenylene group. Of these, a phenylene group is preferable from the viewpoint of exhibiting the above effects.
The substituent group other than optionally R ³ have the said arylene group, for example, a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom.

R ³ is a linear or branched alkyl group having 2 to 10 carbon atoms which may have a substituent, or a linear chain having 2 to 10 carbon atoms which may have a substituent. Alternatively, it represents a branched alkoxy group.
Specific examples of the linear or branched alkyl group having 2 or more and 10 or less carbon atoms include an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. Be done. Among them, a linear alkyl group having 2 or more and 10 or less carbon atoms is preferable, and 3 or more and 10 or less carbon atoms are preferable from the viewpoint of facilitating vertical orientation of the side chains of the liquid crystal constituent unit and exerting the above effects. It is more preferably a linear alkyl group, and even more preferably a linear alkyl group having 4 or more and 10 or less carbon atoms.
Specific examples of ^'the alkyl group R ³ in the straight-chain or branched alkoxy group having 2 to 10 carbon atoms (-OR ^3)', those similar to the specific examples of the alkyl group. Among them, a side chain of the liquid crystalline structural unit easily aligned vertically, from the viewpoint of exhibiting the effect, that the alkyl group R ^{3 'is} a straight-chain alkoxy group having 2 to 10 carbon atoms is a straight-chain It is more preferably a linear alkoxy group having 3 or more and 10 or less carbon atoms, and even more preferably a linear alkoxy group having 4 or more and 10 or less carbon atoms.
Examples of the substituent that the alkyl group or alkoxy group may have include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom.

As the structural unit represented by the general formula (I), at least one selected from the group consisting of the structural units represented by the following general formulas (I-1) and (I-2) exerts the above effect. It is preferable from the viewpoint of

In the general formula (I-1) and (I-2) structural units represented by, n and n ', and, ^{R 3} is, n and n in the general formula (I)', as well, similarly to the ^{R 3} Is.

The structural unit represented by the general formula (I) contained in the copolymer may be one kind or two or more kinds.

For the synthesis of the copolymer, a (meth) acrylic acid ester derivative that derives the structural unit represented by the above general formula (I) can be used as a monomer. The (meth) acrylic acid ester derivative that derives the structural unit represented by the general formula (I) can be used alone or in combination of two or more.

The content ratio of the structural unit represented by the general formula (I) in the copolymer is 20 mol% or more and 60 mol% or less when the total copolymer is 100 mol% from the viewpoint of exhibiting the above effect. It is preferable to set it within the range of 25 mol% or more and 50 mol% or less.
The content ratio of each structural unit in the copolymer can be calculated from the integrated value measured by ^{1 1 H NMR measurement.}

2. Liquid crystal constituent unit In the side chain type liquid crystal polymer of the embodiment of the present disclosure, the liquid crystal constituent unit is preferably a constituent unit containing a mesogen exhibiting liquid crystallinity in the side chain. The liquid crystalline structural unit is a structural unit derived from a liquid crystalline compound (hereinafter, may be referred to as a liquid crystal monomer) in which a polymerizable group is bonded to a mesogen group via a spacer.
In the present disclosure, the mesogen refers to a highly rigid site that exhibits liquid crystallinity, and has, for example, two or more ring structures, preferably three or more ring structures, and the ring structures are directly bonded to each other. Examples thereof include substructures that are linked or whose ring structure is linked via 1 to 3 atoms. Having such a mesogen in the side chain facilitates vertical orientation of the liquid crystal building blocks.
The ring structure may be an aromatic ring such as benzene, naphthalene or anthracene, or a cyclic aliphatic hydrocarbon such as cyclopentyl or cyclohexyl.
When the ring structure is connected via 1 to 3 atoms, the structure of the connecting portion includes, for example, −O−, −S−, −OC (= O) −, −C. (= O) -O-, -OC (= O) -O-, -N (-R')-C (= O)-, -C (= O) -N (-R')-, -O-C (= O) -N (-R')-, -N (-R')-C (= O) -O-, -N (-R')-C (= O) -N ( -R')-, -ON (-R')-, -N (-R')-O-, -CH = CH-, -C≡C-, -N = N-, etc. ( R'is an alkyl group). Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 or more and 6 or less carbon atoms, and among them, linear or branched alkyl groups having 1 or more and 3 or less carbon atoms are preferable. In addition, when the ring structure is connected via 1 to 3 atoms, it is like an atom put in ""of-"N"(-R')-"C" (= O)-"O"-. In addition, the number of atoms connected in series at the connecting portion is counted.
Among them, the mesogen is preferably a rod-shaped mesogen in which benzene is connected at the para position and naphthalene is connected at the 2nd and 6th positions so that the ring structure is connected in a rod shape.

Further, the structural unit containing a mesogen exhibiting liquidity in the side chain preferably has a polar group, an alkyl group, or an alkoxy group at the end of the side chain of the structural unit from the viewpoint of vertical orientation. Examples of the polar group include -F, -Cl, -CN, -OCF ₃ , -OCF ₂ H, -NCO, -NCS, -NO ₂ , -NHC (= O) -R ", -C (= O). ) -OR ", - OH, -SH , -CHO, -SO 3 H, -NR" 2 (R " can be mentioned a hydrogen atom or a hydrocarbon group). Examples of the alkyl group include a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Examples of the alkoxy group include a linear, branched or cyclic alkoxy group having 1 or more and 6 or less carbon atoms.
The liquid crystal constituent units in the side chain type liquid crystal polymer are, for example, HJ Neumann, M. Jalek, and GPHellmann Macromolecules, 26, 2489-2495, (1993) and p. Liquid crystal constituent units derived from conventionally known liquid crystal monomers as described in 8 to 10 may be appropriately selected and used.

The liquid crystal structural unit is preferably a structural unit derived from a monomer having an ethylenic double bond-containing group polymerizable with the general formula (I). Examples of the monomer having such an ethylenic double bond-containing group include derivatives such as (meth) acrylic acid ester, styrene, (meth) acrylamide, maleimide, vinyl ether, and vinyl ester. The liquid crystal constituent unit is preferably a constituent unit derived from the (meth) acrylic acid ester derivative from the viewpoint of vertical orientation.

In the embodiment of the present disclosure, the liquid crystal structural unit preferably includes a structural unit represented by the following general formula (II) from the viewpoint of vertical orientation.

（一般式（ＩＩ）中、Ｒ^１１は、水素原子又はメチル基を、Ｒ^１２は、−（ＣＨ_２）_ｍ−、又は−（Ｃ_２Ｈ_４Ｏ）_ｍ’−で表される基を表す。Ｌ^２は、直接結合、又は、−Ｏ−、−Ｓ−、−Ｏ−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−Ｏ−、−Ｎ（−Ｒ^１４ ）−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｎ（−Ｒ^１４）−、−Ｏ−Ｃ（＝Ｏ）−Ｎ（−Ｒ^１４）−、−Ｎ（−Ｒ^１４）−Ｃ（＝Ｏ）−Ｏ−、−Ｎ（−Ｒ^１４）−Ｃ（＝Ｏ）−Ｎ（−Ｒ^１４）−、−Ｏ−Ｎ（−Ｒ^１４）−、若しくは−Ｎ（−Ｒ^１４）−Ｏ−で表される連結基を、Ｒ^１４は、水素原子又は炭素原子数１以上６以下のアルキル基を表す。Ａｒ^２は、置換基を有していてもよい炭素原子数６以上１０以下のアリーレン基を表し、複数あるＬ^２及びＡｒ^２はそれぞれ同一であっても異なっていても良い。Ｒ^１３は、−Ｆ、−Ｃｌ、−ＣＮ、−ＯＣＦ_３、−ＯＣＦ_２Ｈ、−ＮＣＯ、−ＮＣＳ、−ＮＯ_２、−ＮＨＣ（＝Ｏ）−Ｒ^１５、−Ｃ（＝Ｏ）−ＯＲ^１５、−ＯＨ、−ＳＨ、−ＣＨＯ、−ＳＯ_３Ｈ、−ＮＲ^１５ _２、−Ｒ^１６、又は−ＯＲ^１６を、Ｒ^１５は、水素原子又は炭素原子数１以上６以下のアルキル基を表し、Ｒ^１６は、炭素原子数１以上６以下のアルキル基を表す。ａは２以上４以下の整数、ｍ及びｍ’はそれぞれ独立に２以上１０以下の整数である。）

(In the general formula (II), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a group represented by − (CH ₂ ) _m − or − (C ₂ H ₄ O) _{m ′ −.} . L ² is a direct bond or -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -N (-R ¹⁴ ) -C (= O)-, -C (= O) -N (-R ¹⁴ )-, -OC (= O) -N (-R ¹⁴ )-, -N ( -R ¹⁴ ) -C (= O) -O-, -N (-R ¹⁴ ) -C (= O) -N (-R ¹⁴ )-, -ON (-R ¹⁴ )-, or -N (-R ¹⁴ ) The linking group represented by -O-, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms. Ar ² is a carbon which may have a substituent. It represents an arylene group having 6 or more and 10 or less atoms, and a plurality of L ² and Ar ² may be the same or different, respectively. R ¹³ is -F, -Cl, -CN, -OCF ₃ , -. OCF ₂ H, -NCO, -NCS, -NO ₂ , -NHC (= O) -R ¹⁵ , -C (= O) -OR ¹⁵ , -OH, -SH, -CHO, -SO ₃ H, -NR ¹⁵ _2, ^{-R 16,} or ^{-OR 16, R 15} represents a hydrogen atom or a carbon atoms of 1 to 6. the alkyl ^{group, R 16} represents 1 to 6 alkyl group carbon atoms. a is an integer of 2 or more and 4 or less, and m and m'are independently integers of 2 or more and 10 or less.)

M ^{and m'of R 12} are each independently an integer of 2 or more and 10 or less. From the viewpoint of vertical orientation, m and m'preferably 2 or more and 8 or less, and further preferably 2 or more and 6 or less.

L ² is directly bonded or -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-,- N (-R ¹⁴ ) -C (= O)-, -C (= O) -N (-R ¹⁴ )-, -OC (= O) -N (-R ¹⁴ )-, -N (-N (-) R ¹⁴ ) -C (= O) -O-, -N (-R ¹⁴ ) -C (= O) -N (-R ¹⁴ )-, -ON (-R ¹⁴ )-, or -N ( -R ¹⁴⁾ any of the linking group represented by ^-O-, but are exemplified, R ¹⁴ is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, carbon atoms More preferably, it is a linear or branched alkyl group having a number of 1 or more and 3 or less.
Among them, L ² is a direct bond or a linking group represented by −O−, −OC (= O) −, or −C (= O) −O− from the viewpoint of vertical orientation. Is preferable. Further, the L ^{2 between the two Ar 2} is preferably a direct bond or a linking group represented by −OC (= O) − or −C (= O) −O−. ..

Examples of the arylene group having 6 or more and 10 or less carbon atoms which may have a substituent in ^{Ar 2 include a phenylene group and a naphthylene group, and a phenylene group is more preferable.} The substituent group other than optionally R ¹³ have the said arylene group having 1 to 5 an alkyl group having a carbon atom, a fluorine atom, a chlorine atom and a halogen atom such as a bromine atom.

In R ¹³ , R ¹⁵ is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms, but may be linear, branched, or cyclic, and may be, for example, a methyl group, an ethyl group, or n-. Linear alkyl groups such as propyl group, n-butyl group, n-pentyl group and n-hexyl group, branched alkyl groups such as i-propyl group, i-butyl group, t-butyl group and 2-methylbutyl group, cyclo Examples thereof include cycloalkyl groups such as propyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. Among them, an alkyl group having a hydrogen atom or a carbon atom number of 1 or more and 5 or less is preferable, and an alkyl group having a hydrogen atom or a carbon atom number of 1 or more and 3 or less is preferable. Further, R ^{16 in R 13} includes ^{the same alkyl group as R 15} , but among them, an alkyl group having 1 or more carbon atoms and 5 or less carbon atoms is preferable.
R ¹³ _{has -Cl, -CN, -OCF 3} , -OCF ₂ H, -NCO, -NCS, -NO ₂ , -NHC (= O) -R ¹⁵ , -C (in particular, in terms of vertical orientation. ^{= O) -OR 15, -OH,} -SH, -CHO, -SO 3 H, -NR 15 2, preferably ^{-R 16,} or ^{-OR 16, -Cl, -CN, -OCF} 3 or ^{-C (= O) -OR 15,} -R 16, or more preferably ^{-OR 16.}

The liquid crystal constituent unit is selected from the group consisting of the constituent units represented by the following general formulas (II-1) to (II-3) from the viewpoint of being excellent in vertical orientation and exhibiting the above effects. At least one type is preferable, and further, at least one type selected from the group consisting of the structural units represented by the following general formulas (II-1) to (II-2) is preferable.

Here, the structural unit represented by the above general formula (II-1) ~ (II -3), R 12 ^and, respectively ^{R 13, R 12} in the general formula (II) ^and, similarly to ^{R 13} Is.

In the structural units represented by the general formulas (II-1) to (II-3), R ¹² is preferably − (CH ₂ ) _m −, and m here is a general formula. It is the same as m of (II).

In the structural units represented by the above general formulas (II-1) to (II-3), R ¹³ is, among others, -CN, -C (= O) -OR ¹⁵ , -R ¹⁶ or -OR ¹⁶ . It is preferably -CN, -C (= O) -OR ¹⁵ , -R ¹⁶ or -OR ¹⁶ . Incidentally, ^{R 15,} and ^{R 16} here is the same as ^{R 15,} and ^{R 16} in the general formula (II).

The liquid crystal constituent unit of the copolymer may be one kind or two or more kinds.

For the synthesis of the copolymer, a (meth) acrylic acid ester derivative or the like that induces a liquid crystal constituent unit can be used as a monomer. The monomer such as the (meth) acrylic acid ester derivative that induces the structural unit represented by the general formula (II) can be used alone or in combination of two or more.

The content ratio of the liquid crystal constituent unit in the copolymer shall be set within the range of 40 mol% or more and 80 mol% or less when the total copolymer is 100 mol% from the viewpoint of exhibiting the above effect. Is preferable, and more preferably, it is in the range of 50 mol% or more and 75 mol% or less.

3. 3. Other Constituent Units In the present invention, the copolymer of the side chain type liquid crystal polymer is represented by the general formula (I) in addition to the structural unit represented by the general formula (I) and the liquid crystallinity structural unit. It may have a structural unit that does not correspond to any of the above-mentioned structural unit and the liquid crystalline structural unit. By including other structural units in the copolymer, for example, solvent solubility, heat resistance, reactivity and the like can be enhanced.
These other structural units may be one kind or two or more kinds.

The content ratio of the other constituent units in the copolymer is preferably in the range of 0 mol% or more and 30 mol% or less, and 0 mol% or more and 20 mol% or more, when the total copolymer is 100 mol%. It is more preferably in the range of mol% or less. If the content ratio of the structural unit is large, the content ratio of the liquid crystal structural unit and the structural unit represented by the general formula (I) is relatively small, and it may be difficult to obtain the effect of the present application. be.

4. Copolymer In the embodiment of the present disclosure, the side chain type liquid crystal polymer is a block copolymer having a block portion composed of a structural unit represented by the general formula (I) and a block portion composed of a liquid crystal structural unit. It may be a random copolymer in which the structural unit represented by the general formula (I) and the liquid crystal structural unit are irregularly arranged. In the present embodiment, a random copolymer is preferable from the viewpoint of suppressing the vertical orientation and precipitation of the polymerizable liquid crystal compound and making the retardation layer hard to crack.

The mass average molecular weight Mw of the side chain type liquid crystal polymer, which is a copolymer, is not particularly limited, but is preferably in the range of 500 or more and 20000 or less, and more preferably in the range of 1000 or more and 15000 or less. It is more preferably in the range of 3000 or more and 12000 or less. Within the above range, the stability of the liquid crystal composition is excellent, and the handleability at the time of forming the retardation layer is excellent.

The mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography). For the measurement, HLC-8120GPC manufactured by Toso Co., Ltd. was used, the elution solvent was N-methylpyrrolidone added with 0.01 mol / liter of lithium bromide, and the polystyrene standard for the calibration curve was Mw377400, 210500, 96000, 50400. , 206500, 10850, 5460, 2930, 1300, 580 (above, Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Co., Ltd.), and the measurement columns are TSK-GEL ALPHA-M x 2 (Tosoh). It was carried out as (manufactured by Co., Ltd.).

In the present embodiment, the method for producing the side chain type liquid crystal polymer is not particularly limited, and for example, a monomer for inducing a structural unit represented by the general formula (I) and a monomer for inducing a liquid crystal structural unit are desired. It may be mixed in a ratio and polymerized to a desired average molecular weight by a known polymerization means.
In the case of a block copolymer, for example, after polymerizing the monomer for inducing the structural unit represented by the general formula (I) and the monomer for inducing the liquid crystal structural unit by known polymerization means, respectively. , The obtained polymers may be linked, and one of the monomer for inducing the structural unit represented by the general formula (I) or the monomer for inducing the liquid crystal structural unit may be connected by a known polymerization means. Examples thereof include a method of further polymerizing by adding the other monomer after polymerization.
As the polymerization means, a method generally used for polymerization of a compound having a vinyl group can be adopted, and for example, anionic polymerization, living radical polymerization and the like can be used. In the present embodiment, among them, a method in which the polymerization proceeds in a living room like the group transfer polymerization (GTP) disclosed in "J. Am. Chem. Soc." 105, 5706 (1983) is used. Is preferable. According to this method, it is easy to set the molecular weight, the molecular weight distribution, and the like in a desired range, so that the characteristics of the obtained side chain type liquid crystal polymer can be made uniform.

In the present disclosure, the structures of the side chain liquid crystal polymers are nuclear magnetic resonance spectroscopy (NMR), pyrolysis gas chromatograph mass spectrometry (Py-GC-MS), and matrix-assisted laser desorption / ionization time-of-flight mass spectrometry. Can be analyzed in combination with at least one of (MALDI-TOFMS). By Py-GC-MS or MALDI-TOFMS, it can be confirmed that the linking group contains two or more structural units having different numbers of carbon atoms.

B. Liquid Crystal Composition The liquid crystal composition of the present disclosure contains a side chain type liquid crystal polymer, a polymerizable liquid crystal compound, and a photopolymerization initiator, and the side chain type liquid crystal polymer is represented by the general formula (I). It is a liquid crystal composition containing a copolymer having a liquid crystal constituent unit and a liquid crystal constituent unit.

Since the liquid crystal composition of the present disclosure contains the side chain type liquid crystal polymer of the present disclosure and the polymerizable liquid crystal compound, it is easy to orient at a low temperature, so that a retardation layer having a wide process margin and suppressed precipitation can be obtained. Can be done.

The action of the liquid crystal composition to exert such an effect is presumed as follows, although there are some unclear points.
In the liquid crystal composition of the present disclosure, as a side chain type liquid crystal polymer, in addition to the liquid crystal constituent unit, an alkylene chain {-(CH ₂ ) _n- } or an oligoethylene oxide chain {-(C ₂ H ₄ O) _n' It has a structural unit represented by the general formula (I) having the specific arylene group between −} and an alkyl group or an alkoxy group which may have a substituent.
When the liquid crystal composition containing the side chain type liquid crystal polymer is used as a coating film and appropriately heated, the side chains of the liquid crystal constituent units of the side chain type liquid crystal polymer are the structural units represented by the general formula (I). It is presumed that the combination of the above makes it easy to orient the coating film in the direction perpendicular to the in-plane direction. Further, since the side chain type liquid crystal polymer contains the structural unit represented by the general formula (I), it is presumed that the specific arylene group improves the compatibility with the polymerizable liquid crystal compound described later. Will be done. It is presumed that the improvement in compatibility improves the orientation of the entire liquid crystal material and widens the temperature range in which the entire liquid crystal material is oriented. That is, the compatibility between the side-chain type liquid crystal polymer and the polymerizable liquid crystal compound is improved, and the polymerizable liquid crystal compound easily enters the side-chain type liquid crystal polymer and is easily vertically oriented, and the polymerizable liquid crystal compound once vertically oriented. Is presumed to be difficult to move. From these facts, the liquid crystal composition of the present disclosure tends to be vertically oriented even at a low temperature, the temperature range in which the liquid crystal is oriented is widened, and the precipitation associated with phase separation and crystallization of the polymerizable liquid crystal compound and the like is suppressed. It is estimated that it will be done.
Further, since the side chain type liquid crystal polymer contains a structural unit represented by the general formula (I), there are a wide range of choices of polymerizable liquid crystal compounds to be combined.
Further, the liquid crystal composition of the present disclosure has a wide process margin because it is easily vertically oriented at a low temperature, and is suitable for mass production. A retardation layer formed from the liquid crystal composition and a display device including the retardation layer. Productivity can also be improved.

The liquid crystal composition in the present disclosure contains at least a side chain type liquid crystal polymer, a polymerizable liquid crystal compound, and a photopolymerization initiator, and may further contain other components as long as the effects are not impaired. be. Hereinafter, each component constituting the liquid crystal composition will be described in order.

1. 1. Side-chain type liquid crystal polymer In the liquid crystal composition of the present disclosure, the side-chain type liquid crystal polymer may be the same as that described in "A. Side-chain type liquid crystal polymer", and thus the description thereof is omitted here.
In the liquid crystal composition of the present disclosure, the side chain type liquid crystal polymer may be used alone or in combination of two or more. In the present embodiment, the content ratio of the side chain type liquid crystal polymer is 100 parts by mass of the solid content of the liquid crystal composition from the viewpoint that the precipitation of the liquid crystal is suppressed and the liquid crystal composition capable of widening the temperature range in which the liquid crystal is oriented can be obtained. It is preferably 20 parts by mass or more and 79.9 parts by mass or less, more preferably 25 parts by mass or more and 69.9 parts by mass or less, and 25 parts by mass or more and 59.9 parts by mass or less. Even more preferable.
In the present disclosure, the solid content refers to all the components except the solvent, and for example, the polymerizable liquid crystal compound described later is included in the solid content even if it is in a liquid state.

2. Polymerizable Liquid Crystal Compound In the liquid crystal composition of the present disclosure, the polymerizable liquid crystal compound can be appropriately selected and used from conventionally known ones. In the present embodiment, since it is easy to vertically orient in combination with the side chain type liquid crystal polymer, it is preferable that the polymerized liquid crystal compound has a polymerizable group at at least one end of the rod-shaped mesogen, and both of the rod-shaped mesogens. More preferably, it is a polymerizable liquid crystal compound having a polymerizable group at the terminal.
The mesogen or rod-shaped mesogen contained in the polymerizable liquid crystal compound can be the same as the mesogen or rod-shaped mesogen possessed by the liquid crystal constituent unit in the side chain type liquid crystal polymer.

Examples of the polymerizable group contained in the polymerizable liquid crystal compound include a cyclic ether-containing group such as an oxylane ring and an oxetane ring, and an ethylenic double bond-containing group. Among them, they exhibit photocurability and are excellent in handleability. From the point of view, it is preferably an ethylenic double bond-containing group. Examples of the cyclic ether group include a glycidyl group. Examples of the ethylenic double bond-containing group include a vinyl group, an allyl group, a (meth) acryloyl group, and the like, and among them, a (meth) acryloyl group is preferable.

In the present embodiment, the polymerizable liquid crystal compound is one selected from the compound represented by the following general formula (III) and the compound represented by the following general formula (IV) from the viewpoint of vertical orientation. The above compounds are preferred.

（一般式（ＩＩＩ）中、Ｒ^２１は、水素原子又はメチル基を、Ｒ^２２は、−（ＣＨ_２）_ｐ−、又は−（Ｃ_２Ｈ_４Ｏ）_ｐ’−で表される基を表す。Ｌ^３は、直接結合、又は、−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、若しくは−Ｃ（＝Ｏ）−Ｏ−で表される連結基を、Ａｒ^３は、置換基を有していてもよい炭素原子数６以上１０以下のアリーレン基を表し、複数あるＬ^３及びＡｒ^３はそれぞれ同一であっても異なっていても良い。Ｒ^２３は、−Ｆ、−Ｃｌ、−ＣＮ、−ＯＣＦ_３、−ＯＣＦ_２Ｈ、−ＮＣＯ、−ＮＣＳ、−ＮＯ_２、−ＮＨＣ（＝Ｏ）−Ｒ^２４、−Ｃ（＝Ｏ）−ＯＲ^２４、−ＯＨ、−ＳＨ、−ＣＨＯ、−ＳＯ_３Ｈ、−ＮＲ^２４ _２、−Ｒ^２５、又は−ＯＲ^２５を、Ｒ^２４は、水素原子又は炭素原子数１以上６以下のアルキル基を表し、Ｒ^２５は、炭素原子数１以上６以下のアルキル基を表す。ｂは２以上４以下の整数、ｐ及びｐ’はそれぞれ独立に２以上１０以下の整数である。

(In the general formula (III), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a group represented by − (CH ₂ ) _p − or − (C ₂ H ₄ O) _{p ′ −.} L ³ is a direct bond or a linking group represented by -O-, -OC (= O)-, or -C (= O) -O-, and Ar ³ has a substituent. It represents an arylene group having 6 or more and 10 or less carbon atoms, and a plurality of L ³ and Ar ³ may be the same or different, respectively. R ²³ is -F, -Cl, -CN. , -OCF ₃ , -OCF ₂ H, -NCO, -NCS, -NO ₂ , -NHC (= O) -R ²⁴ , -C (= O) -OR ²⁴ , -OH, -SH, -CHO,- SO ₃ ^H, _-NR 24 ^2, a ^{-R 25,} or ^{-OR 25, R 24} represents a hydrogen atom or an alkyl group having 1 to 6 carbon ^{atoms, R 25} is 1 to 6 carbon atoms B is an integer of 2 or more and 4 or less, and p and p'are independently integers of 2 or more and 10 or less.

（一般式（ＩＶ）中、Ｒ^３１及びＲ^３２は各々独立に、水素原子又はメチル基を、Ｒ^３３は、−（ＣＨ_２）_ｑ−、又は−（Ｃ_２Ｈ_４Ｏ）_ｑ’−で表される基を、Ｒ^３４は、−（ＣＨ_２）_ｒ−、又は−（ＯＣ_２Ｈ_４）_ｒ’−で表される基を表す。Ｌ^４は、直接結合、又は、−Ｏ−、−Ｏ−Ｃ（＝Ｏ）−、若しくは−Ｃ（＝Ｏ）−Ｏ−で表される連結基を、Ａｒ^４は、置換基を有していてもよい炭素原子数６以上１０以下のアリーレン基を表し、複数あるＬ^４及びＡｒ^４はそれぞれ同一であっても異なっていても良い。ｃは２以上４以下の整数、ｑ、ｑ’、ｒ及びｒ’はそれぞれ独立に２以上１０以下の整数である。）

(In general formula (IV), R ³¹ and R ³² are independently hydrogen atoms or methyl groups, and R ³³ is − (CH ₂ ) _q − or − (C ₂ H ₄ O) _{q ′} −. The group represented by R ³⁴ represents a group represented by − (CH ₂ ) _r − or − (OC ₂ H ₄ ) _{r ′} −. L ⁴ represents a direct bond or −O −, ^{Ar 4} may have a substituent as a linking group represented by −O—C (= O) − or −C (= O) −O−. Representing a group, a plurality of L ⁴ and Ar ⁴ may be the same or different. C is an integer of 2 or more and 4 or less, and q, q', r and r'are independently 2 or more and 10 or less. It is an integer of.)

From the viewpoint of vertical orientation, p, p'in the general formula (III) and q, q', r and r'in the general formula (IV) are preferably 2 or more and 8 or less, and 2 or more and 6 or less. More preferably, it is more preferably 2 or more and 5 or less.
Further, Ar ³ and Ar ⁴ can be the same as ^{Ar 2} in the general formula (II).
^{Further, R 23} in the general formula (III) can be the same as ^{R 13} in the general formula (II).

As the mesogen structure contained in the polymerizable liquid crystal compound, partial structures represented by the following chemical formulas (V-1) to (V-6) are preferably used, and among them, the following chemical formula (V) containing three or more ring structures. A partial structure represented by at least one selected from the group consisting of -1), (V-2), (V-4), (V-5), and (V-6) is preferably used. The hydrogen atom in the phenylene group or naphthylene group in the partial structure represented by the following chemical formulas (V-1) to (V-6) may be substituted with an alkyl group having 1 or more and 3 or less carbon atoms or a halogen atom. ..

Preferable specific examples of the compound represented by the general formula (III) and the compound represented by the general formula (IV) include those represented by the following chemical formulas (1) to (17). It is not limited.

In the present embodiment, the polymerizable liquid crystal compound may be used alone or in combination of two or more.
In the present embodiment, the content ratio of the polymerizable liquid crystal compound is such that the precipitation of the liquid crystal is suppressed and a liquid crystal composition capable of widening the temperature range in which the liquid crystal is oriented can be obtained. , 20 parts by mass or more and 79.9 parts by mass or less, 30 parts by mass or more and 74.9 parts by mass or less, more preferably 40 parts by mass or more and 69.9 parts by mass or less. preferable.

3. 3. Photopolymerization Initiator In the present embodiment, the photopolymerization initiator can be appropriately selected and used from conventionally known substances. Specific examples of such a photopolymerization initiator include aromatic ketones including thioxanthone, α-aminoalkylphenones, α-hydroxyketones, acylphosphine oxides, oxime esters, and aromatic onium. Preferred examples include salts, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds. Among them, at least one selected from the group consisting of an acylphosphine oxide-based polymerization initiator, an α-aminoalkylphenone-based polymerization initiator, an α-hydroxyketone-based polymerization initiator, and an oxime ester-based polymerization initiator is selected. preferable.

Examples of the acylphosphine oxide-based polymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide (for example, trade name: Irgacure 819, manufactured by BASF) and bis (2,6-dimethoxy). Benzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name: Lucirin TPO: manufactured by BASF, etc.) and the like can be mentioned.

Examples of the α-aminoalkylphenone-based polymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (for example, Irgacure 907, manufactured by BASF), 2-. Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg, Irgacure 369, manufactured by BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] Examples thereof include -1- [4- (4-morpholinyl) phenyl] -1-butanone (Irgacure 379EG, manufactured by BASF).

Examples of the α-hydroxyketone-based polymerization initiator include 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane. -1-one (for example, trade name: Irgacure 127, manufactured by BASF, etc.), 2-hydroxy-4'-hydroxyethoxy-2-methylpropiophenone (for example, trade name: Irgacure 2959, manufactured by BASF, etc.), 1-Hydroxy-cyclohexyl-phenyl-ketone (for example, trade name: Irgacure 184, manufactured by BASF, etc.), oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone} ( For example, trade name: ESACURE ONE, manufactured by Lamberti, etc.) and the like can be mentioned.

Examples of the oxime ester-based polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (trade name: Irgacure OXE-01, manufactured by BASF), etanone, 1- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (o-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, etanone , 1- [9-Ethyl-6- (1,3-dioxolan, 4- (2-methoxyphenoxy) -9H-carbazole-3-yl]-, 1- (o-acetyloxime) (trade name: ADEKA OPT-) N-1919, manufactured by ADEKA) and the like.

In the present embodiment, the photopolymerization initiator may be used alone or in combination of two or more.
In the present embodiment, the content ratio of the photopolymerization initiator is 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the solid content of the liquid crystal composition from the viewpoint of accelerating the curing of the polymerizable liquid crystal compound. It is preferably 1 part by mass or more and 8 parts by mass or less.

4. Other Ingredients The liquid crystal composition of the present embodiment may further contain other ingredients as long as the effect is not impaired. Specifically, as other components, a leveling agent, an antioxidant, a light stabilizer, a solvent or the like may be contained from the viewpoint of coatability. For these, conventionally known materials may be appropriately selected and used.
As the leveling agent, it is preferable to use a fluorine-based or silicone-based leveling agent. Specific examples of the leveling agent include, for example, the Mega Fvck series manufactured by DIC Corporation, the TSF series manufactured by Momentive Performance Materials Japan Co., Ltd., and Neos Co., Ltd., which are described in JP-A-2010-122325. The footergent series and the like can be mentioned. When a leveling agent is used in the present embodiment, the content ratio thereof is preferably 0.001 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the solid content of the liquid crystal composition.

The liquid crystal composition of the present embodiment may contain a solvent, if necessary, from the viewpoint of coatability. The solvent may be appropriately selected from conventionally known solvents capable of dissolving or dispersing each component contained in the liquid crystal composition. Specifically, for example, hydrocarbon solvents such as hexane and cyclohexane, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether solvents such as tetrahydrofuran and propylene glycol monoethyl ether (PGME), chloroform, dichloromethane and the like. Alkyl halide solvents, ester solvents such as ethyl acetate and propylene glycol monomethyl ether acetate, amide solvents such as N, N-dimethylformamide, and sulfoxide solvents such as dimethyl sulfoxide, methanol, ethanol, propanol and the like. Examples include alcohol solvents. In the present embodiment, the solvent can be used alone or in combination of two or more as a mixed solvent.

The liquid crystal composition of the present embodiment is suitable for producing a liquid crystal alignment film, and the side chain type liquid crystal polymer tends to be vertically oriented, and the polymerizable liquid crystal compound tends to be vertically oriented. Therefore, a positive C type phase difference Suitable for layer production.

C. Phase Difference Film The retardation film of the present disclosure is a retardation film having a retardation layer, wherein the retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, and the side chain type liquid crystal. The polymer comprises a cured product of a liquid crystal composition containing a copolymer having a structural unit represented by the general formula (I) and a liquid crystal constituent unit.
In the retardation film of the present embodiment, since the retardation layer is made of a cured product of the liquid crystal composition, as described above, precipitation of the polymerizable liquid crystal compound is suppressed, and the optical characteristics are excellent. Since the temperature range in which the liquid crystal is oriented is widened, the process margin is wide and the mass productivity is improved.

The layer structure of the retardation film will be described with reference to the drawings. 1 to 3 show one embodiment of the retardation film of the present disclosure, respectively. One embodiment of the retardation film 10 shown in the example of FIG. 1 is a retardation film in which the alignment film 3 and the retardation layer 1 are laminated in this order on the base material 2. One embodiment of the retardation film 10 shown in the example of FIG. 2 is a retardation film composed of only the retardation layer 1. Further, in one embodiment of the retardation film 10 shown in the example of FIG. 3, the retardation layer 1 is formed directly on the base material 2'. The retardation film shown in the example of FIG. 3 may be provided with a means for exerting an orientation regulating force on the surface of the base material 2'on the retardation layer 1 side.
The liquid crystal composition containing a side chain type liquid crystal polymer containing a copolymer having a structural unit represented by the general formula (I) and a liquid crystal structural unit and a polymerizable liquid crystal compound is described above. As described above, since the side chain type liquid crystal polymer is easily vertically oriented and the polymerizable liquid crystal compound is easily vertically oriented, the vertical orientation can be exhibited without using an alignment film.

1. 1. Phase Difference Layer The retardation layer 1 of the embodiment of the present disclosure includes a side chain type liquid crystal polymer containing a copolymer having a structural unit represented by the general formula (I) and a liquid crystal structural unit, and a polymerizable liquid crystal. It comprises a cured product of a liquid crystal composition containing a compound.
Here, the side chain type liquid crystal polymer containing a copolymer having a structural unit represented by the following general formula (I) and a liquid crystal structural unit, and the polymerizable liquid crystal compound are each carried out in the present disclosure. Since it may be the same as that described in the liquid crystal composition of the form, the description here will be omitted.

The retardation layer is preferably cured in a state in which the liquid crystal constituent unit of the side chain type liquid crystal polymer and the polymerizable liquid crystal compound are vertically oriented. The cured product of the liquid crystal composition of the embodiment of the present disclosure includes a structure in which at least a part of the polymerizable groups of the polymerizable liquid crystal compound is polymerized. Since at least a part of the polymerizable group of the polymerizable liquid crystal compound is polymerized, the retardation layer of the present embodiment is a retardation layer having improved durability.

The phase difference can be measured by an automatic birefringence measuring device (for example, manufactured by Oji Measuring Instruments Co., Ltd., trade name: KOBRA-WR). Anisotropy in which the measurement light is incident vertically or diagonally to the surface of the retardation layer and the phase difference of the retardation layer is increased or decreased from the chart of the optical retardation and the incident angle of the measurement light, and the vertical (thickness) of the liquid crystal. The degree of orientation in the direction can be confirmed.

Further, it is a phase difference that the retardation layer includes a side chain type liquid crystal polymer contained in the liquid crystal composition of the present disclosure, and a structure in which at least a part of the polymerizable groups of the polymerizable liquid crystal compound is polymerized. It can be confirmed by collecting and analyzing the material from the layer. As the analysis method, NMR, IR, GC-MS, XPS, TOF-SIMS and a combination method thereof can be applied.

The retardation layer may contain other components such as a photopolymerization initiator, a leveling agent, an antioxidant, and a light stabilizer. In some cases, the retardation layer does not contain components such as a photopolymerization initiator that may decompose when irradiated with light to react the polymerizable groups of the polymerizable liquid crystal compound. be.

The thickness of the retardation layer may be appropriately set according to the intended use. Above all, it is preferably 0.1 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less.

2. Alignment film As used herein, the alignment film refers to a layer for arranging liquid crystal components contained in a retardation layer in a certain direction.
As the alignment film used in the embodiment of the present disclosure, it is preferable to use a vertically oriented film because the liquid crystal composition of the embodiment of the present disclosure is likely to be vertically oriented.
The vertical alignment film is an alignment film having a function of vertically aligning the long axis of the liquid crystal component mesogen contained in the retardation layer by being provided as a coating film.

The vertical alignment film is an alignment film having an orientation regulating force in the vertical direction, and various vertical alignment films used for producing a C plate, various vertical alignment films applied to a VA liquid crystal display device, etc. can be applied. For example, a polyimide alignment film, an alignment film made of an LB film, or the like can be applied. Specifically, as the constituent material of the alignment film, for example, a silane coupling system vertical such as lecithin, a silane-based surfactant, a titanate-based surfactant, a pyridinium salt-based polymer surfactant, and n-octadecyltriethoxysilane. Compositions for alignment membranes, soluble polyimides having long-chain alkyl groups and alicyclic structures in the side chains, and compositions for polyimide-based vertical alignment films such as polyamic acids having long-chain alkyl groups and alicyclic structures in the side chains, A polyfunctional acrylate-based resin composition or the like can be applied.
As the composition for the vertical alignment film, the polyimide-based vertical alignment film composition "JALS-2021" and "JALS-204" manufactured by JSR Co., Ltd. and "RN-1517" manufactured by Nissan Chemical Industries, Ltd. , "SE-1211", "EXPOA-018", "Fine Cure PXV-18" manufactured by Sanyo Chemical Industries, Ltd., and the like can be applied. Further, the vertically oriented film described in Japanese Patent Application Laid-Open No. 2015-191143 may be used.

The method for forming the alignment film is not particularly limited, but for example, the alignment film can be formed by applying the composition for an alignment film described later on a substrate described later and imparting an orientation regulating force. As a means for imparting an orientation regulating force to the alignment film, conventionally known means can be used.

The thickness of the alignment film may be appropriately set as long as the liquid crystal components in the retardation layer can be arranged in a certain direction. The thickness of the alignment film is usually in the range of 1 nm or more and 1000 nm or less, preferably in the range of 60 nm or more and 300 nm or less.

3. 3. Base material In the present embodiment, the base material includes a glass base material, a metal foil, a resin base material, and the like. Above all, the base material preferably has transparency, and can be appropriately selected from conventionally known transparent base materials. Examples of the transparent base material include glass base materials, acetyl cellulose-based resins such as triacetyl cellulose, polyethylene terephthalates, polyethylene naphthalates, polybutylene terephthalates, polyester resins such as polylactic acid, polypropylene, polyethylene, polymethylpentene and the like. Formed using resins such as olefin resin, acrylic resin, polyurethane resin, polyether sulfone, polycarbonate, polysulfone, polyether, polyether ketone, acronitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer, etc. A transparent resin base material can be mentioned.

The transparent substrate preferably has a transmittance of 80% or more in the visible light region, and more preferably 90% or more. Here, the transmittance of the transparent substrate can be measured by JIS K7361-1 (a test method for the total light transmittance of a plastic-transparent material).

Further, when the retardation layer is formed by the roll-to-roll method, the transparent base material is preferably a flexible material having flexibility that can be wound into a roll shape.
Examples of such flexible materials include cellulose derivatives, norbornene polymers, cycloolefin polymers, polymethylmethacrylates, polyvinyl alcohols, polyimides, polyallylates, polyethylene terephthalates, polysulfones, polyethersulfones, amorphous polyolefins, modified acrylic polymers, and polystyrenes. , Epoxy resin, polycarbonate, polyesters and the like can be exemplified. Among them, it is preferable to use a cellulose derivative or polyethylene terephthalate in this embodiment. This is because the cellulose derivative is particularly excellent in optical isotropic properties, so that it can be made excellent in optical properties. Further, polyethylene terephthalate is preferable because it has high transparency and excellent mechanical properties.

The thickness of the base material used in the present embodiment is not particularly limited as long as it can provide the necessary self-supporting property depending on the use of the retardation film and the like, but is usually within the range of about 10 μm or more and 1000 μm or less. Is.
Above all, the thickness of the base material is preferably in the range of 25 μm or more and 125 μm or less, and particularly preferably in the range of 30 μm or more and 100 μm or less. If the thickness is thicker than the above range, for example, when a long retardation film is formed and then cut to obtain a single-wafer retardation film, processing waste increases or the cutting blade is worn. This is because it may become faster.

The structure of the base material used in the present embodiment is not limited to the structure consisting of a single layer, and may have a structure in which a plurality of layers are laminated. When a plurality of layers are laminated, layers having the same composition may be laminated, or a plurality of layers having different compositions may be laminated.
For example, when the alignment film used in the present embodiment contains an ultraviolet curable resin, a primer layer for improving the adhesiveness between the transparent base material and the ultraviolet curable resin is formed on the base material. You may. This primer layer may be any as long as it has adhesiveness to both the base material and the ultraviolet curable resin, is transparent in terms of visible optics, and allows ultraviolet rays to pass through, for example, a vinyl chloride / vinyl acetate copolymer system. , Urethane-based ones and the like can be appropriately selected and used.

Further, when the vertical alignment film is not provided, an anchor coat layer may be laminated on the base material. The anchor coat layer can improve the strength of the substrate and ensure good vertical orientation. As the anchor coat material, a metal alkoxide, particularly a metal silicon alkoxide sol, can be used. The metal alkoxide is usually used as an alcohol-based solution. Since the anchor coat layer requires a uniform and flexible film, the thickness of the anchor coat layer is preferably about 0.04 μm or more and 2 μm or less, and more preferably about 0.05 μm or more and 0.2 μm or less.
When the base material has an anchor coat layer, a binder layer is further laminated between the base material and the anchor coat layer, or the anchor coat layer contains a material for enhancing adhesion to the substrate. The adhesion between the material and the anchor coat layer may be improved. As the binder material used for forming the binder layer, a binder material capable of improving the adhesion between the base material and the anchor coat layer can be used without particular limitation. Examples of the binder material include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and the like.

4. Method for manufacturing a retardation film The method for manufacturing a retardation film according to the embodiment of the present disclosure is as follows.
The step of forming the liquid crystal composition of the embodiment of the present disclosure and
A step of orienting the liquid crystal constituent unit of the side chain type liquid crystal polymer in the film-formed liquid crystal composition and the polymerizable liquid crystal compound.
After the alignment step, there is a step of forming a retardation layer by having a step of polymerizing the polymerizable liquid crystal compound.
As the liquid crystal composition, the same one as in the above-mentioned "B. liquid crystal composition" can be used, and thus the description thereof will be omitted here.

(1) Film formation step of liquid crystal composition The liquid crystal composition is uniformly applied onto the support to form a film formation.
The support here may be on the base material or on the alignment film of the base material provided with the alignment film.

The coating method may be any method as long as it can form a film with a desired thickness with high accuracy, and may be appropriately selected. For example, gravure coating method, reverse coating method, knife coating method, dip coating method, spray coating method, air knife coating method, spin coating method, roll coating method, printing method, immersion pulling method, curtain coating method, die coating method, casting. Examples include a method, a bar coating method, an extrusion coating method, and an E-type coating method.

(2) Step of Aligning Liquid Crystal Component Next, the liquid crystal structural unit of the side chain type liquid crystal polymer in the film-formed liquid crystal composition and the polymerizable liquid crystal compound are adjusted to a temperature at which vertical alignment is possible and heated. .. By the heat treatment, the liquid crystal constituent unit of the side chain type liquid crystal polymer and the polymerizable liquid crystal compound can be vertically oriented and dried, and can be immobilized while maintaining the oriented state.
The temperature at which vertical orientation is possible differs depending on each substance in the liquid crystal composition, and therefore needs to be adjusted as appropriate. For example, it is preferably performed in the range of 60 ° C. or higher and 200 ° C. or lower, and further preferably in the range of 60 ° C. or higher and 100 ° C. or lower. Since the liquid crystal composition of the present embodiment has the side chain type liquid crystal polymer, the temperature range in which vertical orientation is possible is wide and temperature control is easy.
As the heating means, known heating and drying means can be appropriately selected and used.
The heating time may be appropriately selected, but is selected, for example, within the range of 10 seconds or more and 2 hours or less, preferably 20 seconds or more and 30 minutes or less.

(3) Step of Polymerizing a Polymerizable Liquid Crystal Compound In the alignment step, a polymerizable liquid crystal compound is polymerized by, for example, irradiating a coating film immobilized with the liquid crystal component in an oriented state with light. It is possible to obtain a retardation layer made of a cured product of the liquid crystal composition.
As the light irradiation, ultraviolet irradiation is preferably used. As the ultraviolet irradiation, ultraviolet rays emitted from light rays such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp can be used. Irradiation of energy beam source may if appropriately selected, accumulative exposure at an ultraviolet wavelength of 365 nm, it is preferably in the range of, for example, 10 mJ / cm ² or more 10000 mJ / cm ² or less.

5. Applications The retardation film of the present disclosure is suitably used as a retardation film having a positive C-type retardation layer. The retardation film of the present disclosure is preferably used, for example, as a viewing angle compensation film, and is preferably used as an optical member for various display devices as described later.

D. Laminate for Transfer The laminate for transfer of the present disclosure includes a retardation layer and a support that supports the retardation layer in a detachable manner.
The retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, and the side chain type liquid crystal polymer has a structural unit represented by the following general formula (I) and a liquid crystal structural unit. Consists of a cured product of the liquid crystal composition containing the copolymer having
It is a transfer laminate used for transfer of a retardation layer.

In the transfer laminate of the present embodiment, since the retardation layer is made of a cured product of the liquid crystal composition, precipitation of the polymerizable liquid crystal compound is suppressed, the optical characteristics are excellent, and the liquid crystal is oriented. Since the temperature range is widened, the process margin is wide and mass productivity is improved. According to the transfer laminate of the present embodiment, the retardation layer of the present disclosure, for example, a thin film containing no base material, can be transferred to any other optical member or the like.
According to the transfer laminate of the present embodiment, for example, the retardation film 10 composed of only the retardation layer 1 shown in the example of FIG. 2 and the orientation without the base material as shown in the example of FIG. It is possible to provide a retardation film composed of a laminate 26 in which a film 23 and a retardation layer 21 are laminated. That is, an alignment film or the like may be laminated on the retardation layer to be transferred to the transfer laminate as long as the retardation layer can be peeled off at least.
Hereinafter, the configuration of such a transfer laminate will be described, but since the liquid crystal composition of the embodiment of the present disclosure is as described above, the description thereof will be omitted here.

The layer structure of the transfer laminate will be described with reference to the drawings. 4 and 5 show one embodiment of the transfer laminate of the present disclosure, respectively.
One embodiment of the transfer laminate 20 shown in the example of FIG. 4 is formed on a second base material 12 as a retardation layer 16 to be subjected to transfer and a support 15 for detachably supporting the retardation layer. This is a transfer laminate in which the alignment film 13 and the retardation layer 11 are laminated in this order. In the transfer laminate shown in the example of FIG. 4, the peel strength between the second base material 12 and the alignment film 13 is larger than the peel strength between the alignment film 13 and the retardation layer 11. This is an example of a transfer laminate capable of transferring the retardation layer 11 (16) by being peeled off at the interface 17 between the alignment film and the retardation layer.
One embodiment of the transfer laminate 30 shown in the example of FIG. 5 is formed on a second base material 22 as a retardation layer 26 to be transferred and a support 25 for detachably supporting the retardation layer. This is a transfer laminate in which the alignment film 23 and the retardation layer 21 are laminated in this order. In the transfer laminate shown in the example of FIG. 5, the peel strength between the second base material 22 and the alignment film 23 is smaller than the peel strength between the alignment film 23 and the retardation layer 21. The retardation layer 26 that is peeled off at the interface 27 between the second base material 22 and the alignment film 23 and is used for transfer is an example of a transfer laminate capable of transferring the retardation layer 21 and the alignment film 23. be.

For example, whether the peel strength between the second base material and the alignment film is larger or smaller than the peel strength between the alignment film and the retardation layer is determined at which interface the retardation layer is peeled off. You can check with. At which interface the peeling occurs can be analyzed by, for example, IR or the like.

Further, one embodiment of the transfer laminate 40 shown in the example of FIG. 6 is a second base material 32 as a retardation layer 36 to be subjected to transfer and a support 35 in which the retardation layer is detachably supported. This is a transfer laminate in which the retardation layers 31 are laminated in this order.

Hereinafter, the present embodiment will be described, but since the phase difference layer can be the same as the phase layer described in the above “C. Phase difference film”, the description thereof will be omitted here.
Further, as the alignment film and the base material, the same ones as those of the alignment film and the base material described in the above "C. Phase difference film" can be used, and examples of the method for adjusting the peel strength include the following methods. be able to.

In order to obtain the transfer laminate 20 shown in the example of FIG. 4, the peel strength between the second base material 12 and the alignment film 13 is made larger than the peel strength between the alignment film 13 and the retardation layer 11. For example, a method of making the solvent contained in the composition for forming an alignment film soluble in the second base material can be used. It is preferable to use a resin base material as the second base material, and the surface of the base material may be surface-treated to improve the adhesiveness. In such a case, the adhesion between the resin base material and the alignment film can be improved.
Further, in order to reduce the peel strength between the alignment film and the retardation layer so that the peel strength between the base material and the alignment film is larger than the peel strength between the alignment film and the retardation layer, the solvent resistance of the alignment film is increased. It is also preferable to make the value relatively high. When the solvent resistance of the alignment film is relatively high, when the liquid crystal composition is applied onto the alignment film to form a retardation layer, the alignment film is difficult to dissolve in the solvent in the liquid crystal composition. The adhesion between the alignment film and the retardation layer can be lowered.

On the other hand, in order to obtain the transfer laminate 30 shown in the example of FIG. 5, the peel strength between the second base material 22 and the alignment film 23 is smaller than the peel strength between the alignment film 23 and the retardation layer 21. For this purpose, for example, the surface of the base material may be subjected to a mold release treatment, or a mold release layer may be formed. Thereby, the peelability of the base material can be enhanced, and the peel strength of the base material and the alignment layer can be made smaller than the peel strength of the alignment layer and the retardation layer.
Examples of the mold release treatment include surface treatments such as fluorine treatment and silicone treatment.
Examples of the material of the release layer include a fluorine-based release agent, a silicone-based release agent, a wax-based release agent, and the like. Examples of the method for forming the release layer include a method of applying a release agent by a coating method such as a dip coat, a spray coat, or a roll coat.
Further, in order to obtain the transfer laminate 40 shown in the example of FIG. 6, the surface of the base material may be subjected to a mold release treatment, or a mold release layer is formed, if necessary. May be good.

The base material used for the transfer laminate may or may not have flexibility, but it is preferable that the base material has flexibility because the base material can be easily peeled off.
The thickness of the base material used for the transfer laminate is usually described above because of the balance between sufficient self-supporting strength and flexibility sufficient for the production and transfer process of the transfer laminate of the present embodiment. In the case of a sheet of material, it is preferably in the range of 20 μm or more and 200 μm or less.

The retardation layer that can be provided from the transfer laminate of the present disclosure is suitably used for the same purposes as the retardation film, and the positive C-type retardation layer can be transferred to optical members for various display devices. , Suitable for providing a thin film optical member.

E. Optical member The optical member of the present disclosure includes a polarizing plate on the retardation film of the present disclosure.

The optical member of this embodiment will be described with reference to the drawings. FIG. 7 is a schematic cross-sectional view showing one embodiment of the optical member.
In the example of the optical member 60 of FIG. 7, the polarizing plate 50 is arranged on the retardation film 10 of the present disclosure. An adhesive layer (adhesive layer) may be provided between the retardation film 10 and the polarizing plate 50 (not shown), if necessary.

In the present embodiment, the polarizing plate is a plate-like polarizing plate that allows only light vibrating in a specific direction to pass through, and can be appropriately selected and used from conventionally known polarizing plates. For example, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, etc., which are dyed and stretched with iodine or a dye, can be used.
Further, in the present embodiment, the pressure-sensitive adhesive or adhesive for the pressure-sensitive adhesive layer (adhesive layer) may be appropriately selected from conventionally known ones, and is a pressure-sensitive adhesive (adhesive), a two-component curable adhesive, and the like. Any adhesive form such as an ultraviolet curable adhesive, a heat-curable adhesive, and a heat-melt adhesive can be preferably used.

In addition to the polarizing plate, the optical member of the present embodiment may further have another layer included in the known optical member. Examples of the other layer include an antireflection layer, a diffusion layer, an antiglare layer, an antistatic layer, a protective film, and the like, in addition to another retardation layer different from the retardation layer of the present embodiment. , Not limited to these.

The optical member of the present embodiment can be used, for example, as an optical member that suppresses reflection of external light. The optical member of the present disclosure in which the retardation film of the present disclosure and a circularly polarizing plate are laminated is suitably used as, for example, an optical member for suppressing reflection of external light for a light emitting display device, and various types of optical members are also used. It can be suitably used as a wide viewing angle polarizing plate for a display device.

F. Display device The display device according to the present disclosure is characterized by including the retardation film of the present embodiment or the optical member of the present embodiment.
Examples of the display device include, but are not limited to, a light emitting display device, a liquid crystal display device, and the like.

Above all, in order to include the retardation film of the present embodiment or the optical member of the present embodiment, particularly in a light emitting display device such as an organic light emitting display device having a transparent electrode layer, a light emitting layer, and an electrode layer in this order. It has the effect of improving the viewing angle while suppressing the reflection of external light.

An example of the light emitting display device according to the first embodiment will be described with reference to the drawings. FIG. 8 is a schematic cross-sectional view showing one embodiment of the optical member.
In the example of the organic light emitting display device 100 of FIG. 8, the polarizing plate 50 is arranged on the light emitting surface side of the retardation film 10, and the transparent electrode layer 71, the light emitting layer 72, and the electrode layer are arranged on the opposite surface. 73 and in this order.
Examples of the light emitting layer 72 include a configuration in which a hole injection layer, a hole transport layer, a light emitting layer, and an electron injection layer are laminated in this order from the transparent electrode layer 71 side. In the present embodiment, known configurations can be appropriately used as the transparent electrode layer, the hole injection layer, the hole transport layer, the light emitting layer, the electron injection layer, the electrode layer, and other configurations. The light emitting display device produced in this manner can be applied to, for example, both a passive drive type organic EL display and an active drive type organic EL display.
The display device of the present embodiment is not limited to the above configuration, and may have a known configuration appropriately selected.

(Synthesis Example 1: Synthesis of Liquid Crystal Monomer 1)
First, 4- [2- (acryloyloxy) ethyloxy] benzoic acid was synthesized according to Scheme 1 below.

Next, a liquid crystal monomer 1 was obtained according to the following scheme 2. Specifically, 4- [2- (acryloyloxy) ethyloxy] benzoic acid (179.4 g, 759.4 mmol) obtained above, and 4'-cyano-4-hydroxybiphenyl (148.3 g, 759.4 mmol). ), 35% hydrochloric acid solution (2.373 g), N, N-dicyclohexylcarbodiimide (DCC) in a dichloromethane (1243 g) suspension of N, N-dimethylaminopyridine (DMAP) (2.739 g, 22.78 mmol). A solution of (170.8 g, 827.8 mmol) in dichloromethane (170.8 g) was added dropwise. After completion of the dropping, the mixture was stirred overnight, the precipitate was filtered, and then the solvent was distilled off. Methanol (1421 g) was added to the obtained crude product, and the mixture was stirred at room temperature for 1 hour for suspension purification. The precipitate was filtered and the obtained crystals were dried to obtain 4'-cyano-4- {4- [2- (acryloyloxy) ethyloxy] benzoate} (chemical formula (1) below) in a yield of 95. It was obtained at 9% (301.1 g, 728.3 mmol).

(Synthesis Example 2: Synthesis of Liquid Crystal Monomer 2)
A liquid crystal monomer 2 represented by the following chemical formula (2) was obtained in the same manner as in Synthesis Example 1 except that 6-chloro-1-n-hexanol was used instead of 2-bromoethanol in Synthesis Example 1. rice field.

(Synthesis Example 3: Synthesis of Liquid Crystal Monomer 3)
First, 4-propoxycarbonylphenyl = 4-hydroxybenzoart was obtained according to Scheme 3 below. Specifically, 4-acetoxybenzoic acid (524.8 g, 2.91 mol), propyl 4-hydroxybenzoate (500 g, 2.78 mol), N, N-dimethylaminopyridine (DMAP) (20.34 g, 0). A solution of N, N-dicyclohexylcarbodiimide (DCC) (601.3 g, 2.91 mol) in dichloromethane (601.3 g) was added dropwise to a suspension of dichloromethane (2.5 L) of .17 mmol). After completion of the dropping, the mixture was stirred overnight, the precipitate was filtered, and then the solvent was distilled off. Methanol (3.4 L) was added to the obtained oil to dissolve it, and then a solution of potassium carbonate (446.1 g, 3.23 mol) in water (1.7 L) was slowly added dropwise under cooling. After stirring the reaction mixture for 1 hour, the reaction mixture was neutralized with 35% hydrochloric acid (325 mL), the precipitated crystals were filtered, and the crude product was dried to obtain 4-propoxycarbonylphenyl = 4-hydroxybenzoate in two steps 71. It was obtained in a yield of 9.9% (602.17 g, 2.00 mol).

Next, a liquid crystal monomer 3 represented by the following chemical formula (3) was obtained according to the following scheme 4. Specifically, 4-propoxycarbonylphenyl = 4-hydroxybenzoate (664 g, 2.27 mol), 4- [6- (acryloyloxy) hexyloxy] benzoic acid (650 g, 2.16 mol), N, N- Dichloromethane (489 g) of N, N-dicyclohexylcarbodiimide (DCC) (489.0 g, 2.37 mol) in a dichloromethane (2.8 L) suspension of dimethylaminopyridine (DMAP) (7.9 g, 0.06 mol). The solution was added dropwise. After completion of the dropping, the mixture was stirred overnight, the precipitate was filtered, and then the solvent was distilled off. Methanol (5.0 L) was added to the obtained crude product to dissolve it, and then the mixture was stirred under cooling for 5 hours. The precipitated crystals were filtered and the obtained crystals were dried to obtain 4-[(4-propoxycarbonylphenyloxycarbonyl) phenyl = 4- [6- (acryloyloxy) hexyloxy] benzoate in a yield of 87. It was obtained at 7% (1091 g, 1.90 mol).

(Synthesis Example 4: Synthesis of Monomer A)
4-Amilphenol (82.5 g, 502 mmol), 6-chloro-1-hexanol (102.9 g, 753 mmol), potassium carbonate (83.3 g, 603 mmol), N, N-dimethyl in a light-shielded 2 L four-flask. Formamide (198.1 g) was added, the temperature was raised to 100 ° C., and the mixture was stirred for 37 hours. Then, the reaction solution was allowed to cool to room temperature, tap water (413,1 g) was added, and the mixture was stirred for 10 minutes. Then, ethyl acetate (330.5 g) was further added, and the mixture was stirred for 5 minutes, and then the liquid was separated. The separated water tank was re-extracted with ethyl acetate (329.8 g) and the combined organic layers were washed with tap water (412.9 g). Then, the organic layer was washed with tap water (413.8 g) and saturated brine (150 ml), the water tank was removed by liquid separation, and then the solvent was distilled off. The residue was purified by silica gel chromatography (ethyl acetate / hexane = 0/100 → 15/85), and the solvent was distilled off to obtain 44.6 g of ether A.
Next, the etheric body A (39.9 g, 151 mmol), N, N-dimethylaniline (20.0 g, 166 mmol), N, N-dimethylacetamide (10.0 g), tetrahydrofuran was placed in a light-shielded 2 L four flask. (116 g) was added and cooled to an internal temperature of 15 ° C. or lower. A solution prepared by dissolving acrylic acid chloride (15.0 g, 166 mmol) in tetrahydrofuran (4.0 g) was added dropwise to the mixed solution, and the mixture was stirred at 25 ° C. for 5 hours. Then, the reaction solution was added dropwise to tap water (400.0 g) at 11.7-20.1 ° C., and ethyl acetate (320.0 g) was added for extraction. Then, 4-methoxyphenol (2.4 g) and 10% saline solution were added to the organic layer for washing. The separated organic layer was washed by adding 10% saline solution again, and then the solvent of the organic layer was distilled off. The residue was purified by silica gel chromatography (ethyl acetate / hexane = 0/100 → 2/98), and the solvent was distilled off to obtain 14.8 g of monomer A represented by the following chemical formula (A).

(Synthesis Example 5: Synthesis of Monomer B)
Monomer B represented by the following chemical formula (B) was obtained in the same manner as in Synthesis Example 4 except that an equal molar amount of 4-nonylphenol was used instead of 4-amylphenol in Synthesis Example 4.

(Synthesis Example 6: Synthesis of Monomer C)
The monomer represented by the following chemical formula (C) is the same as in Synthesis Example 4 except that an equal molar amount of 3-chloro-1-propanol is used instead of 6-chloro-1-hexanol in Synthesis Example 4. C was obtained.

(Synthesis Example 7: Synthesis of Monomer D)
The monomer represented by the following chemical formula (D) is the same as in Synthesis Example 4 except that an equal molar amount of 12-bromo-1-dodecanol is used instead of 6-chloro-1-hexanol in Synthesis Example 4. I got D.

(Synthesis Example 8: Synthesis of Monomer E)
In Synthesis Example 4, the following chemical formula (E) is used in the same manner as in Synthesis Example 4 except that an equal molar amount of ethylene glycol mono-2-chloroethyl ether is used instead of 6-chloro-1-hexanol. Monomer E was obtained.

(Synthesis Example 9: Synthesis of Monomer F)
In Synthesis Example 4, it is represented by the following chemical formula (F) in the same manner as in Synthesis Example 4 except that an equal molar amount of diethylene glycol mono (2-chloroethyl) ether is used instead of 6-chloro-1-hexanol. Monomer F was obtained.

(Synthesis Example 10: Synthesis of Monomer G)
Monomer G represented by the following chemical formula (G) was obtained in the same manner as in Synthesis Example 4 except that an equal molar amount of 4-hexyloxyphenol was used instead of 4-amylphenol in Synthesis Example 4.

Further, stearyl acrylate (the following chemical formula (H)) was used as the monomer H (manufactured by Tokyo Kasei Co., Ltd.).

(Production Examples 1 to 11, Comparative Production Example 1: Synthesis of side chain type liquid crystal polymers A-01 to A-12)
The liquid crystal monomers 1 to 3 for inducing a liquid crystal structural unit and the monomers A to H as non-liquid crystal monomers for inducing the structural unit represented by the general formula (I) are combined according to Table 1 to form a side chain type liquid crystal. The polymer was synthesized.
A synthetic example of the side chain type liquid crystal polymer A-01 will be specifically described.
The liquid crystal monomer 1 and the monomer A were combined and mixed so as to have a molar ratio of 50:50, N, N-dimethylacetamide (DMAc) was added, and the mixture was stirred and dissolved at 40 ° C. After dissolution, the mixture was cooled to 24 ° C., azobisisobutyronitrile (AIBN) was added, and the mixture was dissolved at the same temperature. The reaction solution was added dropwise to DMAc heated to 80 ° C. over 30 minutes, and after completion of the addition, the mixture was stirred at 80 ° C. for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, methanol at 9 ° C. was added dropwise to another stirring container, and the mixture was stirred for 20 minutes. After removing the supernatant, the slurry was filtered, and the obtained crude product was stirred again in methanol at 9 ° C. for 20 minutes to remove the supernatant and filtered. The obtained crystals were dried to obtain a side chain type liquid crystal polymer A-01 in a yield of 76.5%.

In the production example of the side chain type liquid crystal polymer A-01, the side chain type liquid crystal polymer A-01 is obtained except that the combination of the liquid crystal monomer and the non-liquid crystal monomer and the copolymerization ratio (molar ratio) are changed as shown in Table 1. The side chain type liquid crystal polymers A-02 to A-12 were obtained in the same manner as in the synthesis example of. The mass average molecular weight Mw of each of the obtained side chain type liquid crystal polymers A-01 to A-12 was measured by the above-mentioned GPC, and the structure was analyzed by ^{1 H-NMR.} The mass average molecular weights (Mw) of the side chain type liquid crystal polymers A-01 to A-12 are shown in Table 1, respectively. ^{The results of 1 1} H-NMR are shown below.

<Side chain type liquid crystal polymer A-01>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.60 to 2.12 (m, Alkyl-H), 3.61 to 4.27 (m, -O-CH2-), 6.80 to 7.73 (m, Aromatic-H), 8.18 (bs, CN-C = CH-)

<Side chain type liquid crystal polymer A-02>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): ^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.61 to 2.08 (m, Alkyl-H), 3.60 to 4.28 (M, -O-CH2-), 6.81-7.72 (m, Magnetic-H), 8.12 (bs, CN-C = CH-)

<Side chain type liquid crystal polymer A-03>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): ^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.60 to 2.10 (m, Alkyl-H), 3.61 to 4.27 (M, -O-CH2-), 6.80 to 7.72 (m, Aromatic-H), 8.19 (bs, CN-C = CH-)

<Side chain type liquid crystal polymer A-04>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): ^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.60 to 2.08 (m, Alkyl-H), 3.61 to 4.27 (M, -O-CH2-), 6.80 to 7.73 (m, Aromatic-H), 8.18 (bs, CN-C = CH-)

<Side chain type liquid crystal polymer A-05>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): ^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.61 to 2.10 (m, Alkyl-H), 3.59 to 4.29 (M, -O-CH2-), 6.81-7.75 (m, Aromatic-H), 8.11 (bs, CN-C = CH-)

<Side chain type liquid crystal polymer A-06>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): ^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.62 to 2.09 (m, Alkyl-H), 3.61 to 4.27 (M, -O-CH2-), 6.80 to 7.73 (m, Aromatic-H), 8.10 (bs, CN-C = CH-)

<Side chain type liquid crystal polymer A-07>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): ^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.61 to 2.07 (m, Alkyl-H), 3.63 to 4.29 (M, -O-CH2-), 6.81-7.73 (m, Aromatic-H), 8.15 (bs, CN-C = CH-)

<Side chain type liquid crystal polymer A-08>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): ^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.62 to 2.12 (m, Alkyl-H), 3.65 to 4.32 (M, -O-CH2-), 6.80 to 7.75 (m, Aromatic-H), 8.09 (bs, CN-C = CH-)

<Side chain type liquid crystal polymer A-09>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): ^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.61 to 2.11 (m, Alkyl-H), 3.60 to 4.30 (M, -O-CH2-), 6.82 to 7.77 (m, Aromatic-H), 8.10 (bs, CN-C = CH-)

<Side chain type liquid crystal polymer A-10>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): ^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.61 to 1.83 (m, Alkyl-H), 3.61 to 4.31 (M, -O-CH2-), 6.82 to 7.76 (m, Aromatic-H), 8.11 (bs, CN-C = CH-)

<Side chain type liquid crystal polymer A-11>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): ^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.60 to 2.09 (m, Alkyl-H), 3.61 to 4.26 (M, -O-CH2-), 6.82 to 7.73 (m, Aromatic-H), 8.18 (bs, CN-C = CH-)

<Side chain type liquid crystal polymer A-12>
^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): ^{1 1} H-NMR (400 MHz, DMSO-d6, TMS): 0.61 to 2.08 (m, Alkyl-H), 3.61 to 4.26 (M, -O-CH2-), 6.80 to 7.73 (m, Aromatic-H), 8.17 (bs, CN-C = CH-)

As the polymerizable liquid crystal compound, the compounds of the following chemical formula B-01 and the following chemical formula B-02 were prepared.

The following C-01 and the following C-02 were prepared as photopolymerization initiators (both manufactured by BASF).
C-01: IRGACURE 907
C-02: IRGACUR 184

Further, as a leveling agent, a fluorine-containing surfactant (Megafuck F-554 manufactured by DIC Corporation) was prepared.

(Example 1: Preparation of liquid crystal composition)
400 parts by mass of side chain liquid crystal polymer (A-01), 50 parts by mass of photopolymerizable liquid crystal compound (B-01) and 4 parts by mass of photopolymerization initiator (Irgacure 907, manufactured by Ciba Speciali Chemicals) The liquid crystal composition 1 was prepared by dissolving it in a portion.

(Examples 2 to 15: Preparation of liquid crystal compositions 2 to 15)
Liquid crystal compositions 2 to 15 were obtained in the same manner as in Example 1 except that the composition of each component was changed according to Table 2.

(Comparative Examples 1 and 2: Preparation of Comparative Liquid Crystal Compositions X1 and X2)
Comparative liquid crystal compositions X1 to X2 were obtained in the same manner as in Example 1 except that the composition of each component was changed according to Table 2.

[evaluation]
Fabrication of optical film Using a PET substrate (manufacturer name, product number) with a thickness of 38 μm, a composition for a vertically oriented film (Fine Cure PXV-18 manufactured by Sanyo Kasei Kogyo Co., Ltd.) is applied to one side thereof so that the film thickness is 3 μm. And irradiated with polarized ultraviolet rays of 20 mJ / cm ^{2 to prepare an alignment film.}
Subsequently, on the formed alignment film, the flow rates of the liquid crystal compositions of the above-mentioned Examples and Comparative Examples were adjusted at the time of coating so that the thickness retardation Rth (550) at the measurement wavelength of 550 nm was -100 nm, respectively, and the die head was used. It was applied on the alignment film by a coating method. Regarding the lower and upper limits of the vertical orientation temperature, each liquid crystal composition was spin-coated on a glass substrate, and the state of the sample in the temperature range was observed under a cross Nicol with a polarizing microscope equipped with a hot plate capable of heating and cooling. Was measured.
Then, the lower limit of the vertical orientation temperature shown in Table 2 plus 10 ° C. was set as each drying temperature, and after drying for 120 seconds, ultraviolet rays (UV) were irradiated to form a retardation layer to obtain an optical film.
After that, the retardation layer is transferred to the adhesive glass, and the retardation Rth (nm) in the thickness direction is measured using KOBRA-WR manufactured by Oji Measuring Instruments Co., Ltd. and RETS100 manufactured by Otsuka Electronics Co., Ltd. , It was confirmed that they were oriented in the thickness direction of the phase difference.
The retardation layer was observed under a cross Nicol with a polarizing microscope using the illumination of a light table, and the liquid crystal precipitation was evaluated according to the following evaluation criteria.
[Liquid crystal precipitation evaluation criteria]
A: A state in which liquid crystal molecules are uniformly oriented without precipitation of minute crystals B: A state in which some crystals are precipitated and bright crystal parts can be seen under cross Nicol.

[Summary of results]
From the results in Table 2, in Examples 1 to 15, the liquid crystal precipitation was caused in Examples 1 to 15, wherein the side chain type liquid crystal polymer contained a copolymer having a structural unit represented by the general formula (I) and a liquid crystal structural unit. It has been clarified that the liquid crystal composition is suppressed and the temperature range in which the liquid crystal is oriented can be widened, and is a retardation film having a retardation layer in which precipitation of the liquid crystal is suppressed and mass productivity is improved.

1 Phase difference layer 2, 2'Base material 3 Alignment film 10 Phase difference film 11, 21, 31 Phase difference layer 12, 22, 32 Second base material 13, 23, 33 Alignment film 15, 25, 35 Peelable Supports 16, 26, 36 Phase layer used for transfer 17 Interface between alignment film and retardation layer 27 Interface between second base material and alignment film 20, 30, 40 Transfer laminate 50 Plate plate 60 Optical member 71 Transparent electrode layer 72 Light emitting layer 73 Electrode layer 100 Light emitting display device

Claims (11)

A structural unit represented by the following general formula (I), seen containing a copolymer having a liquid crystalline structure unit, when the entire copolymer as 100 mol%, represented by the general formula (I) A side-chain type liquid crystal polymer in which the content ratio of the constituent units is 20 mol% or more and 60 mol% or less, and the content ratio of the liquid liquid constituent units is 40 mol% or more and 80 mol% or less.

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is − (CH ₂ ) _n −L ¹ −Ar ¹ −R ³ or − (C ₂ H ₄ O) _{n ′.} The group represented by ^{−Ar 1} −R ^{3 is directly bonded to L 1} , or is represented by −O−, −OC (= O) −, or −C (= O) −O−. As the linking group, Ar ¹ is an arylene group having 6 or more and 12 or less ^{carbon atoms which may have a substituent, and R 3} is an arylene group which may have a substituent and has 2 or more and 10 or less carbon atoms. Represents a linear or branched alkyl group or alkoxy group, and n and n'are independently integers of 2 or more and 10 or less.) The side chain type liquid crystal polymer according to claim 1, wherein the liquid crystal structural unit contains a structural unit represented by the following general formula (II).

(In the general formula (II), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a group represented by − (CH ₂ ) _m − or − (C ₂ H ₄ O) _{m ′ −.} . L ² is a direct bond or -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -N (-R ¹⁴ ) -C (= O)-, -C (= O) -N (-R ¹⁴ )-, -OC (= O) -N (-R ¹⁴ )-, -N ( -R ¹⁴ ) -C (= O) -O-, -N (-R ¹⁴ ) -C (= O) -N (-R ¹⁴ )-, -ON (-R ¹⁴ )-, or -N (-R ¹⁴ ) The linking group represented by -O-, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms. Ar ² is a carbon which may have a substituent. It represents an arylene group having 6 or more and 10 or less atoms, and a plurality of L ² and Ar ² may be the same or different, respectively. R ¹³ is -F, -Cl, -CN, -OCF ₃ , -. OCF ₂ H, -NCO, -NCS, -NO ₂ , -NHC (= O) -R ¹⁵ , -C (= O) -OR ¹⁵ , -OH, -SH, -CHO, -SO ₃ H, -NR ¹⁵ _2, ^{-R 16,} or ^{-OR 16, R 15} represents a hydrogen atom or a carbon atoms of 1 to 6. the alkyl ^{group, R 16} represents 1 to 6 alkyl group carbon atoms. a is an integer of 2 or more and 4 or less, and m and m'are independently integers of 2 or more and 10 or less.) The side chain type liquid crystal polymer contains a side chain type liquid crystal polymer, a polymerizable liquid crystal compound, and a photopolymerization initiator, and the side chain type liquid crystal polymer has a structural unit represented by the following general formula (I) and a liquid crystal structural unit. having a copolymer seen including, when the entire copolymer as 100 mol%, the content ratio of structural units represented by the general formula (I) is 60 mol% or less than 20 mol%, the liquid crystal A liquid crystal composition having a content ratio of a sex constituent unit of 40 mol% or more and 80 mol% or less.

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is − (CH ₂ ) _n −L ¹ −Ar ¹ −R ³ or − (C ₂ H ₄ O) _{n ′.} The group represented by ^{−Ar 1} −R ^{3 is directly bonded to L 1} , or is represented by −O−, −OC (= O) −, or −C (= O) −O−. As the linking group, Ar ¹ is an arylene group having 6 or more and 12 or less ^{carbon atoms which may have a substituent, and R 3} is an arylene group which may have a substituent and has 2 or more and 10 or less carbon atoms. Represents a linear or branched alkyl group or alkoxy group, and n and n'are independently integers of 2 or more and 10 or less.) The liquid crystal composition according to claim 3, wherein the liquid crystalline structural unit contains a structural unit represented by the following general formula (II).

(In the general formula (II), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a group represented by − (CH ₂ ) _m − or − (C ₂ H ₄ O) _{m ′ −.} . L ² is a direct bond or -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -N (-R ¹⁴ ) -C (= O)-, -C (= O) -N (-R ¹⁴ )-, -OC (= O) -N (-R ¹⁴ )-, -N ( -R ¹⁴ ) -C (= O) -O-, -N (-R ¹⁴ ) -C (= O) -N (-R ¹⁴ )-, -ON (-R ¹⁴ )-, or -N (-R ¹⁴ ) The linking group represented by -O-, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms. Ar ² is a carbon which may have a substituent. It represents an arylene group having 6 or more and 10 or less atoms, and a plurality of L ² and Ar ² may be the same or different, respectively. R ¹³ is -F, -Cl, -CN, -OCF ₃ , -. OCF ₂ H, -NCO, -NCS, -NO ₂ , -NHC (= O) -R ¹⁵ , -C (= O) -OR ¹⁵ , -OH, -SH, -CHO, -SO ₃ H, -NR ¹⁵ _2, ^{-R 16,} or ^{-OR 16, R 15} represents a hydrogen atom or a carbon atoms of 1 to 6. the alkyl ^{group, R 16} represents 1 to 6 alkyl group carbon atoms. a is an integer of 2 or more and 4 or less, and m and m'are independently integers of 2 or more and 10 or less.) A retardation film having a retardation layer, wherein the retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, and the side chain type liquid crystal polymer is represented by the following general formula (I). a structural unit, seen containing a copolymer having a liquid crystalline structure unit, when the entire copolymer as 100 mol%, the content ratio of structural units represented by the general formula (I) 20 A retardation film made of a cured product of a liquid crystal composition having a molar% or more and 60 mol% or less and a content ratio of the liquid crystal constituent unit of 40 mol% or more and 80 mol% or less.

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is − (CH ₂ ) _n −L ¹ −Ar ¹ −R ³ or − (C ₂ H ₄ O) _{n ′.} The group represented by ^{−Ar 1} −R ^{3 is directly bonded to L 1} , or is represented by −O−, −OC (= O) −, or −C (= O) −O−. As the linking group, Ar ¹ is an arylene group having 6 or more and 12 or less ^{carbon atoms which may have a substituent, and R 3} is an arylene group which may have a substituent and has 2 or more and 10 or less carbon atoms. Represents a linear or branched alkyl group or alkoxy group, and n and n'are independently integers of 2 or more and 10 or less.) The retardation film according to claim 5, wherein the liquid crystalline structural unit includes a structural unit represented by the following general formula (II).

(In the general formula (II), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a group represented by − (CH ₂ ) _m − or − (C ₂ H ₄ O) _{m ′ −.} . L ² is a direct bond or -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -N (-R ¹⁴ ) -C (= O)-, -C (= O) -N (-R ¹⁴ )-, -OC (= O) -N (-R ¹⁴ )-, -N ( -R ¹⁴ ) -C (= O) -O-, -N (-R ¹⁴ ) -C (= O) -N (-R ¹⁴ )-, -ON (-R ¹⁴ )-, or -N (-R ¹⁴ ) The linking group represented by -O-, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms. Ar ² is a carbon which may have a substituent. It represents an arylene group having 6 or more and 10 or less atoms, and a plurality of L ² and Ar ² may be the same or different, respectively. R ¹³ is -F, -Cl, -CN, -OCF ₃ , -. OCF ₂ H, -NCO, -NCS, -NO ₂ , -NHC (= O) -R ¹⁵ , -C (= O) -OR ¹⁵ , -OH, -SH, -CHO, -SO ₃ H, -NR ¹⁵ _2, ^{-R 16,} or ^{-OR 16, R 15} represents a hydrogen atom or a carbon atoms of 1 to 6. the alkyl ^{group, R 16} represents 1 to 6 alkyl group carbon atoms. a is an integer of 2 or more and 4 or less, and m and m'are independently integers of 2 or more and 10 or less.) The step of forming a film of the liquid crystal composition according to claim 3 or 4.
A step of orienting the liquid crystal constituent unit of the side chain type liquid crystal polymer in the film-formed liquid crystal composition and the polymerizable liquid crystal compound.
A method for producing a retardation film, which comprises a step of polymerizing the polymerizable liquid crystal compound after the alignment step to form a retardation layer. A retardation layer and a support that supports the retardation layer in a detachable manner are provided.
The retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, and the side chain type liquid crystal polymer has a structural unit represented by the following general formula (I) and a liquid crystal structural unit. having a copolymer seen including, when the entire copolymer as 100 mol%, the content ratio of structural units represented by the general formula (I) is 60 mol% or less than 20 mol%, the liquid crystal The content ratio of the sex constituent unit is 40 mol% or more and 80 mol% or less, and is composed of a cured product of the liquid crystal composition.
A transfer laminate used for transfer of a retardation layer.

(In the general formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is − (CH ₂ ) _n −L ¹ −Ar ¹ −R ³ or − (C ₂ H ₄ O) _{n ′.} The group represented by ^{−Ar 1} −R ^{3 is directly bonded to L 1} , or is represented by −O−, −OC (= O) −, or −C (= O) −O−. As the linking group, Ar ¹ is an arylene group having 6 or more and 12 or less ^{carbon atoms which may have a substituent, and R 3} is an arylene group which may have a substituent and has 2 or more and 10 or less carbon atoms. Represents a linear or branched alkyl group or alkoxy group, and n and n'are independently integers of 2 or more and 10 or less.) The transfer laminate according to claim 8, wherein the liquid crystalline structural unit includes a structural unit represented by the following general formula (II).

(In the general formula (II), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a group represented by − (CH ₂ ) _m − or − (C ₂ H ₄ O) _{m ′ −.} . L ² is a direct bond or -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -N (-R ¹⁴ ) -C (= O)-, -C (= O) -N (-R ¹⁴ )-, -OC (= O) -N (-R ¹⁴ )-, -N ( -R ¹⁴ ) -C (= O) -O-, -N (-R ¹⁴ ) -C (= O) -N (-R ¹⁴ )-, -ON (-R ¹⁴ )-, or -N (-R ¹⁴ ) The linking group represented by -O-, R ¹⁴ represents a hydrogen atom or an alkyl group having 1 or more carbon atoms and 6 or less carbon atoms. Ar ² is a carbon which may have a substituent. It represents an arylene group having 6 or more and 10 or less atoms, and a plurality of L ² and Ar ² may be the same or different, respectively. R ¹³ is -F, -Cl, -CN, -OCF ₃ , -. OCF ₂ H, -NCO, -NCS, -NO ₂ , -NHC (= O) -R ¹⁵ , -C (= O) -OR ¹⁵ , -OH, -SH, -CHO, -SO ₃ H, -NR ¹⁵ _2, ^{-R 16,} or ^{-OR 16, R 15} represents a hydrogen atom or a carbon atoms of 1 to 6. the alkyl ^{group, R 16} represents 1 to 6 alkyl group carbon atoms. a is an integer of 2 or more and 4 or less, and m and m'are independently integers of 2 or more and 10 or less.) An optical member comprising a polarizing plate on the retardation film according to claim 5 or 6. A display device comprising the retardation film according to claim 5 or 6 or the optical member according to claim 10.

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