JP7172053B2 - Liquid crystal composition, retardation film, method for producing retardation film, laminate for transfer, optical member, method for producing optical member, and display device - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to a liquid crystal composition, a retardation film, a method for producing a retardation film, a transfer laminate, an optical member, a method for producing an optical member, and a display device.

2. Description of the Related Art Conventionally, regarding display devices such as liquid crystal display devices and light-emitting display devices, there have been proposed configurations in which various optical members are arranged on a panel surface. Further, for such an optical member, a configuration is proposed 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 highly reflective metal electrode is provided in order to efficiently utilize light from a light-emitting layer. On the other hand, since the use of the metal electrode increases the reflection of external light, the light-emitting display device has a circularly polarizing plate or the like for suppressing the reflection of external light.

Light transmitted through the polarizing plate has optical anisotropy, and in a display device, the anisotropy causes deterioration in contrast depending on the viewing angle. On the other hand, there is known a method of improving the viewing angle by using a retardation film, particularly a positive C-type retardation film (positive C plate).

A positive C plate can be obtained, for example, by aligning rod-like liquid crystal molecules in the plate perpendicularly to the plane of the plate.
For example, Patent Document 1 discloses a retardation film having a homeotropically aligned liquid crystal film formed from a homeotropically aligned liquid crystalline composition containing a specific homeotropically aligned side chain type liquid crystal polymer and a photopolymerizable liquid crystal compound. A plate is disclosed.

Japanese Patent Application Laid-Open No. 2003-149441

In addition, as display devices and the like equipped with retardation films are becoming more versatile, retardation films are required to have improved durability such as heat resistance. However, the conventional positive C-plate has insufficient heat resistance, and there is a problem that the phase difference is likely to fluctuate due to heat.

Embodiments of the present disclosure are excellent in vertical alignment, capable of forming a retardation layer with improved heat resistance, a liquid crystal composition with excellent coating properties, excellent in vertical alignment, and a retardation layer with improved heat resistance. A retardation film and a method for producing the same, a laminate for transfer that is used for transferring a retardation layer having excellent vertical alignment and improved heat resistance, an optical member having the retardation film, a method for producing the same, and a display device intended to provide

One embodiment of the present disclosure contains a side chain type liquid crystal polymer, a polymerizable liquid crystal compound, and a photopolymerization initiator,
The side chain type liquid crystal polymer has a non-liquid crystalline structural unit having a structure represented by the following general formula (I) and an SP value of 9.25 (cal/cm ³ ) ^1/2 or more; and a liquid crystalline structural unit having a side chain containing a moiety,
Provided is a liquid crystal composition in which the mass ratio of the side chain type liquid crystal polymer to the total mass of the side chain type liquid crystal polymer and the polymerizable liquid crystal compound is 2% by mass or more and 20% by mass or less.

（一般式（Ｉ）中、Ｒ^１は、水素原子又はメチル基を表し、Ｒ^２は、－（Ｃ_２Ｈ_４Ｏ）_ｎ－Ｒ^３、又は－Ｒ^４－Ｘ－Ｙ－Ｒ^５で表される基を表す。ｎは７以上１６以下の整数を表し、Ｒ^３は炭素数１以上３以下のアルキル基を表す。Ｒ^４は炭素数１以上２２以下のアルキレン基を表し、Ｒ^５は炭素数１以上９以下のアルキル基を表し、Ｒ^４及びＲ^５の少なくとも１つが炭素数３以上の直鎖構造を有する。Ｘは－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－、－Ｏ－ＣＨ_２－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨ－Ｃ（＝Ｏ）－Ｏ－又は－Ｏ－Ｃ（＝Ｏ）－ＣＨ＝ＣＨ－で表される連結基を表し、Ｙは１，４－フェニレン基又は１，４－シクロヘキシレン基を表す。前記Ｙにおいて、１，４－フェニレン基は、１個又は隣接しない２個以上の－ＣＨ＝が－Ｎ＝によって置換されていてもよく、１，４－シクロヘキシレン基は、１個又は隣接しない２個以上の－ＣＨ_２－が－Ｏ－又は－Ｓ－によって置換されていてもよく、１，４－フェニレン基及び１，４－シクロヘキシレン基は、ハロゲン原子、シアノ基及びニトロ基から選ばれる少なくとも１種の置換基を有していてもよい。）

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents -(C ₂ H ₄ O) _n -R ³ or -R ⁴ -XY-R ⁵ n represents an integer of 7 to 16, R ³ represents an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkylene group having 1 to 22 carbon atoms, and R ⁵ represents represents an alkyl group having 1 to 9 carbon atoms, and at least one of R ⁴ and R ⁵ has a straight chain structure having 3 or more carbon atoms, X represents -O-, -C(=O)-O-, -O -C(=O)-, -O-CH ₂ -, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -O-C(=O)- represents a linking group represented by CH=CH-, Y represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and in Y, the number of 1,4-phenylene groups is one or two which are not adjacent; One or more -CH= may be substituted by -N=, and the 1,4-cyclohexylene group is a group in which one or two or more non-adjacent -CH ₂ - are substituted by -O- or -S- and the 1,4-phenylene group and 1,4-cyclohexylene group may have at least one substituent selected from halogen atoms, cyano groups and nitro groups.)

One embodiment of the present disclosure is a retardation film having a retardation layer,
The retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, the side chain type liquid crystal polymer has a structure represented by the general formula (I), and has an SP value of 9.0. 25 (cal/cm ³ ) ^1/2 or more having a non-liquid crystalline structural unit and a liquid crystalline structural unit having a side chain containing a liquid crystalline portion, the side chain type liquid crystalline polymer and the polymerizable liquid crystal compound and the side chain type liquid crystal polymer in a mass ratio of 2% by mass or more and 20% by mass or less.

One embodiment of the present disclosure has a substrate and the retardation layer on the substrate,
Provided is a retardation film, wherein the surface free energy of the retardation layer side surface of the substrate is 30 mJ/m ² or more.

An embodiment of the present disclosure provides a step of preparing a substrate having a surface free energy of 30 mJ/m ² or more on at least one surface;
forming a film of the liquid crystal composition of the embodiment of the present disclosure on the surface of the substrate;
a step of aligning the liquid crystal constitutional units of the side chain type liquid crystal polymer in the formed liquid crystal composition and the polymerizable liquid crystal compound;
Provided is a method for producing a retardation film, comprising a step of polymerizing the polymerizable liquid crystal compound after the orienting step, thereby forming a retardation layer.

One embodiment of the present disclosure comprises a retardation layer and a support having a peelable support layer,
The retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, the side chain type liquid crystal polymer has a structure represented by the general formula (I), and has an SP value of 9.0. 25 (cal/cm ³ ) ^1/2 or more having a non-liquid crystalline structural unit and a liquid crystalline structural unit having a side chain containing a liquid crystalline portion, the side chain type liquid crystalline polymer and the polymerizable liquid crystal compound A cured product of a liquid crystal composition in which the mass ratio of the side chain type liquid crystal polymer to the total mass of the liquid crystal composition is 2% by mass or more and 20% by mass or less,
A transfer layered product is provided for transferring the retardation layer.

An embodiment of the present disclosure provides a transfer laminate, wherein the surface free energy of the retardation layer-side surface of the support is 30 mJ/m ² or more.

An embodiment of the present disclosure provides an optical member comprising a polarizing plate on the retardation film of the embodiment of the present disclosure.

An embodiment of the present disclosure provides a step of preparing the transfer laminate of the embodiment of the present disclosure;
A transfer target containing at least a polarizing plate and the retardation layer of the transfer laminate are opposed to each other,
a transfer step of transferring the transfer layered product onto the transferred object;
and a peeling step of peeling the peelable support layer from the transfer laminate transferred onto the transfer target.

An embodiment of the present disclosure provides a display device including the retardation film of the embodiment of the present disclosure or an optical member including a polarizing plate on the retardation film.

According to the embodiments of the present disclosure, it is possible to form a retardation layer with excellent vertical alignment and improved heat resistance, a liquid crystal composition with excellent coating properties, and a retardation with excellent vertical alignment and improved heat resistance. A retardation film having a layer and a method for producing the same, a laminate for transfer with excellent vertical alignment and improved heat resistance for transferring a retardation layer, an optical member having the retardation film and a method for producing the same, and a display Equipment can be provided.

FIG. 1 is a schematic cross-sectional view showing one embodiment of the 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 an embodiment of the transfer laminate. FIG. 5 is a schematic cross-sectional view showing an 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, examples, and the like of the present disclosure will be described with reference to the drawings and the like. However, the present disclosure can be implemented in many different aspects, and should not be construed as being limited to the descriptions of the embodiments, examples, and the like exemplified below. In addition, in order to make the description clearer, the drawings may schematically represent the width, thickness, shape, etc. of each part compared to the actual embodiment, but this is only an example, and the interpretation of the present disclosure It is not limited. In addition, in this specification and each figure, the same reference numerals may be given to the same elements as those described above with respect to the previous figures, and detailed description thereof may be omitted as appropriate. Also, for convenience of explanation, the terms "upper" and "lower" may be used, but the up-down direction may be reversed.
In this specification, when a configuration such as a member or a region is “above (or below)” another configuration such as another member or region, unless otherwise specified, This includes not only being directly above (or directly below) another structure, but also above (or below) another structure, i.e. above (or below) another structure and between another structure. Including when the element is included.

In the present specification, the orientation regulating force means an interaction that aligns the liquid crystalline component in the retardation layer in a specific direction.
In this specification, (meth)acryl represents acrylic and methacrylic, (meth)acrylate represents acrylate and methacrylate, and (meth)acryloyl represents acryloyl and methacryloyl.
Further, in this specification, the terms "plate", "sheet", and "film" are not distinguished from each other based only on the difference in names, and "film surface (plate surface, sheet surface)" A surface that is aligned with the plane direction of the target film-like member (plate-like member, sheet-like member) when the target film-like member (plate-like member, sheet-like member) is viewed as a whole and from a broad perspective. refers to

A. 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,
The side chain type liquid crystal polymer has a non-liquid crystalline structural unit having a structure represented by the following general formula (I) and an SP value of 9.25 (cal/cm ³ ) ^1/2 or more; and a liquid crystalline structural unit having a side chain containing a moiety,
A mass ratio of the side chain type liquid crystal polymer to the total mass of the side chain type liquid crystal polymer and the polymerizable liquid crystal compound is 2% by mass or more and 20% by mass or less.

（一般式（Ｉ）中、Ｒ^１は、水素原子又はメチル基を表し、Ｒ^２は、－（Ｃ_２Ｈ_４Ｏ）_ｎ－Ｒ^３、又は－Ｒ^４－Ｘ－Ｙ－Ｒ^５で表される基を表す。ｎは７以上１６以下の整数を表し、Ｒ^３は炭素数１以上３以下のアルキル基を表す。Ｒ^４は炭素数１以上２２以下のアルキレン基を表し、Ｒ^５は炭素数１以上９以下のアルキル基を表し、Ｒ^４及びＲ^５の少なくとも１つが炭素数３以上の直鎖構造を有する。Ｘは－Ｏ－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－、－Ｏ－ＣＨ_２－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＨ＝ＣＨ－Ｃ（＝Ｏ）－Ｏ－又は－Ｏ－Ｃ（＝Ｏ）－ＣＨ＝ＣＨ－で表される連結基を表し、Ｙは１，４－フェニレン基又は１，４－シクロヘキシレン基を表す。前記Ｙにおいて、１，４－フェニレン基は、１個又は隣接しない２個以上の－ＣＨ＝が－Ｎ＝によって置換されていてもよく、１，４－シクロヘキシレン基は、１個又は隣接しない２個以上の－ＣＨ_２－が－Ｏ－又は－Ｓ－によって置換されていてもよく、１，４－フェニレン基及び１，４－シクロヘキシレン基は、ハロゲン原子、シアノ基及びニトロ基から選ばれる少なくとも１種の置換基を有していてもよい。）

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents -(C ₂ H ₄ O) _n -R ³ or -R ⁴ -XY-R ⁵ n represents an integer of 7 to 16, R ³ represents an alkyl group having 1 to 3 carbon atoms, R ⁴ represents an alkylene group having 1 to 22 carbon atoms, and R ⁵ represents represents an alkyl group having 1 to 9 carbon atoms, and at least one of R ⁴ and R ⁵ has a straight chain structure having 3 or more carbon atoms, X represents -O-, -C(=O)-O-, -O -C(=O)-, -O-CH ₂ -, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -O-C(=O)- represents a linking group represented by CH=CH-, Y represents a 1,4-phenylene group or a 1,4-cyclohexylene group, and in Y, the number of 1,4-phenylene groups is one or two which are not adjacent; One or more -CH= may be substituted by -N=, and the 1,4-cyclohexylene group is a group in which one or two or more non-adjacent -CH ₂ - are substituted by -O- or -S- and the 1,4-phenylene group and 1,4-cyclohexylene group may have at least one substituent selected from halogen atoms, cyano groups and nitro groups.)

A positive C-type retardation film (positive C plate) is formed by forming a coating film of a liquid crystal composition on a substrate and heating it appropriately to align the liquid crystalline component in the liquid crystal composition perpendicularly to the substrate. Obtainable.
Conventional liquid crystal compositions, as shown in Comparative Examples 1 and 2 to be described later, have insufficient applicability to substrates, so that repelling may occur in the retardation layer or crystals may precipitate. Further, the vertical alignment property is also insufficient, and the vertical alignment property tends to be deteriorated by heating, so the heat resistance of the retardation layer is also insufficient. In a conventional liquid crystal composition, if the content of the liquid crystal polymer is increased in order to improve the vertical alignment, the vertical alignment is improved, but the content of the polymerizable liquid crystal compound is relatively decreased, so the retardation The cross-linking density of the layer becomes small, and the durability such as heat resistance of the retardation layer is further deteriorated.
On the other hand, the liquid crystal composition of the present disclosure contains the side chain type liquid crystal polymer, so that it is possible to form a retardation layer having excellent vertical alignment and improved heat resistance, and excellent coatability to the substrate. . The action of the liquid crystal composition of the present disclosure exerting such effects is partially unexplained, but is presumed as follows.
The liquid crystal composition of the present disclosure contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound as liquid crystalline components, and the side chain type liquid crystal polymer includes a liquid crystalline structural unit having a side chain containing a liquid crystalline portion. and a non-liquid crystalline structural unit having a structure represented by the general formula (I) and an SP value of 9.25 (cal/cm ³ ) ^1/2 or more. On the other hand, the substrate used for forming the retardation layer generally has polar groups on its surface. The present inventors have found a side having a non-liquid crystalline structural unit having a specific structure represented by the general formula (I) and having an SP value of 9.25 (cal/cm ³ ) ^1/2 or more By containing the chain-type liquid crystal polymer, the liquid crystal composition easily spreads on the substrate surface regardless of whether the surface of the substrate used for forming the retardation layer has a high polarity state or a low polarity state. I found out. The non-liquid crystalline structural unit has an SP value of 9.25 (cal/cm ³ ) ^1/2 or more and has polarity, and R ² in the general formula (I) is —(C ₂ H ₄ O ) _n —R ³ or —R ⁴ —X—Y—R ⁵ . When R ² in the general formula (I) is —(C ₂ H ₄ O) _n —R ³ , the SP value tends to increase due to —(C ₂ H ₄ O) _n —. The SP value of the structural unit can be 9.25 (cal/cm ³ ) ^1/2 or more. When R ² in the general formula (I) is —R ⁴ —X—Y—R ⁵ , by appropriately selecting and combining X and Y, the SP value can be increased. The SP value of the structural unit can be 9.25 (cal/cm ³ ) ^1/2 or more. In addition, by having a structure represented by —(C ₂ H ₄ O) _n —R ³ or a structure represented by —R ⁴ —X—Y—R ⁵ , the unit deriving the non-liquid crystalline structural unit Since the monomer is excellent in solubility and dispersibility, there is also an advantage that the side chain type liquid crystal polymer can be easily synthesized using the monomer. In addition, the structure represented by -(C ₂ H ₄ O) _n -R ³ and the structure represented by -R ⁴ -XY-R ⁵ are single bonds with a high degree of rotational freedom such as CC bonds. and has flexibility by including a chain structure having a certain length. Therefore, if there are even a few polar groups on the substrate surface, the non-liquid crystalline structural units can approach the polar groups on the substrate surface, and the liquid crystal composition is likely to wet and spread on the substrate surface. In addition, since the specific non-liquid crystalline structural unit has a flexible structure and thus easily moves in the coating film, in the coating film of the liquid crystal composition of the present disclosure, the specific non-liquid crystalline structural unit is By moving while adhering to the surface of the substrate, the entire side chain type liquid crystal polymer tends to be unevenly distributed near the surface of the substrate, and the liquid crystal composition tends to wet and spread on the substrate surface. Since the liquid crystal composition of the present disclosure easily wets and spreads on the substrate surface in this way, it is possible to suppress repelling of the substrate, and as a result, a retardation layer in which repelling and crystal precipitation are suppressed can be formed. .
In addition, the side chain type liquid crystal polymer used in the liquid crystal composition of the present disclosure has a structure represented by the general formula (I) and has an SP value of 9.25 (cal/cm ³ ) ^1/2 or more. By having the non-liquid crystalline structural unit, the side chain of the liquid crystalline structural unit in the side chain type liquid crystal polymer is considered to be easily aligned vertically, and the coating film of the liquid crystal composition of the present disclosure is appropriately applied When heated, the side chain type liquid crystal polymer is unevenly distributed near the surface of the substrate, and the side chains of the liquid crystalline structural units are oriented perpendicularly to the substrate, and the side chains of the vertically oriented liquid crystalline constitutional units are It is thought to induce vertical alignment of the polymerizable liquid crystal compound. In the coating film of the liquid crystal composition of the present disclosure, it is believed that the side chains of the liquid crystalline constitutional units are aligned vertically from the vicinity of the surface of the substrate, and the liquid crystal polymer is also present in regions distant from the surface of the substrate. It is considered that the polymerizable liquid crystal compound is more likely to be vertically aligned than when it is uniformly dispersed, and furthermore, bleeding of the liquid crystal polymer and fluctuation of the molecules are less likely to occur, so that the vertically aligned state is likely to be maintained. Since the liquid crystal polymer tends to disperse uniformly in the conventional liquid crystal composition coating film, it is assumed that the liquid crystal polymer tends to bleed from the coating film surface and molecular fluctuations are likely to occur, resulting in deterioration of the vertical alignment. be done.
Furthermore, in the coating film of the liquid crystal composition of the present disclosure, the side chain type liquid crystal polymer is unevenly distributed near the surface of the substrate, so that the density of the polymerizable liquid crystal compound is high in a region away from the surface of the substrate. Therefore, it is presumed that the density of the crosslinked structure in the retardation layer formed by the polymerizable liquid crystal compound also increases. It is believed that this improves the durability of the retardation layer, makes it easier to maintain vertical alignment even in a high-temperature, high-humidity environment, and suppresses fluctuations in retardation due to heating.
In addition, since the liquid crystal composition of the present disclosure contains the side chain type liquid crystal polymer, the vertical alignment is excellent and the vertical alignment after heating is easily maintained. To form a retardation layer excellent in vertical alignment and heat resistance even in a small amount of 2% by mass or more and 20% by mass or less with respect to 100% by mass of the total mass of the side chain type liquid crystal polymer and the polymerizable liquid crystal compound. can be done. In the liquid crystal composition of the present disclosure, since the content of the liquid crystal polymer is small, the content of the polymerizable liquid crystal compound can be increased, thereby further improving the heat resistance and the like of the retardation layer. In addition, since the liquid crystal composition of the present disclosure contains a small amount of the liquid crystal polymer, it is possible to reduce the thickness of the retardation layer.

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 within a range that does not impair the effect. be. Each component constituting the liquid crystal composition will be described in order below.

1. Side-chain type liquid crystal polymer In the liquid crystal composition of the present disclosure, the side-chain type liquid crystal polymer has a structure represented by the general formula (I) and has an SP value of 9.25 (cal/cm ³ ) ^1/2 . It has the above non-liquid crystalline structural unit and a liquid crystalline structural unit having a side chain containing a liquid crystalline portion, and can exhibit vertical alignment.

(1) A non-liquid crystal structural unit having a structure represented by general formula (I) In the non-liquid crystal structural unit having a structure represented by general formula (I), the side chain R ² is -(C ₂ H ₄ O) _n —R ³ or a group represented by —R ⁴ —X—Y—R ⁵ ;
In —(C ₂ H ₄ O) _n —R ³ , n represents an integer of 7 or more and 16 or less, and R ³ represents an alkyl group having 1 or more and 3 or less carbon atoms. Among them, the side chain type liquid crystal polymer tends to be unevenly distributed near the surface of the substrate, and from the viewpoint of improving the applicability of the liquid crystal composition and the vertical alignment property and heat resistance of the retardation layer, n is 9 or more and 16 or less. is preferred, and R ³ is preferably a methyl group or an ethyl group.
In —R ⁴ —XY-R ⁵ , R ⁴ represents an alkylene group having 1 to 22 carbon atoms, R ⁵ represents an alkyl group having 1 to 9 carbon atoms, and at least one of R ⁴ and R ⁵ One has a linear structure with 3 or more carbon atoms. X is -O-, -C(=O)-O-, -OC(=O)-, -O-CH ₂ -, -CH=CH-, -C≡C-, -CH=CH- represents a linking group represented by C(=O)-O- or -OC(=O)-CH=CH-, and Y represents a 1,4-phenylene group or a 1,4-cyclohexylene group; In Y, the 1,4-phenylene group may be substituted with one or two or more non-adjacent -CH= by -N=, and the 1,4-cyclohexylene group may be one or non-adjacent. Two or more —CH ₂ — may be substituted by —O— or —S—, and the 1,4-phenylene group and 1,4-cyclohexylene group are selected from halogen atoms, cyano groups and nitro groups. may have at least one substituent group.
The alkylene group for R ⁴ and the alkyl group for R ⁵ may be linear or branched as long as at least one of R ⁴ and R ⁵ has a linear structure with 3 or more carbon atoms. By improving the flexibility of the side chain of the structural unit, the side chain type liquid crystal polymer becomes easier to be unevenly distributed near the surface of the substrate, improving the applicability of the liquid crystal composition, and the vertical alignment and heat resistance of the retardation layer. From the point of view of improvement, it is preferably straight chain. Further, it is preferable that the number of carbon atoms of R ⁴ is 11 or more and 22 or less and the number of carbon atoms of R ⁵ is 3 or more and 9 or less, since the flexibility of the side chain is easily improved.
X is -O-, -C(=O)-O, because the SP value of the non-liquid crystalline structural unit can be easily made 9.25 (cal/cm ³ ) ^1/2 or more and the synthesis is easy. - or -OC(=O)- is preferred.
Further, when Y is a 1,4-phenylene group in which one or two or more non-adjacent -CH= are substituted by -N=, one or two or more non-adjacent -CH ₂ - are - When it is a 1,4-cyclohexylene group substituted by O- or -S- and when it has at least one substituent selected from a halogen atom, a cyano group and a nitro group, the non-liquid crystalline structural unit Since the solubility or dispersibility of the monomer that induces is easily improved, the side chain type liquid crystal polymer is easily synthesized, and the SP value of the non-liquid crystalline structural unit is easily increased, resulting in a liquid crystal composition It is preferable in terms of easily improving the applicability and vertical alignment of the product. Among the halogen atoms, I, Br, Cl, and F are preferable from the viewpoint of improving the SP value, and the order of I, Br, Cl, and F is preferable from the viewpoint of further improving the SP value.

The SP value of the non-liquid crystal structural unit having the structure represented by the general formula (I) is not particularly limited as long as it is 9.25 (cal/cm ³ ) ^1/2 or more. From the viewpoint of properties, it is preferably 9.29 (cal/cm ³ ) ^1/2 or more, more preferably 9.66 (cal/cm ³ ) ^1/2 or more.
In addition, the SP value in the present disclosure refers to the SP value calculated from the chemical structure using the Fedors method. The non-liquid crystalline structural unit has an SP value of at least the lower limit, so that it has a high affinity with the substrate, improves the applicability of the liquid crystal composition, and improves the vertical alignment property and heat resistance of the retardation layer. can do.
On the other hand, the SP value of the non-liquid crystal structural unit is not particularly limited, but can be, for example, 11.0 (cal/cm ³ ) ^1/2 or less.

(2) Liquid crystalline structural unit The liquid crystalline structural unit has a side chain containing a liquid crystalline portion, that is, a portion exhibiting liquid crystallinity. The liquid crystalline structural unit is preferably a structural unit containing a mesogen exhibiting liquid crystallinity in a side chain. The liquid crystalline structural unit is preferably a structural unit derived from a liquid crystalline compound in which a polymerizable group is bonded to a mesogenic group via a spacer. In the present disclosure, the mesogen refers to a highly rigid site that exhibits liquid crystallinity, for example, has two or more ring structures, preferably three or more ring structures, and the ring structures are connected by direct bonds. or a partial structure in which the ring structure is linked via 1 to 3 atoms. By having such a portion exhibiting liquid crystallinity in the side chain, the constitutional unit exhibiting liquid crystallinity is easily vertically aligned.
The ring structure may be an aromatic ring such as benzene, naphthalene or anthracene, or a cyclic aliphatic hydrocarbon such as cyclopentyl or cyclohexyl.
Further, when the ring structure is linked via one to three atoms, the structure of the linking portion includes -O-, -S-, -OC(=O)-, -C(= O)-O-, -OC(=O)-O-, -NR-C(=O)-, -C(=O)-NR-, -OC(=O)-NR-, -NR-C(=O)-O-, -NR-C(=O)-NR-, -O-NR-, or -NR-O- (R is a hydrogen atom or a hydrocarbon group) and the like. .
Among them, the mesogen is preferably a rod-like mesogen in which the ring structures are connected in the para position in the case of benzene and in the 2 and 6 positions in the case of naphthalene so that the ring structures are connected in a rod shape.

Further, when the liquid crystalline structural unit is a structural unit containing a mesogen exhibiting liquid crystallinity in a side chain, the end of the side chain of the structural unit should be a polar group or have an alkyl group from the viewpoint of vertical alignment. is preferred. Specific examples of such polar groups 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 ^' ', or -OR ^' '(R' is a hydrogen atom or a hydrocarbon group, R'^' is alkyl group) and the like.
In the embodiment of the present disclosure, one type of liquid crystalline structural unit can be used alone, or two or more types can be used in combination.

The liquid crystalline structural unit is preferably a structural unit derived from a monomer having an ethylenic double bond-containing group polymerizable with the monomer from which the non-liquid crystalline structural unit is derived. Examples of monomers having such an ethylenic double bond-containing group include derivatives such as (meth)acrylate, styrene, (meth)acrylamide, maleimide, vinyl ether, and vinyl ester. From the viewpoint of vertical alignment, the liquid crystalline structural unit is preferably a structural unit derived from a (meth)acrylic acid ester derivative.

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

（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－、－Ｏ－Ｃ（＝Ｏ）－、若しくは－Ｃ（＝Ｏ）－Ｏ－で表される連結基を、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^１４、－Ｃ（＝Ｏ）－ＯＲ^１４、－ＯＨ、－ＳＨ、－ＣＨＯ、－ＳＯ_３Ｈ、－ＮＲ^１４ _２、－Ｒ^１５、又は－ＯＲ^１５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し、Ｒ^１５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 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 a linking group represented by -O-, -OC(=O)-, or -C(=O)-O-, and Ar ² has a substituent represents an arylene group having 6 or more and 10 or less carbon atoms which may be substituted, and a plurality of L ² and Ar ² may be the same or different, and R ¹³ is —F, —Cl, —CN; , -OCF ₃ , -OCF ₂ H, -NCO, -NCS, -NO ₂ , -NHC(=O)-R ¹⁴ , -C(=O)-OR ¹⁴ , -OH, -SH, -CHO, - SO ₃ H, —NR ¹⁴ ₂ , —R ¹⁵ or —OR ¹⁵ , R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁵ represents 1 to 6 carbon atoms represents an alkyl group of a is an integer of 2 or more and 4 or less, and m and m' are each independently an integer 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 standpoint of vertical alignment, m and m' are preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less.

Examples of the optionally substituted arylene group having 6 to 10 carbon atoms in Ar ² include a phenylene group and a naphthylene group, among which a phenylene group is more preferable. Examples of substituents other than R ¹³ that the arylene group may have include alkyl groups having 1 to 5 carbon atoms, and halogen atoms such as fluorine, chlorine, and bromine atoms.

R ¹⁴ in R ¹³ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹⁵ in R ¹³ is an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms.

Preferred specific examples of the liquid crystalline structural unit represented by general formula (II) include those represented by the following chemical formulas (II-1), (II-2) and (II-3). but not limited to these.

In an embodiment of the present disclosure, the side chain type liquid crystal polymer may be a block copolymer having a block portion composed of the non-liquid crystalline structural unit and a block portion composed of the liquid crystalline structural unit. It may be a random copolymer in which structural units and liquid crystalline structural units are arranged irregularly. In the present embodiment, a random copolymer is preferable from the viewpoint of improving the vertical alignment property of the polymerizable liquid crystal compound and the in-plane uniformity of the retardation value and making the retardation layer less crackable.

The ratio of the non-liquid crystal structural units in the side chain type liquid crystal polymer is not particularly limited, but is preferably 20 mol % or more and 80 mol % or less in 100 mol % of all structural units. In particular, from the viewpoint of vertical alignment and heat resistance, the content is preferably 25 mol % or more, more preferably 30 mol % or more. On the other hand, from the viewpoint of sufficiently containing the liquid crystalline structural units, the proportion of the non-liquid crystalline structural units is preferably 50 mol % or less, more preferably 40 mol % or less, and more preferably 35 mol %. The following are even more preferable.
Further, in the side-chain type liquid crystal polymer, the ratio of the liquid crystalline structural unit to 100 mol % of all structural units is preferably 20 mol % or more and 80 mol % or less from the viewpoint of vertical alignment and heat resistance. , more preferably 50 mol % or more and 75 mol % or less, even more preferably 60 mol % or more and 70 mol % or less, and particularly preferably 65 mol % or more and 70 mol % or less.
The content ratio of each constitutional unit in the copolymer can be calculated from the integrated value obtained by ¹ H-NMR measurement.

(3) Other structural units In the embodiment of the present disclosure, the copolymer includes the non-liquid crystalline structural unit and the liquid crystalline structural unit in addition to the non-liquid crystalline structural unit, as long as the effects of the present embodiment are not impaired. It may have another structural unit that does not fall under either the unit or the liquid crystalline structural unit. By including the other structural unit in the copolymer, for example, solvent solubility, heat resistance, reactivity, etc. can be enhanced.
These other structural units may be of one type or two or more types. The content of the other structural unit is preferably 30 mol% or less, more preferably 20 mol% or less, and 10 mol% or less with respect to 100 mol% of the total copolymer. Even more preferably, it is most preferably 5 mol % or less. If the content ratio of the other structural unit is high, the content ratio of the liquid crystalline structural unit and the non-liquid crystalline structural unit becomes relatively small, and it may be difficult to obtain the effects of the embodiments of the present disclosure. .

In the embodiment of the present disclosure, the mass average molecular weight Mw of the side chain type liquid crystal polymer is not particularly limited, but it is preferably in the range of 500 to 60000, more preferably in the range of 3000 to 50000, More preferably, it falls within the range of 5,000 or more and 40,000 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.

In addition, the said mass average molecular weight Mw is the value measured by GPC (gel permeation chromatography). The measurement was performed using HLC-8120GPC manufactured by Tosoh Corporation, the elution solvent was N-methylpyrrolidone to which 0.01 mol/liter of lithium bromide was added, and the polystyrene standard for the calibration curve was Mw 377400, 210500, 96000, 50400. , 206500, 10850, 5460, 2930, 1300, 580 (Easi PS-2 series manufactured by Polymer Laboratories) and Mw1090000 (manufactured by Tosoh Corporation), and the measurement column is TSK-GEL ALPHA-M × 2 (Tosoh Co., Ltd.).

The side chain type liquid crystal polymer may be used singly or in combination of two or more.

In the present embodiment, when the total mass of the side chain type liquid crystal polymer and the polymerizable liquid crystal compound is 100% by mass, the mass ratio of the side chain type liquid crystal polymer is 2% by mass or more and 20% by mass or less. Even if the content of the side chain type liquid crystal polymer is small, it is possible to form a retardation layer excellent in vertical alignment and heat resistance. In a more preferred embodiment, the mass ratio of the side-chain type liquid crystal polymer can be 2% by mass or more and 15% by mass or less, and further can be 2% by mass or more and 10% by mass or less. By setting the content of the side chain type liquid crystal polymer to the above upper limit or less, the content of the polymerizable liquid crystal compound can be increased, thereby improving durability such as heat resistance of the retardation layer. can. On the other hand, by setting the content ratio of the side chain type liquid crystal polymer to the above lower limit or more, the applicability of the liquid crystal composition and the vertical alignment property of the retardation layer can be improved. From the same point of view, the content of the side chain type liquid crystal polymer in 100 parts by mass of the solid content of the liquid crystal composition of the present disclosure can be 1 part by mass or more and 20 parts by mass or less. , 1 part by mass or more and 15 parts by mass or less, or 2 parts by mass or more and 10 parts by mass or less.
In the present disclosure, the solid content refers to all components other than the solvent, and for example, even if the polymerizable liquid crystal compound described later is liquid, it is included in the solid content.

(4) Method for producing a side chain type liquid crystal polymer In the present embodiment, the method for producing the side chain type liquid crystal polymer is not particularly limited. It may be mixed with a monomer from which a structural unit is derived in a desired ratio, and polymerized by a known polymerization means so as to obtain a desired average molecular weight.
In the case of forming a block copolymer, for example, after polymerizing a monomer that induces the non-liquid crystalline structural unit and a monomer that induces the liquid crystalline structural unit by a known polymerization means, Each of the obtained polymers may be linked, and either the monomer that induces the non-liquid crystalline structural unit or the monomer that induces the liquid crystalline structural unit is polymerized by a known polymerization means. After that, the other monomer is added to further polymerize, and the like.
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, or the like can be used. In the present embodiment, among others, it is possible to use a method in which the polymerization proceeds in a living manner, such as group transfer polymerization (GTP) disclosed in "J. Am. Chem. Soc." 105, 5706 (1983). preferable. According to this method, the molecular weight, the molecular weight distribution, etc. can be easily controlled within the desired ranges, so that the properties of the resulting side chain type liquid crystal polymer can be made uniform.

In the present disclosure, the structures of side-chain liquid crystalline polymers are analyzed by nuclear magnetic resonance spectroscopy (NMR), pyrolysis gas chromatography-mass spectrometry (Py-GC-MS), and matrix-assisted laser desorption ionization time-of-flight mass spectrometry. (MALDI-TOFMS) can be combined for analysis.

2. Polymerizable Liquid Crystal Compound In the embodiment of the present disclosure, the polymerizable liquid crystal compound can be appropriately selected from conventionally known compounds and used. In the present embodiment, in combination with the side-chain type liquid crystal polymer, it is preferable to use a polymerizable liquid crystal compound having a polymerizable group at at least one end of the mesogen from the viewpoint of vertical alignment and durability of the retardation layer. , and a polymerizable liquid crystal compound having polymerizable groups at both ends of the mesogen.
The mesogen possessed by the polymerizable liquid crystal compound can be the same as the mesogen possessed by the liquid crystalline structural unit in the side-chain type liquid crystal polymer.
Examples of the polymerizable group possessed by the polymerizable liquid crystal compound include a cyclic ether-containing group such as an oxirane ring and an oxetane ring, and an ethylenic double bond-containing group. From the point of view, it is preferably an ethylenic double bond-containing group. Examples of the ethylenic double bond-containing group include a vinyl group, an allyl group, a (meth)acryloyl group, etc. Among them, a (meth)acryloyl group is preferable.

In the present embodiment, the polymerizable liquid crystal compound is selected from compounds represented by the following general formula (III) and compounds represented by the following general formula (IV) from the viewpoint of vertical alignment. More than one species of compound is 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^１４ _２、－Ｒ^２５、又は－ＯＲ^２５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 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 represents an arylene group having 6 or more and 10 or less carbon atoms that may be substituted, and a plurality of L ³ and Ar ³ may be the same or different, and 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 ¹⁴ ₂ , —R ²⁵ or —OR ²⁵ , R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ²⁵ represents 1 to 6 carbon atoms is an integer of 2 or more and 4 or less, and p and p' are each independently an integer 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 each independently a hydrogen atom or a methyl group, R ³³ is —(CH ₂ ) _q — or —(C ₂ H ₄ O) _q′ — R ³⁴ represents a group represented by —(CH ₂ ) _r — or —(OC ₂ H ₄ ) _r′ —, L ⁴ is a direct bond, or —O—, -O-C(=O)- or -C(=O)-O-, and Ar ⁴ is an arylene having 6 to 10 carbon atoms which may have a substituent L ⁴ and Ar ⁴ may be the same or different, c is an integer of 2 or more and 4 or less, q, q′, r and r′ are each independently 2 or more and 10 or less. is an integer of

p and p' in general formula (III) and q, q', r and r' in general formula (IV) are preferably 2 or more and 8 or less, and 2 or more and 6 or less from the viewpoint of vertical alignment. is more preferable, and 2 or more and 5 or less is even more preferable.
L ³ and L ⁴ can be the same as L ² in the general formula (II).
Ar ³ and Ar ⁴ can be the same as Ar ² in the general formula (II).

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

Suitable 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 this embodiment, the polymerizable liquid crystal compound can be used singly or in combination of two or more.
In the liquid crystal composition of the present disclosure, the content of the polymerizable liquid crystal compound can be 75 parts by mass or more with respect to 100 parts by mass of the solid content of the liquid crystal composition. It can be at least 85 parts by mass, furthermore at least 90 parts by mass. Durability such as heat resistance of the retardation layer can be improved by setting the content ratio of the polymerizable liquid crystal compound to the above lower limit or more. On the other hand, the content ratio of the polymerizable liquid crystal compound is, from the viewpoint of sufficiently containing the side chain type liquid crystal polymer and improving the vertical alignment property and heat resistance, relative to the solid content of 100 parts by mass of the liquid crystal composition, It is preferably 98 parts by mass or less, and may be 95 parts by mass or less.

3. Photopolymerization Initiator In the present embodiment, the photopolymerization initiator can be appropriately selected from conventionally known substances and used. Specific examples of such photopolymerization initiators include aromatic ketones including thioxanthone, α-aminoalkylphenones, α-hydroxyketones, acylphosphine oxides, oxime esters, and aromatic oniums. Preferred examples include salts, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime 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 acylphosphine oxide-based polymerization initiators, α-aminoalkylphenone-based polymerization initiators, α-hydroxyketone-based polymerization initiators, and oxime ester-based polymerization initiators. preferable.

Acylphosphine oxide-based polymerization initiators include, for example, bis(2,4,6-trimethylbenzoyl)-phenyl-phosphine oxide (eg, trade name: Irgacure 819, manufactured by BASF), 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.

Examples of α-aminoalkylphenone-based polymerization initiators include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (eg 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] -1-[4-(4-morpholinyl)phenyl]-1-butanone (Irgacure 379EG, manufactured by BASF) and the like.

Examples of α-hydroxyketone-based polymerization initiators include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane -1-one (e.g., trade name: Irgacure 127, manufactured by BASF, etc.), 2-hydroxy-4'-hydroxyethoxy-2-methylpropiophenone (e.g., trade name: Irgacure 2959, manufactured by BASF, etc.), 1-hydroxy-cyclohexyl-phenyl-ketone (e.g., 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.).

Examples of oxime ester polymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(o-acetyloxime) (trade name: manufactured by Irgacure OXE-04ASF), methanone, ethanone, 1 -[9-ethyl-6-(1,3-dioxolane,4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (trade name ADEKA OPT-N- 1919, manufactured by ADEKA) and the like.

In this embodiment, the photopolymerization initiator can be used singly or in combination of two or more.
In the present embodiment, the content of the photopolymerization initiator is 0.1 parts 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 promoting 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 Components The liquid crystal composition of the present embodiment may further contain other components as long as the effects are not impaired. Specifically, it may contain a leveling agent, a polymerization inhibitor, an antioxidant, a light stabilizer, and a solvent from the viewpoint of coating properties. For these materials, 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, Megafac series manufactured by DIC Corporation described in JP-A-2010-122325, TSF series manufactured by Momentive Performance Materials Japan, and NEOS Co., Ltd. Futergent series and the like. When a leveling agent is used in this embodiment, the content is preferably 0.001 parts 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.

From the viewpoint of coating properties, the liquid crystal composition of the present embodiment may contain a solvent, if necessary. 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); halogenated alkyl 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, and propanol. Alcohol-based solvents and the like are included. In this 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 positive C-type retardation layer because the side chain type liquid crystal polymer is easily vertically aligned, and accordingly the polymerizable liquid crystal compound is easily vertically aligned.

B. Retardation film The retardation film of the present disclosure is a retardation film having a retardation layer,
The retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, the side chain type liquid crystal polymer has a structure represented by the general formula (I), and has an SP value of 9.0. 25 (cal/cm ³ ) ^1/2 or more having a non-liquid crystalline structural unit and a liquid crystalline structural unit having a side chain containing a liquid crystalline portion, the side chain type liquid crystalline polymer and the polymerizable liquid crystal compound The retardation film includes a cured product of a liquid crystal composition, wherein the side chain type liquid crystal polymer has a mass ratio of 2% by mass or more and 20% by mass or less with respect to the total mass of the above.

In the retardation film of the present disclosure, since the retardation layer contains a cured product of the liquid crystal composition of the present disclosure, the retardation layer has excellent vertical alignment properties and improved heat resistance, and the retardation layer cissing and precipitation of crystals are suppressed. In addition, the retardation layer containing the cured product of the liquid crystal composition of the present disclosure is typically composed of the cured product of the liquid crystal composition of the present disclosure, and contains other configurations as long as the effects of the present disclosure are not impaired. It's okay to be
The layer structure of the retardation film will be described with reference to the drawings. 1, 2 and 3 each show one embodiment of the retardation film of the present disclosure. The retardation film 10 shown in the example of FIG. 1 is a retardation film in which the substrate 2 and the retardation layer 1 are laminated in this order, and the substrate 2 adjusts the surface free energy on the substrate 3. It has a surface adjustment layer 4 for
The retardation film 10' shown in the example of FIG. 2 is a retardation film consisting of the retardation layer 1 only.
The retardation film 10 ″ shown in the example of FIG. 3 is a retardation film in which a substrate 2 ′ and a retardation layer 1 are laminated in this order. have
As described above, the liquid crystal composition of the present disclosure is capable of exhibiting vertical alignment without using an alignment film because the liquid crystal component is easily vertically aligned.

1. Retardation Layer The retardation layer 1 of the embodiment of the present disclosure has a structure represented by the general formula (I) and has an SP value of 9.25 (cal/cm ³ ) ^1/2 or more. Non-liquid crystal A cured product of a liquid crystal composition containing a polymerizable liquid crystal compound and a side chain type liquid crystal polymer having a liquid crystalline structural unit and a liquid crystalline structural unit having a side chain containing a liquid crystalline portion.
Here, a non-liquid crystalline structural unit having a structure represented by the general formula (I) and having an SP value of 9.25 (cal/cm ³ ) ^1/2 or more and the liquid crystalline structural unit are combined. Since the side-chain type liquid crystal polymer and the polymerizable liquid crystal compound may be the same as those described in the liquid crystal composition of the embodiment of the present disclosure, description thereof will be omitted here.

The retardation layer is preferably cured in a state in which the liquid crystalline constitutional units of the side chain type liquid crystal polymer and the polymerizable liquid crystal compound are vertically aligned. A 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 such a structure in which at least a part of the polymerizable groups of the polymerizable liquid crystal compound is polymerized is included, the retardation layer of the present embodiment has improved durability such as heat resistance.

The liquid crystalline structural unit contained in the retardation layer is nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), gas chromatogram mass spectroscopy (GC-MS), X-ray photoelectron spectroscopy (XPS), It can be confirmed by using one or more known analytical methods capable of obtaining molecular structure information, such as time-of-flight secondary ion mass spectrometry (TOF-SIMS).
In addition, the fact that the polymerizable liquid crystal compound is vertically aligned can be confirmed by measuring the phase difference with an automatic birefringence measuring device (for example, manufactured by Oji Scientific Instruments Co., Ltd., trade name: KOBRA-WR). .

The phase difference can be measured by an automatic birefringence measuring device (for example, manufactured by Oji Scientific Instruments Co., Ltd., trade name: KOBRA-WR). The anisotropy that increases the retardation of the retardation layer can be confirmed from the chart of the optical retardation and the incident angle of the measurement light when the measurement light is incident on the surface of the retardation layer perpendicularly or obliquely.
In terms of vertical alignment, the retardation layer of the embodiment of the present disclosure preferably has a thickness retardation Rth (550) of less than -80 nm at a measurement wavelength of 550 nm, more preferably less than -100 nm. Even more preferably less than -110 nm.

Further, in the retardation layer of the embodiment of the present disclosure, when visually observed under crossed Nicols, in the range of 100 mm × 100 mm, the total of the parts observed as white is 3% or less. and from the point of suppressing unevenness in the retardation layer, and it is more preferably 1% or less.

Further, the retardation layer of the embodiment of the present disclosure can have a retardation variation rate of less than 15% after heating at 100° C. for 60 minutes. The phase difference variation rate is calculated by the following formula.
Retardation change rate after heating (%) = {(Rth before heating-Rth after heating)/Rth before heating} x 100
In the above formula, Rth represents the thickness retardation Rth (550) at the measurement wavelength of 550 nm.

Further, the retardation layer includes a side chain type liquid crystal polymer contained in the liquid crystal composition of the embodiment 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 sampling material from the layer and analyzing it. As analytical methods, NMR, IR, GC-MS, XPS, TOF-SIMS and combinations thereof can be applied.

The retardation layer may contain other components such as a photopolymerization initiator, a leveling agent, a polymerization inhibitor, an antioxidant, and a light stabilizer. A component such as a photopolymerization initiator, which may be completely decomposed when irradiated with light for reacting the polymerizable group of the polymerizable liquid crystal compound, may not be contained in the retardation layer. be.

The thickness of the retardation layer may be appropriately set depending on the application. Among them, the thickness 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. Substrate The retardation film of the present disclosure may have a substrate for supporting the retardation layer, that is, may have a substrate and the retardation layer on the substrate. . The substrate has a surface free energy of 30 mJ/m ² on the side of the retardation layer because the substrate easily improves the vertical orientation and heat resistance of the retardation layer and further suppresses repelling and crystal precipitation of the retardation layer. It is preferable that it is above. When using the preferable substrate, it is preferable that the substrate and the retardation layer are adjacent to each other. Moreover, the surface free energy of the substrate is preferably within the preferred range when forming the liquid crystal composition of the present disclosure. When the surface free energy of the substrate is 30 mJ/m ² or more, the applicability of the liquid crystal composition of the present disclosure can be improved, and the vertical alignment property and heat resistance of the retardation layer can be improved.
The surface free energy of the retardation layer-side surface of the substrate is preferably 35 mJ/m ² or more from the viewpoint of easily improving the applicability of the liquid crystal composition and the vertical alignment and heat resistance of the retardation layer. more preferred. On the other hand, the surface free energy of the retardation layer side surface of the substrate is not particularly limited, but can be, for example, 80 mJ/m ² or less, and may be 70 mJ/m ² or less.

In the present disclosure, the surface free energy of the substrate is calculated by measuring the contact angles of n-hexadecane, methylene iodide, and pure water on the surface of the substrate with a contact angle meter, and from the measured values and Kitazaki-Hata theory. can do. As the contact angle meter, for example, the DropMaster series manufactured by Kyowa Interface Science Co., Ltd. can be preferably used.

The surface free energy of the substrate can be adjusted by, for example, the material forming the surface of the substrate, the manufacturing conditions of the substrate, the surface treatment of the substrate, and the like. Among them, it is preferable that the substrate has a polar group on the surface because it is easy to adjust the surface free energy to 30 mJ/m ² or more. It preferably has at least one polar group selected from the group consisting of groups, fluorine-containing groups, sulfur atom-containing groups, lactone skeleton-containing groups, and acetal structure-containing groups.
Further, for example, when the surface of the substrate is composed of a material containing a cured product of an ionizing radiation-curable resin composition, when curing the ionizing radiation-curable resin composition, the The surface free energy can be increased by curing with light irradiation. In order to increase the surface free energy, the oxygen concentration is preferably 1% by volume or more, more preferably 8% by volume or more.
Moreover, the surface free energy can be adjusted by adding an appropriate kind and amount of leveling agent to the material forming the surface of the substrate. As a leveling agent for increasing the surface free energy, for example, an oligomer containing a fluorine atom and a lipophilic group can be preferably used. Preferable leveling agents include, for example, MEGAFACE series manufactured by DIC Corporation. The content of the leveling agent is adjusted as appropriate and is not particularly limited, but is preferably 0.01% by mass or more and 0.2% by mass or less in the total solid content of the material constituting the surface of the substrate. It is more preferably 0.03% by mass or more and 0.1% by mass or less.
The surface free energy of the substrate can also be increased by subjecting the surface of the substrate to surface treatment such as corona treatment or plasma treatment.

The substrate used for the retardation film of the present disclosure preferably has a surface free energy within the preferred range described above and is preferably used by appropriately selecting it. It may have a multi-layer structure in which layers are laminated.
As the substrate, for example, (i) one consisting of only a base material, (ii) a base material, and a surface adjustment layer for adjusting the surface free energy on the surface of the base material on the retardation layer side. (iii) a substrate and an alignment film on the surface of the substrate on the retardation layer side; (iv) an alignment film. Among them, the range of material selection is wide, and the surface free energy of the substrate can be easily adjusted to a desired value. It is preferable to have the surface adjustment layer.
In addition, when the substrate does not have an alignment film, means for exerting an alignment regulating force may be attached to the surface of the substrate on the side of the retardation layer.
In addition, the substrate may further have other layers different from the substrate, the surface adjustment layer, or the alignment film within a range that does not impair the effects of the present disclosure.

(1) Substrate Examples of the substrate include glass substrates, metal foils, and resin substrates. Above all, the substrate preferably has transparency, and can be appropriately selected from conventionally known transparent substrates. Examples of transparent substrates include glass substrates, acetylcellulose resins such as triacetylcellulose, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polylactic acid, polypropylene, polyethylene, polymethylpentene, and the like. It is formed using resins such as olefin resin, acrylic resin, polyurethane resin, polyethersulfone, polycarbonate, polysulfone, polyether, polyetherketone, acrylonitrile, methacrylonitrile, cycloolefin polymer, and cycloolefin copolymer. and a transparent resin substrate.

As the base material used for the substrate consisting only of the base material (i), a curable resin composition used for the surface adjustment layer described later is used because it is easy to set the surface free energy to 30 mJ/m ² or more. is preferably a substrate containing a cured product of the above, and more preferably a substrate comprising a cured product of the curable resin composition.

The transparent substrate preferably has a transmittance of 80% or more, more preferably 90% or more, in the visible light region. Here, the transmittance of the transparent base material can be measured according to JIS K7361-1 (Plastics—Testing method for total light transmittance of transparent materials).

When the retardation layer is formed by the roll-to-roll method, the substrate is preferably a flexible material that can be wound into a roll.
Examples of such flexible materials include cellulose derivatives, norbornene-based polymers, cycloolefin-based polymers, polymethyl methacrylate, polyvinyl alcohol, polyimides, polyarylates, polyethylene terephthalate, polysulfones, polyethersulfones, amorphous polyolefins, modified acrylic polymers, and polystyrene. , epoxy resins, polycarbonates, and polyesters. Among them, it is preferable to use a cellulose derivative or polyethylene terephthalate in the present embodiment. This is because the cellulose derivative is particularly excellent in optical isotropy, and therefore can be made excellent in optical properties. Moreover, polyethylene terephthalate is preferable because of its high transparency and excellent mechanical properties.

The thickness of the substrate can be appropriately adjusted according to the use of the retardation film, and is not particularly limited as long as it is within a range in which necessary self-supporting properties can be imparted. is within.
Above all, the thickness of the substrate is preferably in the range of 25 μm or more and 125 μm or less, and more preferably in the range of 30 μm or more and 100 μm or less. If the thickness is greater than the above range, for example, when a long retardation film is formed and then cut to form a single-sheet retardation film, processing waste increases or the cutting blade wears. This is because the

(2) Surface adjustment layer The surface adjustment layer can be used by appropriately selecting one having a desired surface free energy, and is not particularly limited. Ether bond, hydroxyl group, amino group, cyano group, carboxyl group, carbonyl group, fluorine-containing group, sulfur atom-containing group, lactone skeleton-containing group, acetal structure from the viewpoint of improving vertical orientation and heat resistance It is preferable to have at least one polar group selected from the group consisting of groups on the surface.
In addition, the surface adjustment layer can easily adjust the surface free energy, has excellent mechanical strength and moldability, and has good leveling property and transferability. It is preferable to contain.
Examples of the curable resin include those containing at least one of a thermosetting resin and an ionizing radiation curable resin. The thermosetting resin includes, for example, a two-liquid curing urethane resin system composed of a polyol compound and an isocyanate compound, an epoxy resin system, and the like. Examples of ionizing radiation-curable resins include (meth)acrylate-based, epoxy-based, and oxetane-based ionizing radiation-curable resins. Incidentally, ionizing radiation means electromagnetic waves or charged particles having energy capable of polymerizing and curing molecules, for example, all ultraviolet rays (UV-A, UV-B, UV-C), visible rays, gamma rays , X-rays, electron beams, and the like.
The curable resin composition used for forming the surface adjustment layer is preferably an ionizing radiation-curable resin composition containing an ionizing radiation-curable resin, from the viewpoint of excellent moldability and mechanical strength.

Among the ionizing radiation-curable resins, compounds having ethylenically unsaturated bonds such as (meth)acryloyl groups, vinyl groups, and allyl groups are preferably used because of their excellent moldability and mechanical strength. A (meth)acrylate having a (meth)acryloyl group and a compound having a vinyl group are preferably used. Here, "excellent moldability" means that a desired shape can be molded with high accuracy.
Among (meth)acrylates, acrylates having an acryloyl group are preferably used from the viewpoint of curing reactivity.

Among others, the ionizing radiation-curable resin composition contains a polyfunctional compound having two or more ethylenically unsaturated bonds in order to increase the crosslink density in the surface adjustment layer and improve moldability and mechanical strength. Preferably, it contains a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups.
Examples of polyfunctional (meth)acrylates include difunctional (meth)acrylates such as ethylene glycol di(meth)acrylate and di(meth)acrylates such as pentaerythritol di(meth)acrylate monostearate; pentaerythritol tri(meth) ) acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane hexa(meth)acrylate, and modified products thereof. Examples of modified polyfunctional (meth)acrylates having three or more (meth)acryloyl groups, such as ethylene oxide modified, propylene oxide modified, caprolactone modified, and isocyanuric acid modified. Among them, polyfunctional (meth)acrylates having three or more (meth)acryloyl groups are preferable from the viewpoint of the mechanical strength of the surface adjustment layer. At least one polyfunctional (meth)acrylate selected from the group consisting of erythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate is preferred, particularly dipentaerythritol. Triacrylates are preferred.

The content of the polyfunctional (meth)acrylate in the total solid content of the ionizing radiation-curable resin composition is preferably 20% by mass or more and 70% by mass or less from the viewpoint of the strength and moldability of the surface adjustment layer. It is preferably 30% by mass or more and 50% by mass or less.
In addition, in the total amount of 100 parts by mass of the ionizing radiation-curable resin contained in the ionizing radiation-curable resin composition, the content of the polyfunctional (meth)acrylate is determined from the viewpoint of the strength and moldability of the surface adjustment layer. , preferably 20 to 70 parts by mass, more preferably 30 to 50 parts by mass.

Moreover, the ionizing radiation-curable resin composition preferably contains a monofunctional (meth)acrylate having only one (meth)acryloyl group from the viewpoint of applicability. Monofunctional (meth)acrylates include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid, 2-ethylhexyl (meth)acrylate, 2-ethylhexylethylene oxide (hereinafter referred to as EO) adduct (meth) ) acrylate, ethoxydiethylene glycol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, caprolactone adduct of 2-hydroxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, nonylphenol EO adduct (meth)acrylate, nonylphenol EO adduct with caprolactone addition (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, caprolactone adduct (meth)acrylate of furfuryl (meth)alcohol, acryloylmorpholine, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, (Meth)acrylate of caprolactone adduct of 4,4-dimethyl-1,3-dioxolane, (meth)acrylate of caprolactone adduct of 3-methyl-5,5-dimethyl-1,3-dioxolane, and the like. can. Among them, the surface free energy tends to be a desired value, and the compatibility with the non-liquid crystalline structural units of the side chain type liquid crystal polymer is improved to improve the applicability of the liquid crystal composition to the surface adjustment layer, From the viewpoint of improving the vertical alignment and heat resistance of the retardation layer, it preferably contains a monofunctional (meth)acrylate having an ether bond, particularly 2-phenoxyethyl (meth)acrylate and tetrahydrofurfuryl (meth) It preferably contains at least one selected from acrylates.

The content of the monofunctional (meth)acrylate in the total solid content of the ionizing radiation-curable resin composition is preferably 5% by mass or more, and preferably 10% by mass or more, from the viewpoint of coatability and moldability. On the other hand, it is preferably 40% by mass or less, more preferably 30% by mass or less, from the viewpoint of the strength of the surface adjustment layer.
Among them, from the viewpoint of improving the applicability of the liquid crystal composition to the surface adjustment layer and improving the vertical alignment property and heat resistance of the retardation layer, it has an ether bond in the total solid content of the ionizing radiation curable resin composition. The content of the monofunctional (meth)acrylate is preferably 10% by mass or more and 30% by mass or less, more preferably 15% by mass or more and 25% by mass or less.
In addition, in the total amount of 100 parts by mass of the ionizing radiation-curable resin contained in the ionizing radiation-curable resin composition, the content of the monofunctional (meth)acrylate is 5 parts by mass from the viewpoint of coatability and moldability. It is preferably 10 parts by mass or more, more preferably 10 parts by mass or more. On the other hand, it is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, from the viewpoint of the strength of the surface adjustment layer.

In addition, when the ionizing radiation-curable resin composition contains a vinyl ether compound having a vinyl ether group, the surface free energy tends to be a desired value, and the side chain type liquid crystal polymer has the non-liquid crystalline structural unit. It is preferable from the viewpoint of improving the affinity of the liquid crystal composition, improving the applicability of the liquid crystal composition to the surface adjustment layer, and improving the vertical alignment property and heat resistance of the retardation layer.
Examples of the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, diethylene glycol mono Monofunctional vinyl ether compounds such as vinyl ether; Bifunctional vinyl ether compounds; Trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, and dipentaerythritol hexavinyl ether. Among them, from the viewpoint of controlling the strength and surface free energy of the surface adjustment layer, bifunctional vinyl ether compounds are preferred, and diethylene glycol divinyl ether is particularly preferred.

The content of the vinyl ether compound in the total solid content of the ionizing radiation-curable resin composition improves the applicability of the liquid crystal composition to the surface adjustment layer, and improves the vertical alignment and heat resistance of the retardation layer. Therefore, the content is preferably 20% by mass or more, more preferably 30% by mass or more. It is more preferable to have
In addition, in the total amount of 100 parts by mass of the ionizing radiation-curable resin contained in the ionizing radiation-curable resin composition, the content of the vinyl ether compound improves the coating properties of the liquid crystal composition on the surface adjustment layer, The amount is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, from the viewpoint of improving the vertical orientation and heat resistance of the layer, and 60 parts by mass from the viewpoint of the strength of the surface adjustment layer. It is preferably 50 parts by mass or less, more preferably 50 parts by mass or less.

Further, the total content of the ionizing radiation-curable resin group in the total solid content of the ionizing radiation-curable resin composition is preferably 90% by mass or more from the viewpoint of the strength and moldability of the surface adjustment layer. It is more preferably 95% by mass or more.

The ionizing radiation curable resin composition further optionally contains a polymerization initiator, a leveling agent, a release agent, a photosensitizer, an antioxidant, a polymerization inhibitor, a cross-linking agent, an infrared absorber, and an antistatic agent. , a viscosity modifier, an adhesion improver, and the like, and may contain a solvent from the viewpoint of coatability. The solvent that may be contained in the ionizing radiation-curable resin composition may be appropriately selected from conventionally known solvents capable of dissolving or dispersing each component contained in the ionizing radiation-curable resin composition. , but not limited to, for example, the same solvent as the solvent that may be contained in the liquid crystal composition.
The content of the additive in the total solid content of the ionizing radiation-curable resin composition is not particularly limited, but is preferably 5% by mass or less, more preferably 3% by mass or less.
When the ionizing radiation-curable resin composition contains a solvent, the solid content concentration of the ionizing radiation-curable resin composition is not particularly limited. From the viewpoint of easy control of the properties, it is preferably 5% by mass or more and 30% by mass or less,
It is more preferably 10% by mass or more and 20% by mass or less.

In the case where the substrate has the base material (ii) and the surface adjustment layer, the thickness of the surface adjustment layer is not particularly limited, but is preferably 0.1 μm or more from the standpoint of formability. , is more preferably 0.5 μm or more, and on the other hand, from the viewpoint of thinning the substrate and transparency, it is preferably 10 μm or less, more preferably 5 μm or less.

The method for forming the surface adjustment layer on the substrate may be appropriately selected according to the material of the surface adjustment layer, and is not particularly limited. is applied to form a coating film, and the coating film is cured.
The method of applying the curable resin composition is not particularly limited as long as it is a method capable of uniformly applying the curable resin composition onto the substrate, and examples thereof include gravure coating and reverse coating. , knife coating method, dip coating method, spray coating method, air knife coating method, spin coating method, roll coating method, printing method, dip method, slide coating method, curtain coating method, die coating method, casting method, bar coating method, A known coating method such as an extrusion coating method or an E-type coating method can be used.
It is preferable to adjust the coating amount of the curable resin composition onto the base material so as to obtain a surface adjustment layer having a desired thickness.
The coating film may be dried if necessary. Examples of the drying method include drying under reduced pressure, drying by heating, and combinations thereof. When drying under normal pressure, it is preferable to dry within a temperature range that does not deteriorate the substrate, for example, within the range of 30°C to 110°C.

The method for curing the coating film is appropriately selected according to the type of curable resin in the curable resin composition, and for example, at least one of light irradiation and heating can be used.
Ultraviolet rays, visible light, electron beams, etc. are mainly used for light irradiation, and among them, ultraviolet rays are preferably used. In the case of ultraviolet curing, ultraviolet rays emitted from light beams such as ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs and metal halide lamps are used. The irradiation dose of the energy ray source is preferably in the range of, for example, 50 mJ/cm ² or more and 5000 mJ/cm ² or less as an integrated exposure dose at an ultraviolet wavelength of 365 nm.
In the case of heating, it is preferable to heat within a temperature range in which the substrate is not deteriorated, for example, within a range of 40°C to 120°C. Alternatively, the reaction may be carried out by allowing to stand at room temperature of about 25° C. for 24 hours or more.
Further, from the viewpoint of improving the adhesion of the surface adjustment layer and the applicability of the liquid crystal composition, the surface adjustment layer is in a semi-cured state when the liquid crystal composition is formed. After aligning the liquid crystalline component in the product, it is preferable to further cure the semi-cured surface adjustment layer when polymerizing the polymerizable liquid crystal compound. The surface adjustment layer in a semi-cured state can be formed, for example, by exposing the coating film of the curable resin composition to irradiation within the range of 30 mJ/cm ^{2 or more and 122 mJ/cm 2 or} less in an environment where nitrogen purge is performed as necessary. A method of irradiating with a certain amount of light can be mentioned. Further, as a method for further curing the semi-cured surface adjustment layer, for example, a film of a liquid crystal composition is formed on the semi-cured surface adjustment layer, the liquid crystalline component is aligned, and then the liquid crystal composition is applied. The coating film of the liquid crystal composition and the semi-cured surface adjustment layer are irradiated from the surface of the film with an irradiation amount within the range of 72 mJ/cm ² or more and 440 mJ/cm ² or less in an environment where nitrogen purge is performed as necessary. A method of irradiating light onto the

(3) Alignment film The substrate used for the retardation film of the present disclosure includes a substrate and an alignment film on the surface of the substrate on the retardation layer side, or a substrate consisting of only an alignment film. can also be used. In the present specification, the alignment film refers to a layer for aligning the liquid crystalline component contained in the retardation layer in a certain direction.
As the alignment film used in the embodiment of the present disclosure, it is preferable to use a vertical alignment film because the liquid crystal composition of the embodiment of the present disclosure is easily vertically aligned.
The vertical alignment film is an alignment film having a function of vertically aligning the long axis of the mesogen of the liquid crystalline component contained in the retardation layer by providing it as a coating film.

The vertical alignment film is an alignment film having an alignment control force in the vertical direction, and various vertical alignment films used for manufacturing C plates and various vertical alignment films applied to VA liquid crystal display devices and the like can be applied. For example, a polyimide alignment film, an alignment film made of an LB film, or the like can be applied. Concretely, the constituent materials of the alignment film include, for example, lecithin, silane-based surfactants, titanate-based surfactants, pyridinium salt-based polymer surfactants, and silane coupling-based vertical surfactants such as n-octadecyltriethoxysilane. Alignment film compositions, polyimide-based vertical alignment film compositions such as soluble polyimides having long-chain alkyl groups or alicyclic structures in side chains and polyamic acids having long-chain alkyl groups or alicyclic structures in side chains can be applied.
As the vertical alignment film composition, JSR Corporation's polyimide-based vertical alignment film composition "JALS-2021" and "JALS-204", and Nissan Chemical Industries, Ltd.'s "RN-1517". , “SE-1211”, “EXPOA-018” and the like can be applied. Also, a vertical alignment film described in JP-A-2015-191143 may be used.

Although the method for forming the alignment film is not particularly limited, the alignment film can be formed, for example, by applying an alignment film composition on the substrate and imparting an alignment regulating force. Conventionally known means can be used as a means for imparting an alignment regulating force to the alignment film.

The thickness of the alignment film may be set appropriately as long as the liquid crystalline component in the retardation layer can be aligned in a certain direction. The thickness of the alignment film is usually in the range of 1 nm to 10 μm, preferably in the range of 60 nm to 5 μm.

(4) Other Layers When the substrate has a multilayer structure, it may have a primer layer for improving the adhesion of each layer. The primer layer preferably has adhesiveness to the adjacent layer, is optically transparent, and allows ultraviolet rays to pass through. can be used

Further, the substrate may have an anchor coat layer on its surface. The anchor coat layer can improve the strength of the substrate and ensure good vertical alignment. A metal alkoxide, especially a metal silicon alkoxide sol can be used as a material for the anchor coat layer. Metal alkoxides are usually used as alcoholic solutions. 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, more preferably about 0.05 μm or more and 0.2 μm or less.
When the substrate has an anchor coat layer on the base material, a binder layer is further laminated between the base material and the anchor coat layer, or a material that enhances adhesion to the base material is added to the anchor coat layer. By doing so, the adhesion between the substrate and the anchor coat layer may be improved. As the binder material used for forming the binder layer, any material capable of improving the adhesion between the substrate and the anchor coat layer can be used without particular limitation. Examples of binder materials include silane coupling agents, titanium coupling agents, and zirconium coupling agents.

3. 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 suitably used, for example, as a viewing angle compensation film, and is suitably used as an optical member for various display devices as described later. Specifically, for example, it is suitably used as a viewing angle compensation film for a light-emitting display device such as an organic light-emitting display device provided with a circularly polarizing plate.

C. Method for producing retardation film The method for producing the retardation film of the present disclosure is not particularly limited as long as it is a method capable of obtaining the retardation film of the present disclosure.
preparing a substrate having a surface free energy of 30 mJ/m ² or more on at least one surface;
forming a film of the liquid crystal composition of the present disclosure on the surface of the substrate;
a step of aligning the liquid crystal constitutional units of the side chain type liquid crystal polymer in the formed liquid crystal composition and the polymerizable liquid crystal compound;
A method for producing a retardation film may include a step of polymerizing the polymerizable liquid crystal compound after the orienting step to form a retardation layer.
In the production method, since the liquid crystal composition of the present disclosure is formed on the surface of the substrate having a surface free energy of 30 mJ / m ² or more, as described above, the coating properties of the liquid crystal composition are improved, and the retardation The vertical orientation and heat resistance of the layer can be improved.
Hereinafter, each step of the method will be described in order.

1. Step of preparing a substrate The substrate used in the production method is appropriately selected from the substrates that the "B. Retardation film" can have and having a surface free energy of at least one surface of 30 mJ / m ² or more. It can be selected and used. Among the substrates used in the production method, since it is easy to set the surface free energy of at least one surface to 30 mJ / m ² or more, the substrate of (ii) and the retardation of the substrate A material having the surface adjustment layer on the layer side surface can be preferably used.
In the case where the substrate has the surface adjustment layer, the surface adjustment layer should be in a semi-cured state in the step of preparing the substrate in order to improve the adhesion of the surface adjustment layer and the coating properties of the liquid crystal composition. is preferably That is, the step of preparing the substrate includes a step of applying the curable resin composition on the substrate to form a coating film, and semi-curing the coating film to form a semi-cured surface adjustment layer. and forming a film of the liquid crystal composition on the surface of the semi-cured surface adjustment layer. In the step of polymerizing the polymerizable liquid crystal compound, which will be described later, the polymerizable liquid crystal compound is polymerized. At the same time, it is preferable to further cure the semi-cured surface adjustment layer.

2. Liquid Crystal Composition Film Forming Step As the liquid crystal composition used in the manufacturing method, the same liquid crystal composition as described above in "A. Liquid Crystal Composition" can be used.
Examples of the method of forming a film of the liquid crystal composition on the surface of the substrate having a surface free energy of 30 mJ/m ² or more include a method of coating the surface of the substrate with the liquid crystal composition. The coating method is not particularly limited as long as the liquid crystal composition can be uniformly coated. Examples include gravure coating, reverse coating, knife coating, dip coating, spray coating, and air coating. Knife coating method, spin coating method, roll coating method, printing method, dipping method, slide coating method, curtain coating method, die coating method, casting method, bar coating method, extrusion coating method, E-type coating method, etc. method can be used.

3. Step of Aligning Liquid Crystalline Component Next, the liquid crystal constitutional units of the side-chain type liquid crystal polymer in the formed liquid crystal composition and the polymerizable liquid crystal compound are adjusted to a temperature at which they can be vertically aligned and heated. By the heat treatment, the liquid crystalline structural units of the side chain type liquid crystal polymer and the polymerizable liquid crystal compound can be vertically aligned and dried, and can be fixed while maintaining the alignment state.
Since the temperature at which vertical alignment is possible varies depending on each substance in the liquid crystal composition, it must be adjusted as appropriate. For example, the temperature is preferably 40° C. or higher and 200° C. or lower, and more preferably 40° C. or higher and 100° C. or lower.
As the heating means, known heating and drying means can be appropriately selected and used.
Moreover, the heating time may be selected as appropriate, and is selected, for example, within the range of 10 seconds to 2 hours, preferably 20 seconds to 30 minutes.

4. Step of polymerizing the polymerizable liquid crystal compound In the step of orienting the liquid crystal component, the polymerizable liquid crystal compound is polymerized by irradiating, for example, light to the coating film fixed while maintaining the alignment state of the liquid crystal component. It is possible to obtain a retardation layer containing a cured product of the liquid crystal composition.
Ultraviolet irradiation is preferably used as the light irradiation. Ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, xenon arcs, metal halide lamps, and the like can emit ultraviolet rays for ultraviolet irradiation. The irradiation dose of the energy ray source may be appropriately selected, and is preferably in the range of, for example, 10 mJ/cm ² or more and 10000 mJ/cm ² or less as an integrated exposure dose at an ultraviolet wavelength of 365 nm. When the substrate has the surface adjustment layer and the semi-cured surface adjustment layer is further cured in the step of polymerizing the polymerizable liquid crystal compound, in the step of polymerizing the polymerizable liquid crystal compound, the energy The radiation dose of the radiation source is preferably in the range of 72 mJ/cm ² or more and 440 mJ/cm ² or less as an integrated exposure dose at an ultraviolet wavelength of 365 nm. Moreover, the light irradiation may be performed under a nitrogen stream, if necessary.

D. Transfer laminate The transfer laminate of the present disclosure includes a retardation layer and a support having a peelable support layer,
The retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, the side chain type liquid crystal polymer has a structure represented by the general formula (I), and has an SP value of 9.0. 25 (cal/cm ³ ) ^1/2 or more having a non-liquid crystalline structural unit and a liquid crystalline structural unit having a side chain containing a liquid crystalline moiety, the side chain type liquid crystalline polymer and the polymerizable liquid crystal compound A cured product of a liquid crystal composition in which the mass ratio of the side chain type liquid crystal polymer to the total mass of the liquid crystal composition is 2% by mass or more and 20% by mass or less,
A transfer layered product to be used for transfer of the retardation layer.

The transfer laminate of the present embodiment is used for transferring the retardation layer, and the retardation layer contains the cured product of the liquid crystal composition, so that the vertical alignment is excellent and the heat resistance is improved. The retardation layer can be transferred to a transfer target such as any other optical member.
According to the transfer laminate of the present embodiment, for example, a retardation film 10 ′ composed only of the retardation layer 1 shown in the example of FIG. 2, or a laminate having a surface adjustment layer or an alignment film and a retardation layer A thin retardation film containing no substrate, such as a retardation film comprising The retardation layer transferred using the transfer laminate of the present embodiment may further include a layer of a thin film different from the retardation layer such as the surface adjustment layer and the alignment film and the substrate. .
The configuration of such a transfer laminate will be described below.

The layer structure of the transfer laminate will be described with reference to the drawings. Figures 4, 5 and 6 each illustrate one embodiment of the transfer laminate of the present disclosure.
The transfer laminate 20 shown in the example of FIG. 4 includes a retardation layer 11 and a support 14, and the support 14 has a substrate 12 and a surface adjustment layer 13 for adjusting surface free energy. . In the transfer laminate 20 shown in the example of FIG. 4, the peel strength at the interface between the base material 12 and the surface adjustment layer 13 is greater than the peel strength between the surface adjustment layer 13 and the retardation layer 11. As a result, separation is likely to occur at the interface 17 between the surface adjustment layer 13 and the retardation layer 11 . Therefore, the entire support 14, which is a laminate of the substrate 12 and the surface adjustment layer 13, can be peeled off from the transfer laminate 20 transferred onto the transfer target as a peelable support layer 15. , the retardation layer 11 can be transferred as the transfer layer 16 .
The transfer laminate 30 shown in the example of FIG. 5 includes a retardation layer 21 and a support 24. The support 24 has a substrate 22 and a surface adjustment layer 23 for adjusting surface free energy. . In the transfer laminate 30 shown in the example of FIG. 5, the peel strength at the interface between the base material 22 and the surface adjustment layer 23 is lower than the peel strength between the surface adjustment layer 23 and the retardation layer 21. As a result, the interface 27 between the surface adjustment layer 23 and the substrate 22 is easily peeled off. Therefore, the base material 22 can be peeled off as the support layer 25 that can be peeled off from the transfer layered product 30 transferred onto the object to be transferred, and the layered product of the retardation layer 21 and the surface adjustment layer 23 can be transferred. It can be transferred as layer 26 .

When the support used in the transfer laminate of the present embodiment has a multilayer structure, is the peel strength at the interface of each layer in the multilayer structure greater than the peel strength at the interface between the support and the retardation layer? Whether it is small can be confirmed, for example, by peeling off the retardation layer from the transfer laminate and checking at which interface the separation occurs. At which interface the peeling occurs can be analyzed, for example, by IR or the like.

A transfer laminate 40 shown in the example of FIG. 6 includes a retardation layer 31 and a support 34, and the support 34 is made of a single-layer base material. In the transfer laminate 40 shown in the example of FIG. 6, since it is easy to peel off at the interface between the retardation layer 31 and the support 34, the transfer laminate 40 transferred onto the transfer target is separated from the support. 34 can be peeled off as a peelable support layer 35 and the retardation layer 31 can be transferred as a transfer layer 36 .

1. Retardation layer The retardation layer used in the transfer laminate of the present disclosure is a retardation layer containing a cured product of the liquid crystal composition of the present disclosure, and the retardation layer described in "B. Retardation film". can be similar to

2. Support The support used in the transfer laminate of the present disclosure is a support having a peelable support layer.
Examples of the support include those similar to the substrate used in the above "B. Retardation film", and those preferable as the substrate are also preferable as the support of the transfer laminate of the present disclosure. can be used. Further, from the viewpoint of improving the vertical alignment property and heat resistance of the retardation layer, a support having a surface free energy of 30 mJ/m ² or more on the retardation layer side surface and the retardation layer are arranged adjacent to each other. more preferably located.

Further, the support may be the whole support can be peeled off from the retardation layer, or may have a peelable support layer and a non-peeling layer adhered to the retardation layer. good. The thickness of the layer adhered to the retardation layer and not peeled off is preferably 10 μm or less, more preferably 5 μm or less, from the viewpoint of thinning.
The peelable support layer of the support may be a single layer or multiple layers. A peelable support layer can be formed from the interface having the lowest peel strength among the interfaces between the layers of the transfer laminate to the surface of the support on the side opposite to the retardation layer.
Among them, it is preferable that the interface between the retardation layer and the support is peelable, and the entire support is a peelable support layer. As a result, the retardation layer can be transferred as a single layer, so that it is possible to reduce the thickness and improve the optical properties.

In order to obtain the transfer laminate 20 shown in the example of FIG. For example, a method of using a solvent capable of dissolving the base material 12 as a solvent contained in the material used for forming the surface adjustment layer 13 can be used. In this case, it is preferable to use a resin base material as the base material 12, and the surface of the base material may be subjected to a surface treatment to improve adhesion. In such a case, the adhesion between the resin substrate and the surface adjustment layer can be improved.
Moreover, in order to reduce the peel strength between the surface adjustment layer 13 and the retardation layer 11, it is also preferable to increase the solvent resistance of the surface adjustment layer 13 by, for example, increasing the degree of curing of the surface adjustment layer 13. When the solvent resistance of the surface adjustment layer 13 is relatively high, when the liquid crystal composition is applied onto the surface adjustment layer 13 to form the retardation layer 11, the solvent in the liquid crystal composition may be added to the surface adjustment layer 13. becomes difficult to dissolve, it is possible to suppress an improvement in adhesion between the surface adjustment layer 13 and the retardation layer 11 . It is also preferable to use a solvent having low solubility for the surface adjustment layer 13 as the solvent in the liquid crystal composition.

On the other hand, in order to obtain the transfer laminate 30 shown in the example of FIG. Examples of the method include a method of applying a release treatment to the surface of the base material 22, a method of forming a release layer on the surface of the base material 22, and the like. Thereby, the peelability of the base material can be enhanced, and the peel strength between the base material 22 and the surface adjustment layer 23 can be made smaller than the peel strength between the surface adjustment layer 23 and the retardation layer 21 .
Examples of the release treatment include surface treatments such as fluorine treatment and silicone treatment.
Materials for the release layer include, for example, fluorine-based release agents, silicone-based release agents, wax-based release agents, and the like. Examples of the method of forming the release layer include a method of applying a release agent by a coating method such as dip coating, spray coating, or roll coating.
Also, in order to obtain the transfer laminate 40 shown in the example of FIG. good too.

The support used for the transfer laminate may or may not have flexibility, but from the viewpoint of easy peeling, it is preferable to have flexibility.
The thickness of the support used for the transfer laminate is usually 20 μm from the balance between sufficient self-supporting strength and flexibility that can be adapted to the production and transfer process of the transfer laminate of the present embodiment. It is preferably within the range of 200 μm or more.

3. Method for producing transfer laminate The method for producing the transfer laminate of the present disclosure is not particularly limited as long as it is a method capable of obtaining the transfer laminate of the present disclosure.
preparing a support having a surface free energy of 30 mJ/m ² or more on at least one surface;
forming a film of the liquid crystal composition of the present disclosure on the surface of the support;
a step of aligning the liquid crystal constitutional units of the side chain type liquid crystal polymer in the formed liquid crystal composition and the polymerizable liquid crystal compound;
A method for producing a transfer layered product may include a step of polymerizing the polymerizable liquid crystal compound after the orienting step, thereby forming a retardation layer.

In the step of preparing a support having at least one surface with a surface free energy of 30 mJ/m ² or more, at least one surface of the support having a surface free energy of 30 mJ/m ² or more is selected as appropriate. It can be selected and used, and among others, the method preferable in the step of preparing the substrate in the above "C. Method for producing a retardation film" can also be preferably used in the step of preparing the support.
In the method for producing the transfer laminate, the steps of forming a film of a liquid crystal composition, orienting the liquid crystal constitutional unit and the polymerizable liquid crystal compound, and polymerizing the polymerizable liquid crystal compound each include: It can be the same method as the above "C. Method for producing a retardation film".

4. Applications The retardation layer that can be provided from the transfer laminate of the present disclosure is suitably used for the same applications as the retardation film, and the positive C-type retardation layer can be transferred to optical members for various display devices. and is preferably used to provide 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 plate that allows passage of only light vibrating in a specific direction, and can be appropriately selected from conventionally known polarizing plates. For example, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, a saponified ethylene-vinyl acetate copolymer film, and the like which are dyed with iodine or a dye and stretched can be used.
In addition, 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, such as pressure-sensitive adhesives (adhesives), two-component curing adhesives, Any form of adhesion such as an ultraviolet curable adhesive, a heat curable adhesive, and a hot melt adhesive can be suitably used.

In addition to the polarizing plate, the optical member of this embodiment may further have other layers that are provided in known optical members. Examples of the other layers include other retardation layers different from the retardation layer of the present embodiment, antireflection layers, diffusion layers, antiglare layers, antistatic layers, protective films, and the like. , but not limited to these.

The optical member of this 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 the circularly polarizing plate are laminated, is suitably used, for example, as an optical member for suppressing external light reflection for a light-emitting display device. It can be suitably used as a wide viewing angle polarizing plate for display devices.

F. Method for Manufacturing Optical Member The method for manufacturing the optical member of the present disclosure is not particularly limited, and a method of laminating a polarizing plate on the retardation film of the present disclosure can be appropriately selected and used. For example, there is a production method of laminating a polarizing plate on the retardation film of the present disclosure via an adhesive layer or an adhesive layer.

Further, as a method for manufacturing an optical member according to an embodiment of the present disclosure,
A transfer laminate preparation step of preparing the transfer laminate of the present disclosure;
A transfer step of placing a transfer target including at least a polarizing plate and the retardation layer of the transfer laminate to face each other, and transferring the transfer laminate onto the transfer target;
and a peeling step of peeling the peelable support layer from the transfer laminate transferred onto the transfer target.

According to the method for manufacturing an optical member according to one embodiment of the present disclosure using the transfer laminate, a thin retardation film of the retardation film of the present disclosure that does not contain a substrate and a polarizing plate are provided. An optical member can be obtained.
The transfer laminate used in the method for manufacturing an optical member according to an embodiment of the present disclosure can be the same as that described in the above "D. Transfer laminate", so the description is omitted here. do.
In addition, a transfer target used in the method for manufacturing an optical member according to an embodiment of the present disclosure typically includes a transfer target having an adhesive layer and a polarizing plate, but is not limited to these. , and may further have the same layers as the other layers that the optical member of the present disclosure described above may have.

G. Display Device A display device according to the present disclosure includes the retardation film of the present disclosure or the optical member of the present disclosure.
Examples of the display device include, but are not limited to, a light-emitting display device, a liquid crystal display device, and the like.

Among them, since the retardation film of the present disclosure or the optical member of the present disclosure is provided, in particular, 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, external light This has the effect of improving the viewing angle while suppressing reflection.

An example of a light-emitting display device according to one embodiment will be described with reference to the drawings. FIG. 8 is a schematic cross-sectional view showing one embodiment of an organic light-emitting display device.
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 in this order.
As the light-emitting layer 72, for example, a structure in which a hole injection layer, a hole transport layer, a light-emitting layer, and an electron injection F-input layer are stacked in this order from the transparent electrode layer 71 side. In this embodiment, 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 structures can be appropriately used known ones. The light-emitting display device manufactured in this manner can be applied to, for example, a passive drive type organic EL display and an active drive type organic EL display.
It should be noted that the display device of the present embodiment is not limited to the configuration described above, and may have an appropriately selected known configuration.

Examples 1 to 9, 11, and 12 below are reference examples.
(Synthesis Example 1: Synthesis of Liquid Crystal Monomer 1)
First, according to Scheme 1 below, 4-[2-(acryloyloxy)ethoxy]benzoic acid was synthesized.
2-Bromoethanol (20 g, 162 mmol) was added to a DMF (1 L) suspension of ethyl 4-hydroxybenzoate (28 g, 170 mmol) and potassium carbonate (26 g, 187 mmol), and the mixture was stirred at 80° C. for 8 hours. After completion of the reaction, the reaction solution was diluted with water, extracted with ethyl acetate, and the solvent was distilled off. An aqueous solution of potassium hydroxide (11 g, 187 mmol) was added to the resulting crude product, and the mixture was reacted at 100° C. for 4 hours for hydrolysis. After completion of the reaction, an aqueous hydrochloric acid solution was added, and then ethyl acetate was added for extraction, and the solvent was distilled off. The residue was purified by silica gel chromatography, and the solvent was distilled off to obtain p-(2-hydroxyethoxy)benzoic acid with a yield of 89% (26 g, 145 mmol).
Then, a suspension of p-(2-hydroxyethoxy)benzoic acid (16 g, 90 mmol), acryloyl chloride (7.4 g, 82 mmol), dimethylaniline (DMA) (9.9 g, 82 mmol) in tetrahydrofuran (400 mL) was stirred for 12 hours. After completion of the reaction, water and ethyl acetate were added for liquid separation. The solvent was distilled off, the residue was purified by silica gel chromatography, and the solvent was distilled off to obtain 4-[2-(acryloyloxy)ethoxy]benzoic acid with a yield of 90% (17.4 g, 73.8 mmol). ).

Next, according to the scheme 2 below, a liquid crystal monomer 1 represented by the following chemical formula (1) was obtained.
4-[2-(acryloyloxy)ethoxy]benzoic acid (17 g, 70 mmol) obtained above, 4′-cyano-4-hydroxybiphenyl (14 g, 70 mmol), N,N-dimethylaminopyridine (DMAP) ( 252 mg, 2.10 mmol) in dichloromethane (90 mL) was added dropwise with a dichloromethane (10 mL) solution of N,N-dicyclohexylcarbodiimide (DCC) (16 g, 76 mmol). After completion of dropping, the mixture was stirred for 12 hours, the precipitate was filtered, and the solvent was distilled off. Methanol (200 mL) was added to the resulting crude product, and the mixture was stirred for 1 hour for suspension purification. 4′-cyano-4-{4-[6-(acryloyloxy)ethyloxy]benzoate} (chemical formula (1) below) was obtained by filtering the precipitate and drying the obtained crystals, yield 93%. (28 g, 67 mmol).

(Synthesis Example 2: Synthesis of Liquid Crystal Monomer 2)
First, according to Scheme 3 below, 4-propoxycarbonylphenyl-4-hydroxybenzoate represented by the following chemical formula (a) was obtained.
A suspension of 4-acetoxybenzoic acid (15 g, 84 mmol), propyl 4-hydroxybenzoate (14 g, 80 mmol) and N,N-dimethylaminopyridine (DMAP) (0.59 g, 4.9 mmol) in dichloromethane (100 mL) To the solution was added dropwise a solution of N,N-dicyclohexylcarbodiimide (DCC) (17 g, 84 mmol) in dichloromethane (450 mL). After completion of dropping, the mixture was stirred for 12 hours, the precipitate was filtered, and the solvent was distilled off. Methanol (100 mL) was added to the resulting oil to dissolve it, and a solution of potassium carbonate (13 g, 93 mmol) in water (50 mL) was added dropwise under cooling. After stirring the reaction mixture for 1 hour, it was neutralized with 35% hydrochloric acid (9.4 mL). Obtained step by step 73% (17 g, 58 mmol) yield.

Next, according to Scheme 4 below, a liquid crystal monomer 2 represented by the following chemical formula (2) was obtained.
4-propoxycarbonylphenyl-4-hydroxybenzoate (15 g, 50 mmol), 4-[6-(acryloyloxy)hexyloxy]benzoic acid (14 g, 48 mmol), N,N-dimethylaminopyridine (DMAP) (0. 17 g, 1.3 mmol) in dichloromethane (60 mL) was added dropwise with a dichloromethane (10 mL) solution of N,N-dicyclohexylcarbodiimide (DCC) (11 g, 52 mmol). After the dropwise addition was completed, the mixture was stirred for 12 hours, the precipitate was filtered, and the solvent was distilled off. Methanol is added to the obtained crude product, recrystallization is performed, and the obtained crystal is dried to give 4-[(4-propoxycarbonylphenyloxycarbonyl)phenyl-4-[6-(acryloyloxy)hexyloxy ] benzoate was obtained in 88% yield (24 g, 44 mmol).

(Synthesis Example 3: Synthesis of Monomer A)
4-Amylphenol (8.25 g, 50.2 mmol), 6-chloro-1-hexanol (7.20 g, 52.7 mmol), and potassium carbonate (8.33 g, 60.3 mmol) were placed in four 2 L flasks shielded from light. , N,N-dimethylformamide (20 mL) was added, and the mixture was heated to 100° C. and stirred for 37 hours. After that, the reaction solution was allowed to cool to room temperature, water (50 mL) was added, and the mixture was stirred for 10 minutes. After that, ethyl acetate (40 mL) was further added, and the mixture was stirred for 5 minutes and then separated. The separated aqueous layer was re-extracted with ethyl acetate (40 mL) and the organic layers were combined and washed with water (50 mL). Further, the mixture was washed with water (50 mL) and saturated brine (20 mL), and the aqueous layer was removed by liquid separation, followed by distilling off the solvent. The residue was purified by silica gel chromatography, and 12.1 g of ether A was obtained by distilling off the solvent.
Next, the ether A (11.5 g, 39.2 mmol), N,N-dimethylaniline (5.23 g, 43.2 mmol), N,N-dimethylacetamide (3. 0 mL) and tetrahydrofuran (37 mL) were added, and the internal temperature was cooled to 15° C. or lower. A solution of acryloyl chloride (5.68 g, 62.8 mmol) dissolved in tetrahydrofuran (10 mL) was added dropwise to the mixture, and the mixture was stirred at 25° C. for 5 hours. Thereafter, the reaction solution was added dropwise to water (120 mL), ethyl acetate (100 mL) was added for extraction, and then the solvent in the organic layer was distilled off. The residue was purified by silica gel chromatography, and the solvent was distilled off to obtain a monomer A represented by the following chemical formula (A) with a yield of 82% (8.87 g, 32.1 mmol).
The SP value of the non-liquid crystalline structural unit formed by the polymerization reaction of the acryloyl group of the monomer A is 9.82 (cal/cm ³ ) ^1/2 .

Light Acrylate 130A (Kyoeisha Chemical Co., Ltd.) was used as the monomer B represented by the following chemical formula (B).
The SP value of the non-liquid crystalline structural unit formed by the polymerization reaction of the acryloyl group of the monomer B is 9.71 (cal/cm ³ ) ^1/2 .

(Synthesis Example 4: Synthesis of Monomer C)
In the same manner as in Synthesis Example 3 except that 4-nonylphenol was used in place of 4-amylphenol and 16-bromo-1-hexadecanol was used in place of 6-chloro-1-hexanol in Synthesis Example 3, the following A monomer C represented by the chemical formula (C) was obtained.
The SP value of the non-liquid crystalline structural unit formed by the polymerization reaction of the acryloyl group of Monomer C is 9.29 (cal/cm ³ ) ^1/2 .

(Synthesis Example 5: Synthesis of Monomer D)
A monomer D represented by the following chemical formula (D) was obtained in the same manner as in Synthesis Example 3 except that 2,3-difluoro-4-methylphenol was used instead of 4-amylphenol. .
The SP value of the non-liquid crystalline structural unit formed by the polymerization reaction of the acryloyl group of the monomer D is 10.60 (cal/cm ³ ) ^1/2 .

(Synthesis Example 6: Synthesis of Monomer E)
A monomer E represented by the following chemical formula (E) was obtained in the same manner as in Synthesis Example 3 except that 4-methylcyclohexanol was used instead of 4-amylphenol.
The SP value of the non-liquid crystalline structural unit formed by the polymerization reaction of the acryloyl group of the monomer E is 9.66 (cal/cm ³ ) ^1/2 .

(Synthesis Example 7: Synthesis of Monomer F)
In Synthesis Example 1, 4-[2-(acryloyloxy)ethoxy]benzoic acid was replaced with 4-methylbenzoic acid, and 4′-cyano-4-hydroxybiphenyl was replaced with 6-chloro-1-hexanol. Ester F was obtained in the same manner as in Synthesis Example 1, except that it was used. Next, a monomer F represented by the following chemical formula (F) was obtained in the same manner as in Synthesis Example 3 except that the obtained ester F was used in place of the ether A in Synthesis Example 3. rice field.
The SP value of the non-liquid crystalline structural unit formed by the polymerization reaction of the acryloyl group of the monomer F is 10.74 (cal/cm ³ ) ^1/2 .

(Synthesis Example 8: Synthesis of Monomer G)
A monomer G represented by the following chemical formula (G) was obtained in the same manner as in Synthesis Example 3 except that 5-hydroxy-2-methylpyridine was used in place of 4-amylphenol in Synthesis Example 3. .
The SP value of the non-liquid crystalline structural unit formed by the polymerization reaction of the acryloyl group of the monomer G is 10.70 (cal/cm ³ ) ^1/2 .

Stearyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the monomer F represented by the following chemical formula (H).
The SP value of the non-liquid crystalline structural unit formed by the polymerization reaction of the acryloyl group of the monomer H is 9.14 (cal/cm ³ ) ^1/2 .

Hereinafter, the monomers A to H are sometimes referred to as non-liquid crystal monomers A to H.

(Production Example 1: Synthesis of side chain type liquid crystal polymer A-01)
The liquid crystal monomer 1 and the non-liquid crystal monomer A were combined and mixed at a molar ratio of 65:35, N,N-dimethylacetamide (DMAc) was added, and the mixture was stirred at 40° C. to dissolve. After dissolution, the mixture was cooled to 24° C., and azobisisobutyronitrile (AIBN) was added and dissolved at the same temperature. The above reaction solution was added dropwise to DMAc heated to 80°C over 30 minutes, and after the dropwise addition was completed, the mixture was stirred at 80°C for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, dropped into another container containing methanol, and stirred for 20 minutes. After removing the supernatant liquid, the slurry was filtered, and the obtained crude product was again stirred in methanol for 20 minutes, and after removing the supernatant liquid, filtration was performed. By drying the obtained crystals, a side chain type liquid crystal polymer A-01 was obtained with a yield of 76.5%. As a result of measuring the weight average molecular weight Mw of the obtained side-chain type liquid crystal polymer A-01 by the GPC described above, it was 8,700. Structural analysis of the obtained side-chain type liquid crystal polymer A-01 by ¹ H-NMR revealed that the copolymerization ratio (molar ratio) of the liquid crystal monomer 1 and the non-liquid crystal monomer A was 67:33. there were.

(Production Examples 2 to 7: Synthesis of Side Chain Type Liquid Crystal Polymers A-02 to A-09)
In the production example of the side chain type liquid crystal polymer A-01, except that the combination of the liquid crystal monomer and the non-liquid crystal monomer and the copolymerization ratio (molar ratio) were changed as shown in Table 1, the side chain type liquid crystal polymer A-01 Side chain type liquid crystal polymers A-02 to A-09 were obtained in the same manner as in Synthesis Example 1. For each of the obtained side-chain type liquid crystal polymers A-02 to A-09, the weight average molecular weight Mw was measured by GPC described above, and structural analysis was performed by ¹ H-NMR. Table 1 shows the measurement results of the mass average molecular weight (Mw) and the copolymerization ratio (molar ratio) between the liquid crystal monomer and the non-liquid crystal monomer.

A compound represented by the following chemical formula B-01 was prepared as a polymerizable liquid crystal compound.

As a photopolymerization initiator, the following C-01 was prepared.
C-01: IRGACURE907 (manufactured by Ciba Specialty Chemicals)

D-01 below was prepared as a leveling agent.
D-01: Megafac F-554 (manufactured by DIC)

(Example 1)
(1) Preparation of liquid crystal composition Side chain type liquid crystal polymer (A-01) 20 parts by weight, polymerizable liquid crystal compound (B-01) 80 parts by weight, photopolymerization initiator (C-01) 4 parts by weight, and leveling Liquid crystal composition 1 of Example 1 was prepared by dissolving 0.2 parts by mass of agent (D-01) in 400 parts by mass of a 50:50 mixed solvent of methyl ethyl ketone and cyclohexanone.

(2) Production of retardation film or laminate for transfer On one side of a PET substrate having a thickness of 38 μm, a curable resin composition for a surface adjustment layer is coated so that the film thickness after curing becomes 3 μm, and nitrogen By performing nitrogen purge for 15 seconds at a supply pressure of about 0.010 to 0.015 MPa, in an environment where the residual oxygen concentration is 8 to 10% by volume, ultraviolet rays are irradiated at an irradiation dose of 76 mJ/cm ² to a semi-cured state. was formed to form a substrate 1. The curable resin composition for the surface adjustment layer includes 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, dipentaerythritol triacrylate, and bis(2-vinyloxyethyl) in methyl isobutyl ketone (MIBK). and ether at a ratio (mass ratio) of 1:1:4:5, Lucirin TPO (manufactured by BASF) as a polymerization initiator was added at a rate of 4% by mass in the total solid content, and Megafac was added as a leveling agent. A mixture (solid concentration: 15% by mass) in which 0.05% by mass of F-554 (manufactured by DIC) was added to the total solid content was used.

The contact angles of n-hexadecane, methylene iodide and pure water on the surface of the obtained substrate 1 were measured by a contact angle meter (DropMaster manufactured by Kyowa Interface Science Co., Ltd.). The calculated surface free energy was 36 mJ/m ² .

Subsequently, the liquid crystal composition 1 is applied onto the semi-cured surface adjustment layer of the obtained substrate 1 by a die head coating method while adjusting the flow rate during coating so that the film thickness after curing is 1 μm. and formed a film. Then, after drying at 85° C. for 60 seconds, ultraviolet rays are irradiated at a dose of 120 mJ/cm ² under a nitrogen stream to further cure the surface adjustment layer in a semi-cured state, and the liquid crystal composition 1. A retardation layer was formed by polymerizing the polymerizable liquid crystal compound therein, and the retardation film or the transfer laminate of Example 1 was obtained.

(Example 2)
(1) Preparation of liquid crystal composition Example 1 (1) except that side chain type liquid crystal polymer A-02 was used instead of side chain type liquid crystal polymer A-01 in Example 1 (1). Liquid crystal composition 2 of Example 2 was obtained in the same manner.

(2) Preparation of Retardation Film or Transfer Laminate In the same manner as in Example 1 (2), except that the liquid crystal composition 2 was used instead of the liquid crystal composition 1 in (2) of Example 1. Thus, a retardation film or a transfer laminate of Example 2 was obtained.

(Example 3)
(1) Preparation of liquid crystal composition Example 1 (1) was the same as in Example 1 (1), except that the side chain type liquid crystal polymer A-03 was used instead of the side chain type liquid crystal polymer A-01. Liquid crystal composition 3 of Example 3 was obtained in the same manner.

(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, a substrate 2 obtained by the following method was used instead of the substrate 1, and a liquid crystal composition was used instead of the liquid crystal composition 1. A retardation film or a transfer laminate of Example 3 was obtained in the same manner as in (2) of Example 1, except that No. 3 was used.
The substrate 2 was prepared by coating one side of a PET base material having a thickness of 38 μm with the curable resin composition for the surface adjustment layer so that the film thickness after curing was 3 μm. The bottom layer was prepared by irradiating ultraviolet rays with an exposure amount of 76 mJ/cm ² to form a semi-cured surface adjustment layer.
The surface free energy of the obtained substrate 2 was calculated by the same method as for the substrate 1 and was 41 mJ/m ² .

(Example 4)
(1) Preparation of liquid crystal composition The same as the liquid crystal composition 3 obtained in Example 3 was used.
(2) Preparation of Retardation Film or Transfer Laminate In (2) of Example 3, except that the substrate 2 was replaced with the substrate 3 obtained by the following method. Similarly, a retardation film or a transfer laminate of Example 4 was obtained.
The substrate 3 is obtained by coating one side of a 38 μm-thick PET base material with the curable resin composition for the surface adjustment layer so that the film thickness after curing is 3 μm, and the nitrogen supply pressure is 0.010 to 0.01. A semi-cured surface adjustment layer is formed by irradiating ultraviolet rays at an exposure dose of 76 mJ/cm ² in an environment where the residual oxygen concentration is 1% by volume or less by performing a nitrogen purge for 60 seconds at about 015 MPa. made by
The surface free energy of the obtained substrate 3 was calculated by the same method as for the substrate 1 and was 30 mJ/m ² .

(Example 5)
(1) Preparation of liquid crystal composition In (1) of Example 1, the side chain type liquid crystal polymer A-03 was used instead of the side chain type liquid crystal polymer A-01, and the side chain type liquid crystal polymer A-03 and the polymerizability Liquid crystal composition 5 of Example 5 was obtained in the same manner as in Example 1 (1), except that the amount of the liquid crystal compound added was changed to the amount shown in Table 2.

(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, the substrate 3 used in Example 4 was used instead of the substrate 1, and the liquid crystal composition A retardation film or a transfer laminate of Example 5 was obtained in the same manner as in (2) of Example 1, except that product 5 was used.

(Example 6)
(1) Preparation of liquid crystal composition Same as (1) of Example 1 except that in (1) of Example 1, side chain type liquid crystal polymer A-04 was used instead of side chain type liquid crystal polymer A-01. Liquid crystal composition 6 of Example 6 was obtained in the same manner.

(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, the substrate 3 used in Example 4 was used instead of the substrate 1, and the liquid crystal composition A retardation film or a transfer laminate of Example 6 was obtained in the same manner as in (2) of Example 1, except that the product 6 was used.

(Example 7)
(1) Preparation of liquid crystal composition In (1) of Example 1, the side chain type liquid crystal polymer A-04 was used instead of the side chain type liquid crystal polymer A-01, and the side chain type liquid crystal polymer A-04 and the polymerizability Liquid crystal composition 7 of Example 7 was obtained in the same manner as in Example 1 (1), except that the amount of the liquid crystal compound added was changed to that shown in Table 2.

(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, the substrate 3 used in Example 4 was used instead of the substrate 1, and the liquid crystal composition A retardation film or a transfer laminate of Example 7 was obtained in the same manner as in (2) of Example 1, except that product 7 was used.

(Example 8)
The liquid crystal composition 6 obtained in Example 6 was coated on a glass substrate using a spin coater while adjusting the flow rate during coating so that the film thickness after curing was 1 μm to form a film. Then, after drying at 85° C. for 60 seconds, ultraviolet rays were irradiated at an irradiation dose of 120 mJ/cm ² to form a retardation layer, and a retardation film or a transfer laminate of Example 8 was obtained.
The surface free energy of the glass substrate used was calculated in the same manner as for substrate 1 and was 68 mJ/m ² .

(Example 9)
The liquid crystal composition 6 obtained in Example 6 was coated on a stainless steel substrate using a spin coater while adjusting the flow rate during coating so that the film thickness after curing was 1 μm. Then, after drying at 85° C. for 60 seconds, the film was irradiated with ultraviolet rays at an irradiation dose of 120 mJ/cm ² to form a retardation layer, thereby obtaining a retardation film or a transfer laminate of Example 9.
The surface free energy of the stainless steel substrate used was calculated in the same manner as for Substrate 1 and was 53 mJ/m ² .

(Example 10)
(1) Preparation of liquid crystal composition Example 1 (1) was the same as in Example 1 (1) except that the side chain type liquid crystal polymer A-05 was used instead of the side chain type liquid crystal polymer A-01. Liquid crystal composition 10 of Example 10 was obtained in the same manner.

(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, the substrate 3 used in Example 4 was used instead of the substrate 1, and the liquid crystal composition A retardation film or a transfer laminate of Example 10 was obtained in the same manner as in Example 1 (2) except that the product 10 was used.

(Example 11)
(1) Preparation of liquid crystal composition Example 1 (1) was the same as in Example 1 (1) except that the side chain type liquid crystal polymer A-06 was used instead of the side chain type liquid crystal polymer A-01. Liquid crystal composition 11 of Example 11 was obtained in the same manner.

(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, the substrate 3 used in Example 4 was used instead of the substrate 1, and the liquid crystal composition A retardation film or a transfer laminate of Example 11 was obtained in the same manner as in Example 1 (2) except that the product 11 was used.

(Example 12)
In (1) of Example 1, a side chain type liquid crystal polymer A-06 was used instead of the side chain type liquid crystal polymer A-01, and the addition amounts of the side chain type liquid crystal polymer A-06 and the polymerizable liquid crystal compound are shown in Table 2. A liquid crystal composition 12 of Example 12 was obtained in the same manner as in Example 1 (1), except that the amounts shown in 1) were used.

(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, the substrate 3 used in Example 4 was used instead of the substrate 1, and the liquid crystal composition A retardation film or a transfer laminate of Example 12 was obtained in the same manner as in Example 1 (2) except that the product 12 was used.

(Example 13)
(1) Preparation of liquid crystal composition Example 1 (1) was the same as in Example 1 (1) except that the side chain type liquid crystal polymer A-07 was used instead of the side chain type liquid crystal polymer A-01. Liquid crystal composition 13 of Example 13 was obtained in the same manner.

(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, the substrate 3 used in Example 4 was used instead of the substrate 1, and the liquid crystal composition A retardation film or a transfer laminate of Example 13 was obtained in the same manner as in Example 1 (2) except that the product 13 was used.

(Example 14)
(1) Preparation of liquid crystal composition Example 1 (1) was the same as in Example 1 (1) except that the side chain type liquid crystal polymer A-08 was used instead of the side chain type liquid crystal polymer A-01. Liquid crystal composition 14 of Example 14 was obtained in the same manner.

(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, the substrate 3 used in Example 4 was used instead of the substrate 1, and the liquid crystal composition A retardation film or a transfer laminate of Example 14 was obtained in the same manner as in Example 1 (2) except that the product 14 was used.

(Example 15)
(1) Preparation of liquid crystal composition In (1) of Example 1, the side chain type liquid crystal polymer A-08 was used instead of the side chain type liquid crystal polymer A-01, and the side chain type liquid crystal polymer A-08 and the polymerizability A liquid crystal composition 15 of Example 15 was obtained in the same manner as in Example 1 (1), except that the amount of the liquid crystal compound added was changed to that shown in Table 2.

(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, the substrate 3 used in Example 4 was used instead of the substrate 1, and the liquid crystal composition A retardation film or a transfer laminate of Example 15 was obtained in the same manner as in (2) of Example 1, except that the product 15 was used.

(Comparative example 1)
(1) Preparation of liquid crystal composition Example 1 (1) except that side chain type liquid crystal polymer A-09 was used instead of side chain type liquid crystal polymer A-01 in Example 1 (1). Comparative liquid crystal composition 1 of Comparative Example 1 was obtained in the same manner.

(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, the substrate 2 used in Example 3 was used instead of the substrate 1, and the comparative liquid crystal was used instead of the liquid crystal composition 1. A retardation film or a transfer laminate of Comparative Example 1 was obtained in the same manner as in Example 1 (2) except that Composition 1 was used.

(Comparative example 2)
(1) Preparation of Liquid Crystal Composition The same as Comparative Liquid Crystal Composition 1 of Comparative Example 1 was used.
(2) Preparation of retardation film or laminate for transfer In (2) of Example 1, the substrate 3 used in Example 4 was used instead of the substrate 1, and the comparative liquid crystal was used instead of the liquid crystal composition 1. A retardation film or a transfer laminate of Comparative Example 2 was obtained in the same manner as in Example 1 (2) except that Composition 1 was used.

[evaluation]
The retardation film or transfer laminate obtained in each example and each comparative example was transferred to a glass plate with an adhesive layer (100 mm × 100 mm), and the substrate was peeled off, so that it was placed on the glass plate with an adhesive layer. A measurement sample having a laminated retardation layer was obtained. The following evaluation was performed using the obtained measurement sample.

<Applicability>
The measurement sample was observed visually and under crossed Nicols using a polarizing microscope, and the applicability was evaluated based on the following evaluation criteria. Table 2 shows the evaluation results.
[Applicability Evaluation Criteria]
A: In the range of 100 mm × 100 mm, there is almost no repelling, and the liquid crystalline component is uniformly oriented. B: In the range of 100 mm × 100 mm, very slight repelling or bright portions with a diameter of less than 1.0 mm are observed. , No practical problem C: In the range of 100 mm × 100 mm, a slight repelling or bright part with a diameter of 1.0 mm or more and less than 3.0 mm is observed D: In the range of 100 mm × 100 mm, a diameter of 3.0 mm or more Repelling is seen, or crystals precipitate and bright crystal parts are seen

<Vertical orientation>
The measurement sample was visually observed under crossed Nicols, and the vertical alignment property was evaluated based on the following evaluation criteria. Table 2 shows the evaluation results.
[Orientation Evaluation Criteria]
A: There is no white part in the range of 100 mm × 100 mm B: There is a very small amount of white part in the range of 100 mm × 100 mm, but the total white part is 3% or less, and there is no practical problem C: Within the range of 100 mm x 100 mm, the total white part is more than 3% and 10% or less D: The total white part is more than 10% within the range of 100 mm x 100 mm

<Heat resistance>
The measurement sample was heated at 80° C. and a humidity of 90% RH for 1 hour, and the thickness phase difference Rth(550) at a measurement wavelength of 550 nm before and after heating was measured. Using the measured values, the retardation change rate (%) after heating calculated by the following formula was calculated, and the heat resistance was evaluated according to the following evaluation criteria. Table 2 shows the evaluation results.
Retardation change rate after heating (%) = {(Rth before heating - Rth after heating) / Rth before heating} x 100
(Evaluation criteria)
A: The retardation variation rate after heating was less than 15% B: The retardation variation rate after heating was 15% or more In addition, in Comparative Example 2, the retardation layer was not oriented and was completely whitened. Therefore, since Rth could not be measured, the phase difference fluctuation rate could not be obtained.

[Summary of results]
From the results in Table 2, a non-liquid crystalline structural unit having a structure represented by the general formula (I) and having an SP value of 9.25 (cal/cm ³ ) ^1/2 or more and a liquid crystalline portion In Examples 1 to 15 in which a copolymer having a liquid crystalline structural unit having a side chain containing was used as a side chain type liquid crystal polymer, the coating properties of the liquid crystal composition on the substrate were excellent, so the retardation layer was repelled. The liquid crystalline component was suppressed and oriented uniformly, and the vertical orientation and heat resistance were also excellent. Further, in Examples 12 and 15 using a side chain type liquid crystal polymer having a higher SP value of the non-liquid crystalline structural unit, even if the content of the side chain type liquid crystal polymer is small, the coating properties on the substrate and the retardation layer are improved. Since the vertical alignment property was maintained, the use of a side-chain type liquid crystal polymer having a higher SP value of the non-liquid crystalline structural unit can improve the applicability to the substrate, and furthermore, the vertical alignment of the retardation layer to be formed can be improved. It has been clarified that the orientation can be improved.
On the other hand, in Comparative Examples 1 and 2, the side chain type liquid crystal polymer has the structure represented by the general formula (I) and the SP value is 9.25 (cal/cm ³ ) ^1/2 or more. Since it did not have a non-liquid crystalline structural unit, the coating properties of the liquid crystal composition were poor, repelling and the like were observed in the retardation layer, and the vertical alignment property and heat resistance of the retardation layer were also inferior.

1 Retardation Layers 2, 2' Substrate 3 Substrate 4 Surface Adjustment Layer 5 Alignment Films 10, 10', 10'' Retardation Films 11, 21, 31 Retardation Layers 12, 22 Substrates 13, 23 Surface Adjustment Layer 14, 24, 34 supports 15, 25, 35 peelable support layers 16, 26, 36 transfer layer 17 interface 27 between surface adjustment layer and retardation layer interface 20, 30, 40 between substrate and surface adjustment layer for transfer Laminated body 50 Polarizing plate 60 Optical member 71 Transparent electrode layer 72 Light-emitting layer 73 Electrode layer 100 Light-emitting display device

Claims (9)

Containing a side chain type liquid crystal polymer, a polymerizable liquid crystal compound, and a photopolymerization initiator,
The side chain type liquid crystal polymer has a structure represented by the following general formula (I) and has a non-liquid crystal structural unit with an SP value of 9.25 (cal/cm ³ ) ^1/2 or more; and a liquid crystalline structural unit having a side chain containing a moiety,
A liquid crystal composition, wherein the mass ratio of the side chain type liquid crystal polymer to the total mass of the side chain type liquid crystal polymer and the polymerizable liquid crystal compound is 2% by mass or more and 20% by mass or less.

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a group represented by -R ⁴ -XY-R ⁵ , R ⁴ has 1 or more carbon atoms and 22 Represents the following alkylene groups, R ⁵ represents an alkyl group having 1 to 9 carbon atoms, at least one of R ⁴ and R ⁵ has a straight chain structure having 3 or more carbon atoms, X represents —O—, —C (=O)-O-, -O-C(=O)-, -O-CH ₂ -, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or represents a linking group represented by -OC(=O)-CH=CH-, Y represents a 1,4-phenylene group or a 1,4-cyclohexylene group. A phenylene group may be substituted with one or more non-adjacent -CH= by -N=, and a 1,4-cyclohexylene group may be substituted with one or more non-adjacent -CH ₂ - may be substituted by -O- or -S-, and the 1,4-phenylene group and 1,4-cyclohexylene group have at least one substituent selected from a halogen atom, a cyano group and a nitro group. However, the group represented by -R ⁴ -XY-R ⁵ contains at least one structure selected from the group consisting of the following (i) to (iii).
(i) the X represents a linking group represented by -C(=O)-O- or -OC(=O)-;
(ii) in Y, the 1,4-phenylene group has one or two or more non-adjacent -CH= substituted with -N=;
(iii) The 1,4-phenylene group and 1,4-cyclohexylene group have at least one substituent selected from halogen atoms, cyano groups and nitro groups. ) A retardation film having a retardation layer,
The retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, the side chain type liquid crystal polymer has a structure represented by the following general formula (I), and has an SP value of 9.0. 25 (cal/cm ³ ) ^1/2 or more having a non-liquid crystalline structural unit and a liquid crystalline structural unit having a side chain containing a liquid crystalline portion, the side chain type liquid crystalline polymer and the polymerizable liquid crystal compound A retardation film comprising a cured product of a liquid crystal composition, wherein the side chain type liquid crystal polymer has a mass ratio of 2% by mass or more and 20% by mass or less with respect to the total mass of.

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a group represented by -R ⁴ -XY-R ⁵ , R ⁴ has 1 or more carbon atoms and 22 Represents the following alkylene groups, R ⁵ represents an alkyl group having 1 to 9 carbon atoms, at least one of R ⁴ and R ⁵ has a straight chain structure having 3 or more carbon atoms, X represents —O—, —C (=O)-O-, -O-C(=O)-, -O-CH ₂ -, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or represents a linking group represented by -OC(=O)-CH=CH-, Y represents a 1,4-phenylene group or a 1,4-cyclohexylene group. A phenylene group may be substituted with one or more non-adjacent -CH= by -N=, and a 1,4-cyclohexylene group may be substituted with one or more non-adjacent -CH ₂ - may be substituted by -O- or -S-, and the 1,4-phenylene group and 1,4-cyclohexylene group have at least one substituent selected from a halogen atom, a cyano group and a nitro group. However, the group represented by -R ⁴ -XY-R ⁵ contains at least one structure selected from the group consisting of the following (i) to (iii).
(i) the X represents a linking group represented by -C(=O)-O- or -OC(=O)-;
(ii) in Y, the 1,4-phenylene group has one or two or more non-adjacent -CH= substituted with -N=;
(iii) The 1,4-phenylene group and 1,4-cyclohexylene group have at least one substituent selected from halogen atoms, cyano groups and nitro groups. ) having a substrate and the retardation layer on the substrate;
3. The retardation film according to claim 2, wherein the surface of the substrate on the retardation layer side has a surface free energy of 30 mJ/m< ² > or more. preparing a substrate having a surface free energy of 30 mJ/m ² or more on at least one surface;
forming a film of the liquid crystal composition according to claim 1 on the surface of the substrate;
a step of aligning the liquid crystal constitutional units of the side chain type liquid crystal polymer in the formed liquid crystal composition and the polymerizable liquid crystal compound;
A method for producing a retardation film, comprising a step of polymerizing the polymerizable liquid crystal compound after the orienting step, thereby forming a retardation layer. A retardation layer and a support having a peelable support layer,
The retardation layer contains a side chain type liquid crystal polymer and a polymerizable liquid crystal compound, the side chain type liquid crystal polymer has a structure represented by the following general formula (I), and has an SP value of 9.0. 25 (cal/cm ³ ) ^1/2 or more having a non-liquid crystalline structural unit and a liquid crystalline structural unit having a side chain containing a liquid crystalline portion, the side chain type liquid crystalline polymer and the polymerizable liquid crystal compound A cured product of a liquid crystal composition in which the mass ratio of the side chain type liquid crystal polymer to the total mass of the liquid crystal composition is 2% by mass or more and 20% by mass or less,
A transfer layered product used for transfer of the retardation layer.

(In general formula (I), R ¹ represents a hydrogen atom or a methyl group, R ² represents a group represented by -R ⁴ -XY-R ⁵ , R ⁴ has 1 or more carbon atoms and 22 Represents the following alkylene groups, R ⁵ represents an alkyl group having 1 to 9 carbon atoms, at least one of R ⁴ and R ⁵ has a straight chain structure having 3 or more carbon atoms, X represents —O—, —C (=O)-O-, -O-C(=O)-, -O-CH ₂ -, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or represents a linking group represented by -OC(=O)-CH=CH-, Y represents a 1,4-phenylene group or a 1,4-cyclohexylene group. A phenylene group may be substituted with one or more non-adjacent -CH= by -N=, and a 1,4-cyclohexylene group may be substituted with one or more non-adjacent -CH ₂ - may be substituted by -O- or -S-, and the 1,4-phenylene group and 1,4-cyclohexylene group have at least one substituent selected from a halogen atom, a cyano group and a nitro group. However, the group represented by -R ⁴ -XY-R ⁵ contains at least one structure selected from the group consisting of the following (i) to (iii).
(i) the X represents a linking group represented by -C(=O)-O- or -OC(=O)-;
(ii) in Y, the 1,4-phenylene group has one or two or more non-adjacent -CH= substituted with -N=;
(iii) The 1,4-phenylene group and 1,4-cyclohexylene group have at least one substituent selected from halogen atoms, cyano groups and nitro groups. ) 6. The transfer laminate according to claim 5, wherein the surface of the support on the side of the retardation layer has a surface free energy of 30 mJ/m< ² > or more. An optical member comprising a polarizing plate on the retardation film according to claim 2 or 3. A step of preparing the transfer laminate according to claim 5 or 6;
A transfer step of placing a transfer target including at least a polarizing plate and the retardation layer of the transfer laminate to face each other, and transferring the transfer laminate onto the transfer target;
and a peeling step of peeling the peelable support layer from the transfer laminate transferred onto the transferred body. 4. A display device comprising the retardation film according to claim 2 or 3, or an optical member comprising a polarizing plate on the retardation film.

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