JP2018151535A - Phase difference film, transfer laminate, optical member, method for producing optical member, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phase difference film that can control a phase difference in the film plane and a phase difference in the film thickness direction with a single phase difference layer, and can achieve reduction of the film thickness, an optical member including the phase difference film, and a display device including the phase difference film or the optical member.SOLUTION: A phase difference film 10 contains a horizontal oriented film 11, and a phase difference layer 12 on the horizontal oriented film, the phase difference layer containing a cured product of a polymerizable liquid crystal composition containing a homeotropic oriented side chain liquid crystal polymer and a polymerizable bar-like liquid crystal compound.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a retardation film, a transfer laminate, an optical member, a method for producing an optical member, and a display device.

  Conventionally, regarding a display device such as a liquid crystal display device or a light emitting display device, a configuration in which various optical members are arranged on a panel surface has been proposed. As the optical member, for example, an optical member that secures desired optical characteristics by giving a desired phase difference to transmitted light is provided.

For example, in an image display device such as a liquid crystal display device, a technique has been proposed in which a retardation film is disposed in a liquid crystal cell and optical angle characteristics based on birefringence are compensated to improve viewing angle characteristics.
As such a retardation film, for example, a stretched film by uniaxial or biaxial stretching, or a retardation film in which a retardation layer is provided by a liquid crystal layer in which a liquid crystal material is aligned is used.

  In addition, a retardation film in which a liquid crystal film is further laminated on a stretched film has been proposed. For example, Patent Document 1 discloses a homeotropic alignment side chain liquid crystal polymer or the side chain liquid crystal polymer and a photopolymerizable liquid crystal compound. A phase difference plate is described in which a homeotropic alignment liquid crystal film formed from a homeotropic alignment liquid crystalline composition is contained and a stretched film having a retardation function is laminated and integrated.

JP 2003-149441 A

In such a retardation film, it is desired to obtain desired optical characteristics by controlling the retardation.
However, in the case of a stretched film, since there is a limit to stretching in the thickness direction, it is difficult to control the retardation in the film thickness direction.
The retardation plate described in Patent Document 1 is obtained by laminating and integrating a homeotropic alignment liquid crystal film having a retardation in the film thickness direction on a stretched film having a film in-plane retardation. In Patent Document 1, it is a liquid crystal film prepared without using an alignment film. Such a liquid crystal film has an in-plane retardation of the liquid crystal film itself of almost zero, and controls only the retardation in the thickness direction. For example, in Example 1 of Patent Document 1, it is described that the homeotropic alignment liquid crystal film was nx: 1.5315, ny: 1.5314, nz: 1.6472, and the Nz factor of the liquid crystal film itself was − 1157. The retardation plate of Patent Document 1 controls the retardation in the thickness direction by adjusting the thickness of the homeotropic alignment liquid crystal film with respect to a stretched film having a film in-plane retardation, and stretching. Since the thickness of the film affects physical properties, it is difficult to reduce the thickness.

  The embodiment of the present disclosure has been made in view of the above problems, and the retardation in the film plane and the retardation in the film thickness direction can be controlled by a single retardation layer, which corresponds to thinning. It is an object to provide a retardation film, an optical member including the retardation film, and a display device including the retardation film or the optical member.

One embodiment of the present disclosure is:
A horizontal alignment film;
Provided is a retardation film having a retardation layer containing a cured product of a polymerizable liquid crystal composition containing a homeotropic alignment side-chain liquid crystal polymer and a polymerizable rod-like liquid crystal compound on the horizontal alignment film. To do.

One embodiment of the present disclosure is:
A support;
On the support, a horizontal alignment film,
A retardation layer containing a cured product of a polymerizable liquid crystal composition containing a homeotropic alignment side-chain liquid crystal polymer and a polymerizable rod-like liquid crystal compound on the horizontal alignment film,
Provided is a transfer laminate for at least transfer of the retardation layer.

  In one embodiment of the present disclosure, the homeotropic alignment side chain liquid crystal polymer has a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II). A retardation film or a laminate for transfer containing a copolymer is provided.

(In General Formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is represented by — (CH ₂ ) _n —R ³ , or — (C ₂ H ₄ O) _{n ′} -R ^4. R ³ represents a methyl group which may have a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or —OR ⁵ , —O—C (═O) R ⁵ or —C (═O) —OR ⁵ , wherein R ⁴ and R ⁵ each independently have 1 to 10 carbon atoms which may have a substituent. An aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a combination thereof, n is an integer of 2 to 22 and n ′ Is an integer from 1 to 6.
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 ¹ is a direct bond, or —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, — NR ¹⁴ —C (═O) —, —C (═O) —NR ¹⁴ —, —O—C (═O) —NR ¹⁴ —, —NR ¹⁴ —C (═O) —O—, —NR ¹⁴ In the linking group represented by —C (═O) —NR ¹⁴ —, —O—NR ¹⁴ —, or —NR ¹⁴ —O—, Ar ¹ has 6 carbon atoms which may have a substituent. The number of aromatic hydrocarbon groups is 10 or less, and a plurality of L ¹ and Ar ¹ may be the same or different. R ¹³ is —F, —Cl, —CN, —OCF ₃ , —OCF ₂ H, —NCO, —NCS, —NO ₂ , —NHC (═O) —R ¹⁵ , —C (═O) —OR ¹⁵ , —OH, —SH, —CHO, —SO ₃ H, —NR ¹⁵ ₂ , —R ¹⁶ , or —OR ¹⁶ , wherein R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or 1 to 6 carbon atoms. R ¹⁶ represents an alkyl group having 1 to 6 carbon atoms. 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. )

In one embodiment of the present disclosure, the Nz factor (Nz) represented by the following formula (1) of the retardation layer is in the range of −10 <Nz <1, or the retardation film or the transfer layer A laminate is provided.
Formula (1) Nz = (nx−nz) / (nx−ny)
(In formula (1), nx is the in-plane slow axis direction refractive index, ny is the in-plane fast axis direction refractive index, and nz is the thickness direction refractive index.)

  One embodiment of the present disclosure provides an optical member having the retardation film of one embodiment of the present disclosure described above and at least one optical film.

One embodiment of the present disclosure includes a transfer laminate preparing step of preparing the transfer laminate of one embodiment of the present disclosure described above,
A transfer step in which a transfer object including at least one optical film is opposed to the retardation layer of the transfer laminate, and the transfer laminate is transferred onto the transfer object;
And a peeling step of peeling the support or the support and the horizontal alignment film from the transfer laminate transferred onto the transfer object.

  One embodiment of the present disclosure provides a display device including the retardation film of one embodiment of the present disclosure described above or the optical member of one embodiment of the present disclosure described above.

  In an embodiment of the present disclosure, a retardation film capable of controlling a retardation in a film plane and a retardation in a film thickness direction by a single retardation layer, and capable of corresponding to a thin film, the retardation An optical member provided with a film, and a display device provided with the retardation film or the optical member can be provided.

It is a schematic sectional drawing which shows an example of the retardation film of this indication. It is a schematic sectional drawing which shows an example of the laminated body for transfer of this indication. It is a schematic sectional drawing which shows another example of the laminated body for transfer of this indication. It is a schematic sectional drawing which shows an example of the optical member of this indication. It is a schematic sectional drawing which shows another example of the optical member of this indication. It is a schematic sectional drawing which shows an example of the manufacturing method of the optical member of this indication. It is a schematic sectional drawing which shows another example of the manufacturing method of the optical member of this indication.

Hereinafter, embodiments and examples 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 modes, and should not be construed as being limited to the description of the embodiments and examples illustrated below. In addition, the drawings may be schematically represented with respect to the width, thickness, shape, and the like of each part in comparison with actual aspects for clarity of explanation, but are merely examples, and the interpretation of the present disclosure may be interpreted. It is not limited. In addition, in the present specification and each drawing, elements similar to those described above with reference to the previous drawings are denoted by the same reference numerals, and detailed description may be omitted as appropriate. Further, for convenience of explanation, the description may be made using the terms “upper” or “lower”, but the vertical direction may be reversed.
In this specification, when a certain configuration such as a certain member or a certain region is “above (or below)” another configuration such as another member or another region, unless otherwise specified This includes not only when directly above (or directly below) other configurations, but also when above (or below) other configurations, i.e. This includes cases where components are included.

In this specification, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
Further, in the present specification, the terms “plate”, “sheet”, and “film” are not distinguished from each other only based on the difference in designations, and are referred to as “film surface (plate surface, sheet surface)”. Is a surface that coincides with the plane direction of the target film-like member (plate-like member, sheet-like member) when the target film-like (plate-like, sheet-like) member is viewed overall and globally. Refers to that.

The horizontal alignment film refers to a film that aligns the liquid crystal material substantially horizontally with respect to the horizontal alignment film surface (film surface). The homogeneous alignment refers to the alignment direction of the liquid crystal material substantially horizontal to the film surface. However, these are not strictly required to be parallel to the film surface, and horizontal alignment means that the average inclination angle of the director of the liquid crystal material with respect to the film surface is 0 ° to 30 °. It refers to the case of about 0 ° or less, preferably 0 ° to 20 °, more preferably 0 ° to 10 °.
In addition, homeotropic alignment refers to an alignment state in which the alignment direction of the liquid crystal material is substantially perpendicular to the film surface, but does not require that the liquid crystal material is strictly perpendicular. The average inclination angle of the director of the material is about 60 ° to 90 °, preferably 70 ° to 90 °, more preferably 80 ° to 90 °.

  Hereinafter, a retardation film of the present disclosure and a manufacturing method thereof, a transfer laminate used for transfer of a retardation layer included in the retardation film, an optical member including the retardation film, a manufacturing method of the optical member, and the position A display device provided with a phase difference film or the optical film will be described in detail.

A. Retardation film The retardation film of the present disclosure includes a horizontal alignment film,
On the said horizontal alignment film, it has a retardation layer containing the hardened | cured material of the polymeric liquid crystal composition containing a homeotropic alignment side chain type liquid crystal polymer and a polymeric rod-shaped liquid crystal compound.

The retardation film of the present disclosure will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view illustrating an example of the retardation film of the present disclosure. The retardation film 10 illustrated in FIG. 1 includes a horizontal alignment film 11 and a retardation layer 12 on the horizontal alignment film 11.

In the retardation film of the present disclosure, the retardation in the film plane and the retardation in the film thickness direction can be controlled by one retardation layer. This is because the homeotropic alignment side-chain liquid crystal polymer contained in the retardation layer controls the retardation in the direction perpendicular to the film surface, that is, in the film thickness direction, as described below. This is considered to be due to controlling the phase difference in the horizontal direction with respect to the film surface, that is, in the film in-plane direction.
Since the homeotropic alignment side chain type liquid crystal polymer is a polymer, it has a strong homeotropic alignment, is hardly affected by the horizontal alignment film, and is easily aligned in the direction perpendicular to the film surface. It is considered that the retardation in the film thickness direction can be controlled by changing the amount of the oriented side chain type liquid crystal polymer added. On the other hand, the polymerizable rod-like liquid crystal compound is easily oriented in the horizontal direction with respect to the film surface due to the influence of the horizontal alignment film, and therefore by changing the addition amount of the polymerizable rod-like liquid crystal compound, the in-plane direction of the film It is considered that the phase difference can be controlled. In addition, the retardation film of the present disclosure includes a relatively high molecular homeotropic alignment side chain type liquid crystal polymer that is not easily affected by the horizontal alignment film, and a relatively low molecular weight polymerizable rod-shaped that is easily affected by the horizontal alignment film. By using a combination of liquid crystal compounds, a retardation layer having desired physical properties can be stably produced. For example, when a homeotropically oriented low-molecular liquid crystal compound and a homogeneously oriented low-molecular liquid crystal compound are used in combination, both are affected by the alignment film, so that a retardation layer exhibiting the desired physical properties can be stably produced. It is difficult to do.
In addition, since the retardation film of the present disclosure can control the retardation in the film plane and the retardation in the film thickness direction by a single retardation layer, the stretched film can be used for retardation control in the film plane. There is no need to use it, and it can cope with thinning.
In the retardation film of the present disclosure, it is preferable that the polymerizable rod-like liquid crystal compound has a retardation layer adjacent to the horizontal alignment film from the viewpoint of being easily aligned in the horizontal direction under the influence of the horizontal alignment film. .
Hereinafter, each configuration of the retardation film of the present disclosure will be described.

1. Retardation Layer The retardation layer of the present disclosure contains a cured product of a polymerizable liquid crystal composition containing a homeotropic alignment side chain type liquid crystal polymer and a polymerizable rod-like liquid crystal compound.

  The polymerizable liquid crystal composition used in the present disclosure contains a homeotropic alignment side chain type liquid crystal polymer and a polymerizable rod-like liquid crystal compound, and further contains a photopolymerization initiator and other components as necessary.

(1) Homeotropic alignment side chain type liquid crystal polymer The homeotropic alignment side chain type liquid crystal polymer used in the present disclosure is capable of realizing homeotropic alignment. The retardation layer of the present disclosure can control the retardation in the direction perpendicular to the film surface, that is, in the film thickness direction, by changing the amount of homeotropic alignment side chain type liquid crystal polymer added.

The homeotropic alignment side chain type liquid crystal polymer is not particularly limited as long as it can exhibit homeotropic alignment without using a vertical alignment film.
The homeotropic alignment side chain type liquid crystal polymer is, for example, a liquid crystal polymer that exhibits a liquid crystal phase such as a nematic phase or a smectic phase. A liquid crystal polymer is preferable.

  The orientation of the liquid crystal polymer can be determined by whether or not the liquid crystalline polymer takes homeotropic orientation in a liquid crystal state when a polymer film is formed on a glass substrate and heat-treated at the liquid crystal temperature. These substrates are used after the surface is cleaned with an acid, alcohol, detergent or the like, but are used without performing a surface treatment such as a silicon treatment. Since some polymers are specifically homeotropically aligned at a temperature in the vicinity of the liquid crystal phase-isotropic phase transition point, the heat treatment operation is usually 15 ° C. or less, preferably 20 ° C. from the liquid crystal phase-isotropic phase transition temperature. Perform at the following temperature.

Examples of the homeotropic alignment side chain type liquid crystal polymer include polymers having a liquid crystalline constitutional unit containing a mesogen in the side chain.
The liquid crystalline structural unit is a structural unit derived from a compound exhibiting liquid crystallinity in which a polymerizable group is bonded to a mesogenic group via a spacer (hereinafter sometimes referred to as a liquid crystal monomer). In the present disclosure, the mesogen refers to a portion having high rigidity that exhibits liquid crystallinity. For example, the mesogen has two or more ring structures, preferably three or more ring structures, and the ring structures are directly bonded to each other. Examples thereof include a partial structure in which the ring structures are connected to each other via 1 to 3 atoms. By having such a mesogen in the side chain, the liquid crystalline structural unit is easily vertically aligned.
The ring structure may be an aromatic ring such as benzene, naphthalene or anthracene, or may be a cyclic aliphatic hydrocarbon such as cyclopentyl or cyclohexyl.
In addition, when the ring structure is connected through 1 atom to 3 atoms, examples of the structure of the connecting portion include -O-, -S-, -OC (= O)-, -C. (═O) —O—, —O—C (═O) —O—, —NR′—C (═O) —, —C (═O) —NR′—, —O—C (═O) -NR'-, -NR'-C (= O) -O-, -NR'-C (= O) -NR'-, -O-NR'-, -NR'-O-, -CH = CH -, -C≡C-, -N = N- and the like (R 'is an alkyl group). Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms, and among them, linear or branched alkyl groups having 1 to 3 carbon atoms are preferable. Here, in the case where the ring structure is connected through 1 atom to 3 atoms, like the atoms put in “” of “N” R ′ — “C” (═O) — “O” — The number of atoms connected in series at the connecting part is counted.
Among them, the mesogen is preferably a rod-like mesogen that is connected at the para-position for benzene and at the 2- and 6-positions for naphthalene so that the ring structure is connected in a rod shape.

In addition, the structural unit containing a mesogen exhibiting liquid crystallinity in the side chain preferably has a polar group at the end of the side chain of the structural unit, an alkyl group, or an alkoxy group from the viewpoint of vertical alignment. Examples of the polar group, for _{example, -F, -Cl, -CN, -OCF} 3, -OCF 2 H, -NCO, -NCS, -NO 2, -NHC (= O) -R ", - C (= O ) -OR ", - OH, -SH , -CHO, -SO 3 H, -NR" 2 (R " can be mentioned a hydrogen atom or a hydrocarbon group). Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 6 carbon atoms. Examples of the alkoxy group include linear, branched or cyclic alkoxy groups having 1 to 6 carbon atoms.
Examples of the liquid crystalline structural unit in the side chain type liquid crystal polymer include HJ Neumann, M. Jarek, and GP Hellmann Macromolecules, 26, 2489-2495, (1993) and International Publication 2004/113469, p. A liquid crystalline structural unit derived from a conventionally known liquid crystal monomer as described in 8 to 10 may be appropriately selected and used.

  Moreover, it is preferable that the structural unit which comprises the said homeotropic alignment side chain type liquid crystal polymer is a structural unit induced | guided | derived from the monomer which has an ethylenic double bond containing group which can mutually be polymerized. Examples of such a monomer having an ethylenic double bond-containing group include derivatives such as (meth) acrylic acid ester, styrene, (meth) acrylamide, maleimide, vinyl ether, and vinyl ester. A structural unit derived from an acrylate derivative is preferable from the viewpoint of vertical alignment.

As the homeotropic alignment side chain type liquid crystal polymer, from the viewpoint of improving the vertical alignment of the liquid crystalline structural unit, among them, a structural unit not containing a mesogen in the side chain and a liquid crystalline structural unit containing a mesogen in the side chain Are preferred.
In this case, the content ratio of the liquid crystalline structural unit containing mesogen in the side chain in the copolymer is such that the vertical alignment of the liquid crystalline structural unit is improved and the entire copolymer is obtained from the point of sufficient liquid crystal alignment. When it is 100 mol%, it is preferably set within the range of 40 mol% to 80 mol%, and more preferably within the range of 50 mol% to 75 mol%.
Further, the content ratio of the structural unit not containing a mesogen in the side chain is such that when the whole copolymer is 100 mol% from the viewpoint of improving the vertical alignment of the liquid crystalline structural unit and having sufficient liquid crystal alignment. It is preferably set within a range of 20 mol% to 60 mol%, and more preferably within a range of 25 mol% to 50 mol%.
In addition, the content rate of each structural unit in a copolymer can be computed from the integrated value by < ¹ > H NMR measurement.

  As the copolymer, among them, as a structural unit not containing a mesogen in the side chain, it has a structural unit represented by the following general formula (I), and as a liquid crystalline structural unit containing a mesogen in the side chain, the following general formula A copolymer having a structural unit represented by (II) is preferred.

(In General Formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is represented by — (CH ₂ ) _n —R ³ , or — (C ₂ H ₄ O) _{n ′} -R ^4. R ³ represents a methyl group which may have a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or —OR ⁵ , —O—C (═O) R ⁵ or —C (═O) —OR ⁵ , wherein R ⁴ and R ⁵ each independently have 1 to 10 carbon atoms which may have a substituent. An aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a combination thereof, n is an integer of 2 to 22 and n ′ Is an integer from 1 to 6.
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 ¹ is a direct bond, or —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, — NR ¹⁴ —C (═O) —, —C (═O) —NR ¹⁴ —, —O—C (═O) —NR ¹⁴ —, —NR ¹⁴ —C (═O) —O—, —NR ¹⁴ In the linking group represented by —C (═O) —NR ¹⁴ —, —O—NR ¹⁴ —, or —NR ¹⁴ —O—, Ar ¹ has 6 carbon atoms which may have a substituent. The number of aromatic hydrocarbon groups is 10 or less, and a plurality of L ¹ and Ar ¹ may be the same or different. R ¹³ is —F, —Cl, —CN, —OCF ₃ , —OCF ₂ H, —NCO, —NCS, —NO ₂ , —NHC (═O) —R ¹⁵ , —C (═O) —OR ¹⁵ , —OH, —SH, —CHO, —SO ₃ H, —NR ¹⁵ ₂ , —R ¹⁶ , or —OR ¹⁶ , wherein R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or 1 to 6 carbon atoms. R ¹⁶ represents an alkyl group having 1 to 6 carbon atoms. 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. )

In the general formula (I), examples of the substituent that the methyl group of R ³ may have include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, and an alkoxy group such as a methoxy group. .

In the general formula (I), examples of the aromatic ring of the aromatic hydrocarbon group having 6 to 10 carbon atoms that may have a substituent of R ³ , R ⁴ and R ⁵ include a benzene ring, A naphthalene ring etc. are mentioned, A benzene ring is especially preferable.
Examples of the substituent that the aromatic hydrocarbon group may have include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a cyano group, a hydroxyl group, an alkyl group, an alkoxy group, and a nitro group. Examples of the alkyl group include those having 1 to 10 carbon atoms, and examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms.

In the general formula (I), the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent of R ⁴ and R ⁵ is linear, branched or cyclic. Of these, a straight chain is preferable. Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, linear alkyl group such as n-decyl group, branched alkyl group such as i-propyl group, i-butyl group and t-butyl group, alkenyl group such as 1-propenyl group and 1-butenyl group, ethynyl group, Alkynyl groups such as 2-propynyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, norbornyl group, adamantyl group and other cycloalkyl groups, 1-cyclohexenyl group, etc. And the like. In the case of the cycloalkyl group, a cycloalkyl group in which a linear alkyl group is substituted, such as an n-propylcyclohexyl group and an n-butylcyclohexyl group, is preferable.
Examples of the substituent which the aliphatic hydrocarbon group may have include, for example, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group. And an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group.

  Examples of combinations of the aliphatic hydrocarbon group and the aromatic hydrocarbon group include a structure in which the aliphatic hydrocarbon group is substituted for the aromatic hydrocarbon group, and the aromatic hydrocarbon group with the aromatic hydrocarbon group. Examples include a structure in which a group is substituted.

R ¹ in the general formula (I) is a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
Further, in R ² in the general formula (I), n is an integer of 2 or more and 22 or less, preferably an integer of 2 or more and 18 or less. N ′ is an integer of 1 or more and 6 or less, and preferably 2 or more and 6 or less.

In addition, from the point that it is easy to form a retardation layer with excellent bending resistance and high in-plane uniformity of retardation value, in the molecule of the copolymer, in R ² in the general formula (I), The linking group represented by — (CH ₂ ) _n — or — (C ₂ H ₄ O) _{n ′} — may contain two or more structural units having different numbers of carbon atoms.
As a combination of R ² of the structural unit represented by the general formula (I) when including two or more structural units having different numbers of carbon atoms of the linking group, for example,
_{(A) - (CH 2)} n1 -R 3 and, _- contains a _{(CH 2)} n2 -R ^3, combined n1 and n2 are different numbers.
_{(B) - (C 2 H} 4 O) n1 '-R 4 _{and,, - (C 2 H 4} O) n2' include -R ^4, combined n1 'and n2' are different numbers.
_{(C) - (CH 2)} n1 -R 3 and,, _{- 'include} -R ^4, n1 and _{n2' (C 2 H 4 O} ) n2 combination number of carbon atoms out that it is a different number.
The above (A), (B), and (C) may further contain a structural unit represented by another general formula (I).
In this case, the plurality of R ³ and the plurality of R ⁴ are independent without depending on the number of n, and the plurality of R ³ and the plurality of R ⁴ may be the same as or different from each other.

In the structural unit represented by the general formula (I), the combination of the values of n and n ′ is not particularly limited, but an alkylene chain or a polyethylene oxide chain is selected from the viewpoint of bending resistance and in-plane uniformity of retardation value. The difference in the number of constituent carbon atoms is preferably 3 or more, and more preferably 5 or more.
The difference in the case, among the two or more n, largest of the n _M, the smallest ones when the n _m, and n _M and n _m specifically having, for example, having different lengths alkylene chain (N _M −n _m ) is preferably 3 or more, and more preferably 5 or more.
In addition, when having polyethylene oxide chains of different lengths, when n ′ _{M is} the maximum and n ′ _m is the minimum of two or more n ′, n ′ _M and n ′ _m The difference (n ′ _M −n ′ _m ) is preferably 2 or more, and more preferably 3 or more.

  In the structural unit represented by the general formula (I), the ratio of two or more structural units having different alkylene chain or polyethylene oxide chain lengths is not particularly limited. The molar ratio of the structural unit having an ethylene oxide chain and the structural unit having an alkylene chain or polyethylene oxide chain having the smallest number of carbon atoms is preferably 1: 9 to 9: 1, and 2: 8 to 8: 2 is more preferable.

In the general formula (I), R ³ represents a methyl group which may have a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or —OR. ⁵ is preferable, and among them, an optionally substituted methyl group or —OR ⁵ is preferable.

In the general formula (I), R ⁴ and R ⁵ are, among others, an aromatic hydrocarbon group substituted with an aliphatic hydrocarbon group having 2 to 10 carbon atoms, or an alkoxy having 2 to 10 carbon atoms. It is preferably an aromatic hydrocarbon group in which the group is substituted or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.

R ⁴ and R ⁵ are linear or branched alkyl groups having 2 or more and 10 or less carbon atoms because the temperature range in which the liquid crystal is aligned is widened and precipitation of the polymerizable liquid crystal compound described later is easily suppressed. May be substituted, or an aromatic hydrocarbon group substituted with a linear or branched alkoxy group having 2 to 10 carbon atoms. More specifically, a phenylene group substituted with a linear or branched alkyl group or alkoxy group having 2 to 10 carbon atoms, a linear or branched alkyl group or alkoxy group having 2 to 10 carbon atoms, Examples thereof include a substituted naphthylene group, a linear or branched alkyl group having 2 to 10 carbon atoms, or a biphenylene group substituted with an alkoxy group.
The linear or branched alkyl group having 2 to 10 carbon atoms is preferably a linear alkyl group having 2 to 10 carbon atoms from the viewpoint of improving the effect, and has 3 to 10 carbon atoms. The following linear alkyl groups are more preferable, and linear alkyl groups having 4 to 10 carbon atoms are even more preferable. The alkoxy group having 2 to 10 carbon atoms is preferably a linear alkoxy group having 2 to 10 carbon atoms, and more preferably a linear alkoxy group having 3 to 10 carbon atoms. A linear alkoxy group having 4 to 10 carbon atoms is more preferable.

  Specific examples of the structural unit represented by the general formula (I) include the following, but are not limited thereto.

R ¹¹ in the general formula (II) is a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
R ¹² in the general formula (II) is a group represented by — (CH ₂ ) _m — or — (C ₂ H ₄ O) _{m ′} —, and above all, represented by — (CH ₂ ) _m —. It is preferred that

M and m ′ of R ¹² are each independently an integer of 2 or more and 10 or less, and from the viewpoint of vertical alignment, m and m ′ are preferably 2 or more and 8 or less, and more preferably 2 or more. It is preferable that it is 6 or less.

L ¹ in the general formula (II) is a direct bond, or —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C ( ═O) —O—, —NR ¹⁴ —C (═O) —, —C (═O) —NR ¹⁴ —, —O—C (═O) —NR ¹⁴ —, —NR ¹⁴ —C (═O) ^{) -O -, - NR 14 -C} (= O) -NR 14 -, - O-NR 14 -, or a linking group represented by ^-NR 14 -O-, among others a direct bond, or, -O A linking group represented by —, —O—C (═O) — or —C (═O) —O— is preferable. L ¹ between two Ar ¹ is preferably a direct bond or a linking group represented by —O—C (═O) — or —C (═O) —O—. .

Ar ¹ in the general formula (II) is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and the aromatic ring of the aromatic hydrocarbon group is Examples thereof include a benzene ring and a naphthalene ring, and among them, a benzene ring is preferable.
In addition to R ¹³ , the aromatic hydrocarbon group may further have a substituent. Examples of the substituent other than R ¹³ that the aromatic hydrocarbon group may have include, for example, a fluorine atom, Examples include halogen atoms such as chlorine and bromine atoms, cyano groups, hydroxyl groups, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, etc. Among them, fluorine atoms, chlorine A halogen atom such as an atom or a bromine atom, or an alkyl group having 1 to 5 carbon atoms is preferred.

R ¹³ in the general formula (II) is preferably a polar group, an alkyl group, or an alkoxy group, and therefore, -F, -Cl, -CN, -OCF ₃ , -OCF ₂ H, -NCO, -NCS, —NO ₂ , —NHC (═O) —R ¹⁵ , —C (═O) —OR ¹⁵ , —OH, —SH, —CHO, —SO ₃ H, —NR ¹⁵ ₂ , —R ¹⁶ , or —OR is ^16, from among them a vertical alignment _{points, -Cl, -CN, -OCF 3,} -OCF 2 H, -NCO, -NCS, -NO 2, -NHC (= O) -R 15, -C ( ═O) —OR ¹⁵ , —OH, —SH, —CHO, —SO ₃ H, —NR ¹⁵ ₂ , —R ¹⁶ , or —OR ¹⁶ , and —Cl, —CN, —OCF ₃ , -C ^{(= O)} -OR 15, and more is possible ^{-R 16,} or ^{-OR 16 Mashiku, -CN, -C (= O)} -OR 15, -R 16, or even more preferably from ^{-OR 16.}

In the general formula (II), R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ¹⁶ represents an alkyl group having 1 to 6 carbon atoms. . In the general formula (II), the alkyl group having 1 to 6 carbon atoms of R ¹⁴ and R ¹⁵ may be linear, branched, or cyclic. For example, a methyl group, an ethyl group, Linear alkyl groups such as n-propyl group, n-butyl group, n-pentyl group and n-hexyl group, branched structures such as i-propyl group, i-butyl group, t-butyl group and 2-methylbutyl group Examples thereof include cycloalkyl groups such as an alkyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Among them, an alkyl group having 1 to 5 carbon atoms is preferable.

  The structural unit represented by the general formula (II) is from the structural units represented by the following general formulas (II-1), (II-2), and (II-3) because of excellent vertical alignment. And at least one selected from the group consisting of structural units represented by the following general formulas (II-1) and (II-2) is preferable.

Here, in the structural units represented by the general formulas (II-1), (II-2), and (II-3), R ¹² and R ¹³ are each R ^{12 in the} general formula (II). , And R ¹³ .

In the present disclosure, the copolymer has a constitution represented by the general formula (I) in addition to the constitutional unit represented by the general formula (I) and the constitutional unit represented by the general formula (II). You may have another structural unit which does not correspond to any of a unit and the structural unit represented by the said general formula (II). By including other structural units in the copolymer, for example, solvent solubility, heat resistance, reactivity, and the like can be improved.
These other structural units may be one kind or two or more kinds.

  The content of the other structural unit in the copolymer is preferably in the range of 0 mol% or more and 30 mol% or less when the entire copolymer is 100 mol%, and 0 mol% or more. More preferably, it is within the range of 20 mol% or less. When the content ratio of the other structural unit is large, the content ratio of the structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) is relatively small, and the vertical alignment property May be difficult to obtain.

  The homeotropic alignment side chain type liquid crystal polymer is a block copolymer having a block part composed of a structural unit containing no mesogen in the side chain and a block part composed of a liquid crystalline structural unit containing a mesogen in the side chain. Alternatively, it may be a random copolymer in which a structural unit containing no mesogen in the side chain and a liquid crystalline structural unit containing mesogen in the side chain are irregularly arranged. In the embodiment of the present disclosure, a random copolymer is preferable from the viewpoint of suppressing vertical alignment of the polymerizable rod-like liquid crystal compound described later and making the retardation layer difficult to break.

The mass average molecular weight Mw of the homeotropic alignment side chain type liquid crystal polymer is not particularly limited, but is preferably in the range of 500 or more and 60000 or less, more preferably in the range of 1000 or more and 50000 or less, and 3000 or more. More preferably, it is within the range of 40,000 or less. By being in the said range, it is excellent in stability of a polymeric liquid crystal composition, and is excellent in the handleability at the time of retardation layer formation. If the massotropic molecular weight of the homeotropic alignment side chain type liquid crystal polymer is too large, compatibility with the polymerizable rod-like liquid crystal compound described later may be deteriorated, and it may be difficult to produce a uniform film.
The mass average molecular weight Mw is a value measured by GPC (gel permeation chromatography).

The method for producing the homeotropic alignment side chain type liquid crystal polymer is not particularly limited. For example, the monomers corresponding to the respective structural units synthesized by a known method are mixed at a desired ratio so as to obtain a desired mass average molecular weight. Can be prepared by polymerization.
In the case of a block copolymer, for example, a monomer that induces a constituent unit that does not contain a mesogen in the side chain and a monomer that induces a liquid crystalline constituent unit that contains a mesogen in the side chain are each obtained by known polymerization means. After polymerization, each polymer obtained may be linked, and either one of a monomer that induces a constituent unit that does not contain a mesogen in the side chain or a monomer that induces a liquid crystalline constituent unit that contains a mesogen in the side chain And a method of further polymerizing by adding the other monomer after polymerization by a known polymerization means.
As the polymerization means, a method generally used for polymerization of a compound having a vinyl group can be employed, and for example, anionic polymerization, living radical polymerization, or the like can be used. In this embodiment, in particular, a method in which polymerization proceeds in a living manner, such as group transfer polymerization (GTP) disclosed in “J. Am. Chem. Soc.” 105, 5706 (1983), is used. Is preferred. According to this method, the molecular weight, the molecular weight distribution, and the like can be easily set in a desired range, so that the properties of the obtained homeotropically oriented side chain type liquid crystal polymer can be made uniform.

  In the present disclosure, the structure of the homeotropic alignment side chain type liquid crystal polymer includes nuclear magnetic resonance spectroscopy (NMR), pyrolysis gas chromatography mass spectrometry (Py-GC-MS), and matrix-assisted laser desorption / ionization time of flight. Analysis can be performed in combination with at least one of the mass spectrometry (MALDI-TOFMS).

The homeotropic alignment side chain type liquid crystal polymer may be used alone or in combination of two or more. In this embodiment, from the viewpoint of stable production and in-plane uniformity, the content ratio of the homeotropic alignment side chain type liquid crystal polymer is the same as the homeotropic alignment side chain type liquid crystal polymer and the polymerizable rod-shaped liquid crystal compound. It is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 1 part by mass or more, and further more preferably 5 parts by mass with respect to 100 parts by mass of the total solid content. The above is preferable. Moreover, from the point which controls the retardation in a film surface and the phase difference of a film thickness direction, it is preferable that it is 80 mass parts or less, It is more preferable that it is 70 mass parts or less, It is 60 mass parts or less. Even more preferred. Since the homeotropic alignment side chain type liquid crystal polymer has a higher alignment regulating force when the molecular weight of the homeotropic alignment side chain type liquid crystal polymer is increased, the addition amount can be reduced.
In the present disclosure, the solid content refers to all components excluding the solvent. For example, even if the polymerizable rod-like liquid crystal compound described later is in a liquid state, it is included in the solid content.

(2) Polymerizable rod-like liquid crystal compound The polymerizable rod-like liquid crystal compound used in the present disclosure can realize homogeneous alignment by using a horizontal alignment film. It is considered that the retardation layer of the present disclosure can control the retardation in the film plane by changing the addition amount of the polymerizable rod-like liquid crystal compound.
Further, when the retardation layer is formed, the polymerizable rod-like liquid crystal compound used in the present disclosure is polymerized, so that the retardation layer of the present disclosure is excellent in durability and also has an adhesive property with a horizontal alignment film described later. Excellent.

The polymerizable rod-like liquid crystal compound is not particularly limited as long as it can exhibit homogeneous alignment by using a horizontal alignment film described later. Moreover, as said polymeric rod-shaped liquid crystal compound, you may use individually by 1 type, and may mix and use 2 or more types.
The polymerizable rod-like liquid crystal compound is, for example, a liquid crystal compound that expresses a liquid crystal phase such as a nematic phase or a smectic phase. Among them, a liquid crystal compound that expresses a nematic phase because it can be regularly arranged. Preferably there is.

Examples of the polymerizable rod-like liquid crystal compound include a polymerizable liquid crystal compound having a mesogen and having a polymerizable group. The mesogen is preferably a rod-shaped mesogen, and the mesogen or rod-shaped mesogen can be the same as the mesogen or rod-shaped mesogen contained in the liquid crystalline structural unit in the side chain liquid crystal polymer.
Examples of the polymerizable group possessed by the polymerizable liquid crystal compound include cyclic ether-containing groups such as oxirane rings and oxetane rings, and ethylenic double bond-containing groups. Among them, it exhibits photocurability and is excellent in handleability. From the viewpoint, an ethylenic double bond-containing group is preferable. Examples of the cyclic ether group include a glycidyl group. Examples of the ethylenic double bond-containing group include a vinyl group, an allyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group. Among these, a (meth) acryloyl group and a (meth) acryloyloxy group Preferably there is.

  Examples of the polymerizable rod-like liquid crystal compound include a compound represented by the following general formula (III) and a compound represented by the following general formula (IV).

(In General Formulas (III) and (IV), Z ¹ , Z ² and Z ³ each independently represent a polymerizable group, and R ²¹ represents — (CH ₂ ) _p —, or — (C ₂ H ₄ O) _{p '-} a group represented ^{by, R 31} _{is, - (CH 2) q -} , or _{- (C 2 H 4 O)} q' - a group represented ^{by, R 32} is, - (CH _{2) r} -, or _{- (OC 2 H 4) r} '- .L 2, L 3 and ^{L 4} represents a group represented by each independently a direct bond, or, -O -, - S-, -O-C (= O) - , - C (= O) -O -, - O-C (= O) -O -, - NR 24 -C (= O) -, - C (= O) - ^{NR 24 -, - O-C} (= O) -NR 24 -, - NR 24 -C (= O) -O -, - NR 24 -C (= O) -NR 24 -, - O-NR 24 - , or a linking group represented by ^-NR 24 -O- Each independently be .Ar ² and Ar ³ represents an aromatic hydrocarbon group having 10 inclusive good six carbon atoms which may have a substituent, a plurality of L ² and Ar ² are each the same And a plurality of L ³ and Ar ³ may be the same or different, and R ²² represents —F, —Cl, —CN, —OCF ₃ , —OCF ₂ H, — NCO, —NCS, —NO ₂ , —NHC (═O) —R ²⁵ , —C (═O) —OR ²⁵ , —OH, —SH, —CHO, —SO ₃ H, —NR ²⁵ ₂ , —R ²⁶ or -OR ²⁶ , R ²⁴ and R ²⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ²⁶ represents an alkyl group having 1 to 6 carbon atoms. B and c are each independently an integer of 2 or more and 4 or less, p, p ′, q, q ′, r and r ′ are each independently an integer of 2 or more and 10 or less.)

In general formulas (III) and (IV), Z ¹ , Z ² and Z ³ each independently represent a polymerizable group. The polymerizable group may be the same as the polymerizable group, and examples thereof include cyclic ether groups such as an epoxy group, a glycidyl group, and an oxetanyl group, and an ethylenic double bond-containing group. Examples of the ethylenic double bond-containing group in Z ¹ , Z ^2, and Z ³ include a vinyl group, an allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, etc. Among them, a (meth) acryloyl group Preferably there is. In addition, some of the hydrogen atoms of the ethylenic double bond-containing group may be substituted with halogen atoms.

In the general formula (III), p, p ′, and q, q ′, r, and r ′ in the general formula (IV) are preferably 2 or more and 8 or less, preferably 2 or more and 6 or less, from the viewpoint of vertical alignment. It is more preferable that it is 2 or more and 5 or less.
L ² , L ³ and L ⁴ in the general formula (III) and the general formula (IV) can be the same as L ¹ in the general formula (II).
Ar ² and Ar ³ in the general formula (III) and the general formula (IV) may be the same as Ar ¹ in the general formula (II).
R ²² in the general formula (III) can be the same as R ¹³ in the general formula (II).

  Examples of the compound represented by the general formula (III) include a compound represented by the following general formula (III-1). Examples of the compound represented by the general formula (IV) include the following general formula: The compound represented by (IV-1) is mentioned.

(In the general formulas (III-1) and (IV-1), R ²¹ , R ²² , R ³¹ , R ³² , L ² , L ³ , L ⁴ , Ar ² , Ar ³ , b, and c are each (As in general formulas (III) and (IV), R ²³ , R ³³ , and R ³⁴ each independently represents a hydrogen atom or a methyl group.)

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

The polymerizable rod-like liquid crystal compound is a compound represented by the general formula (IV) from the viewpoints of excellent homogeneous alignment, excellent durability of the retardation layer, and excellent adhesion to the horizontal alignment film. It is preferable that it is a compound represented by the general formula (IV-1).
Moreover, as a compound represented by the said general formula (IV), it is excellent in homogeneous orientation, and it is excellent in durability of a phase difference layer, and the adhesiveness with a horizontal alignment film from the point which is excellent in following general formula ( Compounds represented by IV-2) are preferred.

(In General Formula (IV-2), Q ¹⁰ and Q ¹¹ and Q ¹² and Q ¹³ are each independently a direct bond, —O—, —O—C (═O) —, —C (═O) — O— or —O—C (═O) —O—, Ar ′ represents a phenylene group or a naphthylene group, R ³³ and R ³⁴ each independently represent a hydrogen atom or a methyl group, q and r. Each independently represents an integer of 2 or more and 10 or less, s represents an integer of 0 or more and 8 or less, and when s is 0, it represents that it is substituted with a hydrogen atom, t represents 0 or 1, (When t is 0, it represents a direct bond.)

In the general formula (IV-2), q and r are each preferably an integer of 2 or more and 6 or less from the viewpoint of excellent horizontal alignment.
In the general formula (IV-2), Q ¹⁰ is preferably —O— or —O—C (═O) —O— from the viewpoint of excellent horizontal orientation.
In the general formula (IV-2), Q ¹¹ is preferably —O—C (═O) — or —C (═O) —O— from the viewpoint of excellent horizontal alignment.
In the general formula (IV-2), Q ¹² is a direct bond, —O—C (═O) — or —C (═O) —O—, from the viewpoint of excellent horizontal orientation. preferable.
In the general formula (IV-2), Q ¹³ is preferably a direct bond, —O—, or —O—C (═O) —O— from the viewpoint of excellent horizontal alignment.

  In addition, preferred 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 to these.

In the embodiment of the present disclosure, the polymerizable rod-like liquid crystal compound may be used alone or in combination of two or more.
The content of the polymerizable rod-like liquid crystal compound contained in the solid content (component other than the solvent) of the polymerizable liquid crystal composition can be appropriately selected according to the desired physical properties of the retardation film, and is not particularly limited. However, from the viewpoint of controlling the retardation in the film plane, and the durability of the retardation layer and the adhesion between the retardation layer and the horizontal alignment film, homeotropic alignment side chain type liquid crystal polymer and polymerizable rod-shaped liquid crystal The total solid content with the compound is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, and the homeotropic orientation. From the point of functioning the side chain type liquid crystal polymer, it is preferably 99.99 parts by mass or less, more preferably 99.9 parts by mass or less, and 99 parts by mass or less. More preferably Ri, more preferably more or less 95 parts by mass.

  Further, the mass ratio of the polymerizable rod-like liquid crystal compound to the homeotropic alignment side chain type liquid crystal polymer may be appropriately selected so as to adjust to desired optical characteristics. From the viewpoint of setting the Nz factor to be within the range of −10 <Nz <1, the mass ratio of the polymerizable rod-like liquid crystal compound to the homeotropic alignment side chain type liquid crystal polymer (mass of polymerizable rod-like liquid crystal compound / homeotropic) The mass of the oriented side chain type liquid crystal polymer) is preferably 0.5 or more, and more preferably 1 or more. The mass ratio is preferably 10,000 or less, more preferably 1000 or less, and even more preferably 500 or less.

(3) Photopolymerization initiator The polymerizable liquid crystal composition may contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and can be appropriately selected from conventionally known ones. Specific examples of such photopolymerization initiators include, for example, aromatic ketones containing thioxanthone, α-aminoalkylphenones, α-hydroxyketones, acylphosphine oxides, oxime esters, 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 polymerization initiators, α-aminoalkylphenone polymerization initiators, α-hydroxyketone polymerization initiators, and oxime ester polymerization initiators is preferable.

  Examples of the acyl phosphine oxide polymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide (for example, 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 the α-aminoalkylphenone polymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), 2- Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (eg Irgacure 369, manufactured by BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] Examples include -1- [4- (4-morpholinyl) phenyl] -1-butanone (Irgacure 379EG, manufactured by BASF).

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

  Examples of the oxime ester polymerization initiator 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: Irgacure OXE-02, manufactured by BASF), 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).

In this embodiment, a photoinitiator can be used individually by 1 type or in combination of 2 or more types.
In this embodiment, the content ratio of the photopolymerization initiator is 0.1 parts by mass or more with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition from the viewpoint of promoting the curing of the polymerizable rod-like liquid crystal compound. It is preferably 1 part by mass or more, more preferably 10 parts by mass or less, and more preferably 8 parts by mass or less from the viewpoint of improving the orientation of the retardation layer.
When the photopolymerization initiator is included in the polymerizable liquid crystal composition of the present embodiment, the total content ratio of the homeotropic alignment side chain type liquid crystal polymer and the polymerizable rod-like liquid crystal compound is 100% solid content of the polymerizable liquid crystal composition. It is preferably 99.9 parts by mass or less, more preferably 99 parts by mass or less, and preferably 90 parts by mass or more from the viewpoint of improving the orientation of the retardation layer. 92 parts by mass or more is more preferable.
Even if the photopolymerization initiator is contained in the polymerizable liquid crystal composition, all of the photopolymerization initiator may be decomposed when irradiated with light in order to react with the polymerizable group of the polymerizable rod-like liquid crystal compound. Some components may not be included in the retardation layer.

(4) Other components The polymerizable liquid crystal composition may further contain other components as long as the effects are not impaired. Specifically, as other components, a leveling agent, an antioxidant, a light stabilizer, and a solvent from the viewpoint of coating properties may be contained. These may be appropriately selected from conventionally known materials.
As the leveling agent, it is preferable to use a fluorine-based or silicone-based leveling agent. Specific examples of the leveling agent include, for example, the Megafac series manufactured by DIC Corporation described in JP2010-122325A, the TSF series manufactured by Momentive Performance Materials Japan, and the Neos Corporation. Examples include the footage series. When using a leveling agent in this embodiment, it is preferable that the content rate shall be 0.001 mass part or more and 5 mass parts or less with respect to 100 mass parts of solid content of the said polymeric liquid crystal composition.

  Further, the retardation layer includes a structure in which at least a part of a polymerizable group of the homeotropic alignment side chain type liquid crystal polymer and the polymerizable rod-like liquid crystal compound contained in the polymerizable liquid crystal composition is polymerized. Can be confirmed by collecting and analyzing the material from the retardation layer. As an analysis method, NMR, IR, GC-MS, XPS, TOF-SIMS, and a combination thereof can be applied.

  The thickness of the retardation layer may be appropriately set depending on the application, and is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.5 μm or more, and the viewpoint of thinning Therefore, it is preferably 5 μm or less, and more preferably 3 μm or less.

  In the retardation film of the present disclosure, the retardation layer may be formed in a pattern. The retardation film of the present disclosure is used as a pattern retardation film corresponding to an arrangement pattern of pixels of a liquid crystal display device capable of displaying a three-dimensional image in a passive manner by forming the retardation layer in a pattern. be able to.

2. Horizontal Alignment Film The horizontal alignment film may be a film that orients the polymerizable rod-like liquid crystal compound contained in the retardation layer substantially horizontally with respect to the horizontal alignment film surface (film surface).
As the horizontal alignment film, conventionally known ones can be appropriately selected and used, for example, an alignment film imparted with an alignment regulating force by a rubbing method, a photo-alignment method, a shaping method, etc., among others, A horizontal alignment film imparted with an alignment regulating force by a rubbing method, a photo alignment method or a shaping method is preferable.

  When the alignment regulating force is applied by the rubbing method, a polymer that expresses the alignment regulating force by rubbing is used for the horizontal alignment film. Examples of the polymer include polyvinyl alcohol, polyimide, polyamide, and derivatives thereof. Among them, polyvinyl alcohol is preferable.

  The method for forming the horizontal alignment film by the rubbing method may be appropriately selected from conventionally known methods. For example, a horizontal alignment film can be obtained by forming a coating film containing the polymer on the transparent substrate and then rubbing it using a known rubbing roller or the like.

  When forming a horizontal alignment film by the photo-alignment method, the photo-alignment composition containing the photo-alignment material which expresses alignment control power by irradiating polarized light is used as a composition for alignment films. The photo-alignment material may be a photodimerization type material or a photoisomerization type material. Specifically, for example, cinnamate, coumarin, benzylidenephthalimidine, benzylideneacetophenone, diphenylacetylene, stilbazole, uracil, quinolinone, maleimide, or a polymer having a cinnamylideneacetic acid derivative, among others, cinnamate and coumarin are used. Of these, polymers having at least one of these and derivatives thereof are preferably used. Specific examples of such a photodimerization type material include, for example, JP-A-9-118717, JP-T-10-506420, JP-T2003-505561, WO2010 / 150748, and JP-A-2015. And the compounds described in Japanese Patent No. 151548.

  The formation method of the photo-alignment film by the photo-alignment method may be appropriately selected from conventionally known methods. For example, a photo-alignment film can be obtained by uniformly applying the photo-alignment composition on the transparent substrate, irradiating polarized light, and then irradiating the entire coating film with light.

  Further, when forming a horizontal alignment film by a molding method, the composition for the alignment film may be appropriately selected and used from those capable of molding a desired fine uneven shape, for example, an ultraviolet curable resin, a heat A molding composition containing a curable resin, an electron beam curable resin, or the like can be used. Among these, an ultraviolet curable resin is preferably used from the viewpoint that the alignment film can be easily formed. Specific examples of the ultraviolet curable resin include, for example, urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, melamine acrylate, and the like in addition to the above polymerizable monomer and polymerizable oligomer. A combination of more than one species can be used.

  The method for forming the horizontal alignment film by the molding method may be appropriately selected from conventionally known methods. For example, the composition for shaping is applied uniformly on the transparent substrate, and a coating film is brought into contact with a mold on which a desired fine uneven shape is formed, and then pressurized and irradiated with ultraviolet rays. Thus, an alignment film having a desired fine uneven shape can be obtained.

  In addition, the horizontal alignment film may be a film that has been subjected to a patterning process and has portions having alignment performance arranged in a pattern. As the horizontal alignment film subjected to the patterning process, a known one can be used, and is not particularly limited. For example, a rubbing alignment film patterned by mask rubbing, a photo-alignment patterned by mask exposure. Examples thereof include an alignment film obtained by patterning the film and the alignment film by printing or the like.

  The thickness of the horizontal alignment film only needs to be able to align the polymerizable rod-like liquid crystal compound in the horizontal direction and can be set as appropriate, and is not particularly limited, but is usually 1 nm or more, preferably 60 nm or more, From the viewpoint of thinning the film, it may be 15 μm or less, preferably 10 μm or less, more preferably 1 μm or less, and still more preferably 0.3 μm or less.

3. Substrate The retardation film of the present disclosure may have a substrate. The substrate is a member that supports the horizontal alignment film and the retardation layer. When the retardation film of the present disclosure has a substrate, the horizontal alignment film and the retardation layer are formed on the substrate. It is preferable to have this order.

  Examples of the substrate include a glass substrate, a metal foil, and a resin substrate. Especially, it is preferable that a base material has transparency, and it can select suitably from a conventionally well-known transparent base material. As a transparent substrate, in addition to a glass substrate, acetyl cellulose resins such as triacetyl cellulose, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyester resins such as polylactic acid, polypropylene, polyethylene, polymethylpentene, etc. It is formed using resins such as olefin resin, acrylic resin, polyurethane resin, polyether sulfone, polycarbonate, polysulfone, polyether, polyether ketone, acrylonitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer. Transparent resin base materials.

  The transparent substrate preferably has a transmittance in the visible light region of 80% or more, and more preferably 90% or more. Here, the transmittance | permeability of a transparent base material can be measured by JISK7361-1 (the test method of the total light transmittance of a plastic-transparent material).

Moreover, when forming a phase difference film by a roll-to-roll system, it is preferable that a transparent base material is a flexible material which has the flexibility which can be wound up in roll shape.
Such flexible materials include cellulose derivatives, norbornene polymers, cycloolefin polymers, polymethyl methacrylate, polyvinyl alcohol, polyimide, polyarylate, polyethylene terephthalate, polysulfone, polyethersulfone, amorphous polyolefin, modified acrylic polymer, polystyrene. And epoxy resins, polycarbonates, polyesters, and the like. Among these, 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 excellent in optical characteristics. Polyethylene terephthalate is preferable because it has high transparency and excellent mechanical properties.

The thickness of the substrate used in the present embodiment is not particularly limited as long as it is within the range that can provide the necessary self-supporting property, depending on the use of the retardation film, etc., but usually within the range of about 10 μm to 1000 μm. It is.
In particular, the thickness of the substrate is preferably in the range of 25 μm to 125 μm, and more preferably in the range of 30 μm to 100 μm. When the thickness is thicker than the above range, for example, after forming a long retardation film and cutting it into a single-phase retardation film, the processing waste increases or the cutting blade wears out. This is because there is a case that becomes faster.

The configuration of the substrate used in the present embodiment is not limited to a configuration consisting of a single layer, and may have a configuration in which a plurality of layers are laminated. When it has the structure by which the several layer was laminated | stacked, the layer of the same composition may be laminated | stacked, and the several layer which has a different composition may be laminated | stacked.
For example, when the horizontal alignment film used in the present embodiment contains an ultraviolet curable resin, a primer layer for improving the adhesion between the transparent substrate and the ultraviolet curable resin is formed on the substrate. May be. This primer layer has only adhesiveness to both the base material and the ultraviolet curable resin, is visible optically transparent, and can pass ultraviolet light. For example, a vinyl chloride / vinyl acetate copolymer system Urethane-based ones can be appropriately selected and used.

4). Optical characteristic As a value which shows an optical characteristic, there exists Nz factor (Nz) represented by following formula (1), for example.
Formula (1) Nz = (nx−nz) / (nx−ny)
(In formula (1), nx is the in-plane slow axis direction refractive index, ny is the in-plane fast axis direction refractive index, and nz is the thickness direction refractive index.)
nx> ny = nz. In the case of a so-called positive A plate, Nz = 1.
nx = nz> ny, and in the case of a so-called negative A plate, Nz = 0.
nz> nx = ny, and in the case of a so-called positive C plate, Nz approaches negative infinity.
In the retardation film of the present disclosure, both the retardation in the film plane and the retardation in the thickness direction can be controlled by the retardation layer. Therefore, the Nz factor (Nz) represented by the formula (1) Can be controlled in the range of −10 <Nz <1.
In the retardation film of the present disclosure, the Nz factor can be controlled by changing the addition amount of the homeotropic alignment side-chain liquid crystal polymer and the polymerizable rod-like liquid crystal compound contained in the retardation layer. A retardation layer showing physical properties can be easily prepared. Specifically, the Nz factor can be brought close to 1 by increasing the addition amount of the polymerizable rod-like liquid crystal compound, and the Nz factor can be reduced to -10 by increasing the addition amount of the homeotropic alignment side chain type liquid crystal polymer. Can be approached.
According to the retardation film of the present disclosure, it is not necessary to adjust the retardation by combining the stretched film and the liquid crystal layer, and the Nz factor can be adjusted only by the liquid crystal layer. It is also easy to obtain a retardation film having a Nz factor in the range of −10 <Nz <1 at 50 μm or less.
According to the retardation film of the present disclosure, by using the substrate in a peeled form, the film thickness is 1 μm or more and 20 μm or less, the film thickness is 1 μm or more and 15 μm or less, and the Nz factor is −10 <Nz <. It is also easy to obtain a retardation film in the range of 1.

The Nz factor can be obtained by, for example, a method of calculating from the values of nx, ny, and nz obtained when the in-plane phase difference Re is measured using a phase difference measuring device, using the equation (1). The measurement wavelength of the refractive index is a value at λ = 550 nm in the visible light region unless otherwise specified.
Examples of the phase difference measuring apparatus include a KOBRA series manufactured by Oji Scientific Instruments, and a RETS series manufactured by Otsuka Electronics Co., Ltd.

Further, in the retardation layer of the present disclosure, when the film thickness is about 1 μm or more and 10 μm or less, for example, (nx−ny) is preferably more than 0, for example, nx−ny = 0.0001. Also, there is no problem if the Nz coefficient becomes −10 <Nz <1 depending on the value of nz, but (nx−ny) is preferably 0.01 or more, and more preferably 0.05 or more. On the other hand, (nx−ny) is preferably less than 0.3.
Also, (nx−nz) is not a problem as long as the Nz coefficient is −10 <Nz <1, but is preferably −0.5 and less than 0.5.

  Since the Nz factor can be controlled in the range of −10 <Nz <1, the retardation film of the present disclosure is suitable for a retardation film showing optical characteristics of a negative A plate and a positive B plate. .

5. Production method of retardation film The production method of 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 described above.
Forming a horizontal alignment film;
A step of forming a retardation layer on the horizontal alignment film;
Forming the retardation layer comprises:
Forming a polymerizable liquid crystal composition containing a homeotropic alignment side-chain liquid crystal polymer and a polymerizable rod-like liquid crystal compound on the horizontal alignment film;
Aligning the liquid crystalline constituent unit of the homeotropic alignment side chain type liquid crystal polymer in the polymerized liquid crystal composition formed into a film, and the polymerizable rod-shaped liquid crystal compound;
An example of the method for producing a retardation film includes a step of polymerizing the polymerizable rod-like liquid crystal compound after the step of aligning.

(1) Step of forming horizontal alignment film The method of forming the horizontal alignment film has been described in “2. Horizontal alignment film”, and thus the description thereof is omitted here.

(2) Film forming step of polymerizable liquid crystal composition As the polymerizable liquid crystal composition, the same as “(1) polymerizable liquid crystal composition” of “1. retardation layer” can be used. The polymerizable liquid crystal composition may contain a solvent as necessary from the viewpoint of coatability.

The solvent may be appropriately selected from conventionally known solvents that can dissolve or disperse each component contained in the liquid crystal composition. Specifically, for example, hydrocarbon solvents such as hexane and cyclohexane, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether solvents such as tetrahydrofuran and propylene glycol monoethyl ether (PGME), chloroform, dichloromethane and the like Alkyl halide solvents, ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, amide solvents such as N, N-dimethylformamide, and sulfoxide solvents such as dimethyl sulfoxide, methanol, ethanol, propanol, etc. Examples include alcohol solvents, and among them, ketone solvents are preferred because of their excellent solubility in the homeotropic alignment side chain liquid crystal polymer and the polymerizable rod-like liquid crystal compound. There. In addition, the said solvent can be used as a mixed solvent individually by 1 type or in combination of 2 or more types.
When the polymerizable liquid crystal composition contains a solvent, the content ratio of the solid content (components other than the solvent) of the polymerizable liquid crystal composition is not particularly limited, but is preferably 5% by weight or more. More preferably, it is 70% by weight or less, and more preferably 50% by weight or less.

  In the step of forming the polymerizable liquid crystal composition on the horizontal alignment film, the polymerizable liquid crystal composition is uniformly applied on the horizontal alignment film to form a film. The application method may be any method as long as it can form a film with a desired thickness with high accuracy on a horizontal alignment film described later, and may be appropriately selected. For example, gravure coating method, reverse coating method, knife coating method, dip coating method, spray coating method, air knife coating method, spin coating method, roll coating method, printing method, dip pulling method, curtain coating method, die coating method, casting Method, bar coating method, extrusion coating method, E-type coating method and the like.

(3) Step of aligning liquid crystalline component The liquid crystalline constituent unit of the homeotropic alignment side chain liquid crystal polymer in the film-formed polymerizable liquid crystal composition, and the polymerizable rod-shaped liquid crystal compound are Orientation can be achieved by heat-treating the coating film of the polymerizable liquid crystal composition. The temperature of the heat treatment is appropriately adjusted so as to be in the liquid crystal temperature range of the homeotropic alignment side-chain liquid crystal polymer and the polymerizable rod-shaped liquid crystal compound, and is not particularly limited, but is a viewpoint of sufficiently progressing alignment formation. To 60 ° C. or higher, more preferably 70 ° C. or higher. Further, the temperature of the heat treatment is preferably 300 ° C. or less, and more preferably 200 ° C. or less.
The time for the heat treatment is not particularly limited, but is preferably 10 seconds or more, more preferably 20 seconds or more, and preferably 2 hours or less from the viewpoint of sufficiently progressing the alignment formation. Is preferable, and it is more preferable that it is 30 minutes or less.

  After the heat treatment, performing a cooling operation to cool the coating film of the polymerizable liquid crystal composition below the glass transition temperature of the homeotropic alignment side chain liquid crystal polymer and the polymerizable rod-like liquid crystal compound, This is preferable because the orientation is fixed. The cooling operation may be performed by, for example, placing the substrate in a heated atmosphere in a room temperature environment after the heat treatment, or performing forced cooling such as air cooling or water cooling.

(4) Step of polymerizing polymerizable rod-shaped liquid crystal compound The polymerizable property is obtained by, for example, irradiating light onto the coating film in which the alignment of the homeotropic alignment side-chain liquid crystal polymer and the polymerizable rod-shaped liquid crystal compound is fixed. A rod-like liquid crystal compound can be polymerized, and a retardation layer made of a cured product of the polymerizable liquid crystal composition can be obtained.
As the light irradiation, ultraviolet irradiation is preferably used. For the ultraviolet irradiation, ultraviolet rays emitted from light rays such as ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc, metal halide lamp can be used. Irradiation of energy beam source may if appropriately selected, accumulative exposure at an ultraviolet wavelength of 365 nm, is preferably in the range of, for example, 10 mJ / cm ² or more 10000 mJ / cm ² or less.

(5) Other Steps As a method of forming the retardation layer in a pattern, for example, the polymerizable liquid crystal composition is applied on a horizontal alignment film subjected to patterning processing as described later, and the horizontal alignment film A method of curing the polymerizable liquid crystal composition by polymerizing the polymerizable rod-shaped liquid crystal compound after aligning the homeotropic alignment side-chain liquid crystal polymer and the polymerizable rod-shaped liquid crystal compound disposed in a pattern. Etc.

6). Applications The retardation film of the present disclosure is suitably used as a retardation film showing optical characteristics of a negative A plate and a positive B plate. The retardation film of the present disclosure may be further laminated with a retardation layer having different optical characteristics.
The retardation film of the present disclosure can be used as, for example, a retardation film for optical compensation such as various display devices and optical devices, a λ / 4 film, a viewing angle compensation film, and a brightness enhancement film.

B. Transfer Laminate The retardation film of the present disclosure may be a transfer laminate used for transferring a retardation layer included in the retardation film.
The transfer laminate of the present disclosure is an embodiment of the retardation film of the present disclosure,
A support;
On the support, a horizontal alignment film,
A retardation layer containing a cured product of a polymerizable liquid crystal composition containing a homeotropic alignment side-chain liquid crystal polymer and a polymerizable rod-like liquid crystal compound on the horizontal alignment film,
Examples include a transfer laminate that is used for transfer of at least the retardation layer.

In the transfer laminate of the present disclosure, at least the phase difference layer to be transferred is a phase difference layer included in the phase difference film of the present disclosure. Therefore, the phase difference and film thickness in the film plane are formed by one phase difference layer. The phase difference in direction can be controlled, and it is possible to cope with thinning. According to the transfer laminate of the present disclosure, the horizontal alignment film and the phase difference included in the phase difference film of the present disclosure, for example, a thin film that does not include a base material on the transfer target such as any other optical member. Only the layer or the retardation layer can be transferred.
Hereinafter, the configuration of the transfer laminate of the present disclosure will be described. However, the horizontal alignment film and the retardation layer of the embodiment of the present disclosure are as described above, and thus description thereof is omitted here.

  An embodiment of the transfer laminate 20 shown in the example of FIG. 2 includes a second base material as a transfer layer 26 including a retardation layer for transfer and a support 25 that releasably supports the transfer layer. This is a transfer laminate in which a horizontal alignment film 23 and a retardation layer 21 are laminated in this order on 22. In the transfer laminate shown in the example of FIG. 2, the peel strength between the second base material 22 and the horizontal alignment film 23 is smaller than the peel strength between the horizontal alignment film 23 and the retardation layer 21. Thus, the phase difference layer 21 and the horizontal alignment film 23 can be transferred as the transfer layer 26 including the phase difference layer which is peeled off at the interface 27 between the second base material 22 and the horizontal alignment film 23 and used for transfer. It is an example of the laminated body for transfer.

  One embodiment of the transfer laminate 30 shown in the example of FIG. 3 includes a second base material as a transfer layer 36 including a retardation layer for transfer and a support 35 that releasably supports the transfer layer. This is a transfer laminate in which a horizontal alignment film 33 and a retardation layer 31 are laminated in this order on 32. In the transfer laminate shown in the example of FIG. 3, the peel strength between the second substrate 32 and the horizontal alignment film 33 is greater than the peel strength between the horizontal alignment film 33 and the retardation layer 31. Thus, the transfer layer 36 is an example of a transfer laminate that can be peeled off at the interface 37 between the horizontal alignment film 33 and the phase difference layer 31 and only the phase difference layer 31 can be transferred as the transfer layer 36.

  Whether the peel strength between the support and the horizontal alignment film is larger or smaller than the peel strength between the horizontal alignment film and the retardation layer is checked by peeling off the retardation layer and checking at which interface be able to. It can be analyzed, for example, by IR or the like at which interface.

In order to obtain the laminate for transfer according to the present disclosure, the peel strength between the support and the horizontal alignment film is smaller than the peel strength between the horizontal alignment film and the retardation layer. A release treatment may be applied to the surface, or a release layer may be formed. Thereby, the peelability of a 2nd base material can be improved, and the peel strength of a 2nd base material and a horizontal alignment film can be made smaller than the peel strength of a horizontal alignment film and a phase difference layer.
Examples of the mold release treatment include surface treatment such as fluorine treatment and silicone treatment.
Examples of the material for the release layer include a fluorine release agent, a silicone release agent, and a wax release agent. Examples of the method for forming the release layer include a method in which a release agent is applied by a coating method such as dip coating, spray coating, or roll coating.

  In addition, in order to obtain a transfer laminate that is peeled off at the interface between the horizontal alignment film and the retardation layer and transfers the retardation layer, the peeling strength between the support and the horizontal alignment film is such that the horizontal alignment film and the retardation layer In order to make it larger than the peel strength, for example, a method in which a solvent contained in the alignment film forming composition can dissolve the support can be used. As the support, it is preferable to use a resin base material, and surface treatment for improving the adhesion may be performed on the surface of the support. In such a case, the adhesion between the support and the horizontal alignment film can be improved.

The second substrate used as the support in the transfer laminate can be the same as the substrate described in “A. Retardation film”.
The second substrate used for the laminate for transfer may or may not have flexibility, but it has flexibility because it is easy to peel off the second substrate. Is preferred.
The thickness of the second substrate used in the transfer laminate is a balance between sufficient self-supporting strength and flexibility sufficient to adapt to the transfer laminate production and transfer process of this embodiment, Usually, in the case of a sheet of the above material, it is preferably in the range of 20 μm to 200 μm.

  The retardation layer that can be provided from the laminate for transfer of the present disclosure is suitably used for the same application as the retardation film, and displays various retardation layers that can function as a negative A plate, a positive B plate, or the like. It can be transferred to an optical member for an apparatus and is preferably used for providing a thin film optical member.

C. Optical member The optical member of one embodiment of this indication has the phase contrast film of this indication mentioned above, and at least one optical film.

  The optical member of this embodiment will be described with reference to the drawings. FIG. 4 is a schematic cross-sectional view illustrating an example of the optical member of the present disclosure. In the example of the optical member 40 in FIG. 4, the optical film 41 is provided on the retardation film 10 of the present disclosure.

  Since the optical member of the present disclosure has the retardation film of the present disclosure described above, the retardation film can obtain desired optical characteristics by controlling the retardation in the film plane and the retardation in the film thickness direction. Is possible. Moreover, the optical member of this indication can respond | correspond to thin film formation as a whole optical member by making a retardation film into thin film.

  In the optical member of the present disclosure, the optical film 41 may be positioned on the surface of the retardation film on the phase difference layer side as shown in FIG. 4, or the phase difference as shown in FIG. The optical film 41 may be positioned on the surface of the film on the horizontal alignment film side, and although not shown, each of the phase difference film on the surface on the phase difference layer side and on the surface on the horizontal alignment film side An optical film may be located.

Examples of the optical film used in the optical member of the present disclosure include a polarizing plate, an antireflection film, a light diffusion film, an antiglare film, a color tone correction film, a conventionally known retardation film different from the retardation film of the present disclosure, and the like. Is mentioned. Examples of the conventionally known retardation film different from the retardation film of the present disclosure include a stretched film, a retardation film using another liquid crystal coating film different from the retardation layer used in the present disclosure, and the like. . The said optical film can be used individually by 1 type or in combination of 2 or more types. Among them, it is preferable to include a polarizing plate as the optical film. In the present embodiment, the polarizing plate has a plate shape that allows only light oscillating in a specific direction to pass therethrough, and can be appropriately selected from conventionally known polarizing plates. For example, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, which is dyed with iodine or a dye and stretched can be used.
The various optical films can be appropriately selected from conventionally known ones.

Moreover, the optical member of this indication may further have another layer with which well-known optical members, such as an adhesion layer (adhesion layer) and a protective film, are provided as needed.
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 pressure-sensitive adhesives (pressure-sensitive adhesives), two-component curable adhesives, and ultraviolet curing. Any adhesive form such as a mold adhesive, a thermosetting adhesive, and a hot melt adhesive can be suitably used.

  Examples of the optical member of the present disclosure include a wide viewing angle polarizing plate, a circularly polarizing plate, an elliptical polarizing plate, a reflective polarizing plate, a transflective polarizing plate, and an optical member for suppressing external light reflection for a light emitting display device. Can be used as

D. Manufacturing method of optical member The manufacturing method of the optical member of 1 embodiment of this indication which has the retardation film of this indication mentioned above and at least 1 optical film is not specifically limited, The above-mentioned of this indication is disclosed. A method of laminating the retardation film and at least one optical film can be appropriately selected and used. For example, the manufacturing method etc. which laminate | stack the retardation film of this indication mentioned above and at least 1 optical film through an adhesive layer are mentioned.

Moreover, the manufacturing method of the optical member of one embodiment of the present disclosure includes a transfer laminate preparing step of preparing the transfer laminate of the one embodiment of the present disclosure;
A transfer step in which a transfer object including at least one optical film is opposed to the retardation layer of the transfer laminate, and the transfer laminate is transferred onto the transfer object;
A method for producing an optical member, which includes a peeling step of peeling the support, or the support and the horizontal alignment film, from the transfer laminate transferred onto the transfer target.

A method for manufacturing an optical member according to an embodiment of the present disclosure using the transfer laminate will be described with reference to the drawings.
6A to 6D are process diagrams illustrating an example of a method of manufacturing an optical member according to an embodiment of the present disclosure. First, as shown in FIG. 6 (A), a transfer layer 26 including a phase difference layer 21 to be transferred and a support 25 that detachably supports the transfer layer are horizontally aligned on a second substrate 22. A transfer laminate 20 in which the film 23 and the retardation layer 21 are laminated in this order is prepared. In the transfer laminate 20, the peel strength between the second base material 22 and the horizontal alignment film 23 is smaller than the peel strength between the horizontal alignment film 23 and the retardation layer 21. Next, as shown in FIG. 6B, a transfer target 45 including an optical film 41 and an adhesive layer 42 is prepared as a transfer target including at least one optical film, and the optical film 41 and the adhesive layer 42 are prepared. The transfer target body 45 and the retardation layer 21 of the transfer laminate 20 are opposed to each other, and the transfer laminate 20 is transferred onto the optical film 41 via the adhesive layer 42. Next, as shown in FIG. 6C, the second substrate 22 is peeled off as the support 25 from the transfer laminate 20 transferred onto the transfer target 45. Thereby, as shown in FIG. 6D, an optical member 40 having the retardation layer 21 and the horizontal alignment film 23 transferred onto the optical film 41 via the adhesive layer 42 is obtained.

Drawing 7 (A)-Drawing 7 (D) are process drawings showing other examples of a manufacturing method of an optical member of one embodiment of this indication. First, as shown in FIG. 7A, a transfer layer 36 including a phase difference layer 31 to be transferred and a support 35 that releasably supports the transfer layer are horizontally aligned on a second substrate 32. A transfer laminate 30 in which the film 33 and the retardation layer 31 are laminated in this order is prepared. In the transfer laminate 30, the peel strength between the second substrate 32 and the horizontal alignment film 33 is greater than the peel strength between the horizontal alignment film 33 and the retardation layer 31. Next, as shown in FIG. 7B, a transferred object 45 including an optical film 41 and an adhesive layer 42 is prepared as a transferred object including at least one optical film, and the optical film 41 and the adhesive layer 42 are prepared. The transfer target body 45 and the retardation layer 31 of the transfer laminate 30 are made to face each other, and the transfer laminate 30 is transferred onto the optical film 41 through the adhesive layer 42. Next, as shown in FIG. 7C, the second base material 32 and the horizontal alignment film 33 are peeled off as the support 35 from the transfer laminate 30 transferred onto the transfer target body 45. As a result, as shown in FIG. 7D, the optical member 50 having the retardation layer 31 transferred onto the optical film 41 via the adhesive layer 42 is obtained.
As described above, according to the method of manufacturing an optical member of one embodiment of the present disclosure, at least one optical film and an optical member including only the retardation layer of the retardation film of the first embodiment of the present disclosure. That is, an optical system comprising a retardation layer containing a cured product of a polymerizable liquid crystal composition containing the homeotropic alignment side chain type liquid crystal polymer and a polymerizable rod-like liquid crystal compound on at least one optical film. A member can be obtained. The optical member according to an embodiment of the present disclosure thus obtained is one retardation layer, for example, the Nz factor is controlled to be within a range of −10 <Nz <1, and the horizontal alignment film is also used. Since it is not included, it is an optical member corresponding to a thinner film.

  When the second substrate 32 and the horizontal alignment film 33 are peeled off as the support 35 from the transfer laminate 30 transferred onto the transfer target body 45, a part of the horizontal alignment film is destroyed, An embodiment in which a part of the horizontal alignment film is peeled off and a part of the horizontal alignment film exists on the retardation layer may be used.

Since the transfer laminate in the optical member manufacturing method according to an embodiment of the present disclosure can be the same as that described in “B. Transfer laminate”, description thereof is omitted here. .
In addition, examples of the transfer target including at least one optical film include, but are not limited to, a transfer target having an adhesive layer and an optical film. Since the optical film here can be the same as that described for the optical member, description thereof is omitted here.

E. Display Device The display device of the present disclosure includes the retardation film of the present disclosure described above or the optical member of the present disclosure described above.
The display device of the present disclosure can provide a good display image by performing optical compensation with the retardation film of the present disclosure described above or the optical member of the present disclosure described above. Moreover, the display apparatus of this indication can respond | correspond to thin film formation also as a whole display apparatus by thinning a phase difference film or an optical member.

The display device of the present disclosure includes the above-described retardation film of the present disclosure or the above-described optical member of the present disclosure instead of the conventional retardation film or the conventional optical member used in the conventional display device. Things.
The display device of the present disclosure is not particularly limited as long as it includes the retardation film of the present disclosure or the optical member of the present disclosure, and examples thereof include a liquid crystal display device and a light emitting display device. It is not limited to. The liquid crystal display device also includes a liquid crystal display device that displays a three-dimensional image by a passive method.
As the liquid crystal display device, for example, an optical member of the present disclosure having a polarizing plate as an optical film is disposed on one side or both sides of a liquid crystal cell, and further includes components such as a backlight as necessary. Is mentioned.

<Measurement method of mass average molecular weight (Mw)>
For the mass average molecular weight measurement, HLC-8120GPC manufactured by Tosoh Corporation was used, the elution solvent was tetrahydrofuran, and polystyrene standards for calibration curves were Mw 1110000, 707000, 697000, 189000, 98900, 37200, 13700, 9490, 5430, 3120, 1010 and 589 (manufactured by Tosoh Corp.), and the measurement columns are TSK-GEL G2000HXL and G4000HXL (manufactured by Tosoh Corp.).

Examples and comparative examples will be shown below, and embodiments of the present disclosure will be described in more detail.
(Synthesis Example 1: Synthesis of liquid crystal monomer 1)
First, according to the following scheme 1, 4- [2- (acryloyloxy) ethyloxy] benzoic acid was synthesized.

  Next, liquid crystal monomer 1 was obtained according to the following scheme 2. Specifically, 4- [2- (acryloyloxy) ethyloxy] benzoic acid obtained above (179.4 g, 759.4 mmol), 4′-cyano-4-hydroxybiphenyl (148.3 g, 759.4 mmol) ), 35% hydrochloric acid solution (2.373 g), N, N-dimethylaminopyridine (DMAP) (2.739 g, 22.78 mmol) in dichloromethane (1243 g) suspension in N, N-dicyclohexylcarbodiimide (DCC) A solution of (170.8 g, 827.8 mmol) in dichloromethane (170.8 g) was added dropwise. After completion of dropping, the mixture was stirred overnight, the precipitate was filtered, and the solvent was distilled off. Methanol (1421 g) was added to the resulting crude product, and the mixture was stirred for 1 hour at room temperature and purified by suspension. The precipitate was filtered, and the resulting crystal was dried to obtain 4′-cyano-4- {4- [2- (acryloyloxy) ethyloxy] benzoate} (the following chemical formula (1)) in a yield of 92. Obtained in 9% (301.1 g, 728.3 mmol).

(Synthesis Example 2: Synthesis of Liquid Crystal Monomer 2)
First, according to the following scheme 3, 4-propoxycarbonylphenyl = 4-hydroxybenzoate represented by the following chemical formula (2) was obtained. Specifically, 4-acetoxybenzoic acid (524.8 g, 2.91 mol), propyl 4-hydroxybenzoate (500 g, 2.78 mol), N, N-dimethylaminopyridine (DMAP) (20.34 g, 0) .17 mmol) in dichloromethane (2.5 L) was added dropwise a solution of N, N-dicyclohexylcarbodiimide (DCC) (601.3 g, 2.91 mol) in dichloromethane (601.3 g). After completion of dropping, the mixture was stirred overnight, the precipitate was filtered, and then the solvent was distilled off. Methanol (3.4 L) was added to the obtained oil to dissolve it, and then a solution of potassium carbonate (446.1 g, 3.23 mol) in water (1.7 L) was slowly added dropwise under cooling. The reaction mixture was stirred for 1 hour, neutralized with 35% hydrochloric acid (325 mL), the precipitated crystals were filtered, and the crude product was dried to give 4-propoxycarbonylphenyl = 4-hydroxybenzoate in two steps 72 Obtained in a yield of 0.9% (602.17 g, 2.00 mol).

  Next, according to the following scheme 4, the liquid crystal monomer 3 represented by the following chemical formula (3) was obtained. Specifically, 4-propoxycarbonylphenyl = 4-hydroxybenzoate (664 g, 2.27 mol), 4- [2- (acryloyloxy) ethyloxy] benzoic acid (510 g, 2.16 mol), N, N-dimethyl A dichloromethane (489 g) solution of N, N-dicyclohexylcarbodiimide (DCC) (489.0 g, 2.37 mol) in a suspension of aminopyridine (DMAP) (7.9 g, 0.06 mol) in dichloromethane (2.8 L). Was dripped. After completion of dropping, the mixture was stirred overnight, the precipitate was filtered, and then the solvent was distilled off. Methanol (5.0 L) was added to the obtained crude product and dissolved, and then stirred for 5 hours under cooling. The precipitated crystals were filtered and the obtained crystals were dried to give 4-[(4-propoxycarbonylphenyloxycarbonyl) phenyl = 4- [2- (acryloyloxy) ethyloxy] benzoate in a yield of 82% ( 895 g, 1.73 mol).

  As non-liquid crystal monomers, stearyl acrylate (the following chemical formula (A)) was prepared as monomer A, hexyl acrylate (the following chemical formula (B)) was prepared as monomer B, and ethoxydiethylene glycol acrylate (the following chemical formula (C)) was prepared as monomer C ( All are manufactured by Tokyo Chemical Industry Co., Ltd.).

(Synthesis Example 3: Synthesis of Monomer D)
Into a 2 L flask protected from light, 4-amylphenol (82.5 g, 502 mmol), 3-chloro-1-propanol (124.0 g, 753 mmol), potassium carbonate (83.3 g, 603 mmol), N, N-dimethyl Formamide (198.1 g) was added, the temperature was raised to 100 ° C., and the mixture was stirred for 37 hours. Thereafter, the reaction solution was allowed to cool to room temperature, tap water (413, 1 g) was added, and the mixture was stirred for 10 minutes. Thereafter, ethyl acetate (330.5 g) was further added and stirred for 5 minutes, followed by liquid separation. The separated water tank was re-extracted with ethyl acetate (329.8 g), and the combined organic layer was washed with tap water (412.9 g). Thereafter, the organic layer was washed with tap water (413.8 g) and saturated brine (150 ml), the water tank was removed by liquid separation, and the solvent was distilled off. The residue was purified by silica gel chromatography (ethyl acetate / hexane = 0/100 → 15/85), and the solvent was distilled off to obtain 113.0 g of ether A.
Next, the ether A (114.5 g, 392 mmol), N, N-dimethylaniline (52.3 g, 432 mmol), N, N-dimethylacetamide (26.2 g), tetrahydrofuran were added to a 2 L four-flask flask protected from light. (333.2 g) was added, and the internal temperature was cooled to 15 ° C. or lower. A solution of acrylic acid chloride (56.8 g, 628 mmol) dissolved in tetrahydrofuran (11.5 g) was added dropwise to the mixture, and the mixture was stirred at 25 ° C. for 5 hours. Thereafter, the reaction solution was dropped into tap water (1148.4 g) at 11.7-20.1 ° C., and then extracted with ethyl acetate (919.1 g). Thereafter, 4-methoxyphenol (2.4 g) and 10% saline were added to the organic layer and washed. The separated organic layer was washed again with 10% brine, and then the solvent of the organic layer was distilled off. The residue was purified by silica gel chromatography (ethyl acetate / hexane = 0/100 → 2/98), and the solvent was distilled off to obtain 114 g of monomer D represented by the following chemical formula (D).

(Production Examples 1 to 8: Synthesis of side chain type liquid crystal polymers A-01 to A-08)
Side liquid crystal polymers were synthesized by combining the liquid crystal monomers 1 and 2 and monomers A to D as non-liquid crystal monomers according to Table 1.
A synthesis example of the side chain type liquid crystal polymer A-01 will be specifically described.
Liquid crystal monomer 1 and monomer A were combined and mixed at a molar ratio of 5: 5, N, N-dimethylacetamide (DMAc) was added, and the mixture was stirred and dissolved at 40 ° C. After dissolution, the mixture was cooled to 24 ° C., azobisisobutyronitrile (AIBN) was added and dissolved at the same temperature. The above reaction solution was added dropwise to DMAc heated to 80 ° C. over 30 minutes. After completion of the addition, the reaction solution was stirred at 80 ° C. for 6 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, then dropped at 9 ° C. in another vessel stirring, and stirred for 20 minutes. After removing the supernatant, the slurry was filtered, and the resulting crude product was again stirred in methanol at 9 ° C. for 20 minutes, and the supernatant was removed and filtered. The obtained crystals were dried to obtain a polymer with a yield of 76.5%.

  In the production example of the side chain type liquid crystal polymer A-01, the side chain type liquid crystal polymer A-01 was prepared in the same manner as in the synthesis example of the side chain type liquid crystal polymer A-01, except that the combination and blending ratio of non-liquid crystal monomers were changed as shown in Table 1. Chain type liquid crystal polymers A-01 to A-06 were obtained. Further, in the synthesis example of the side chain type liquid crystal polymer A-01, the side chain type liquid crystal polymer A-07 is the same as the side chain type liquid crystal polymer A-01 except that the molecular weight is changed as shown in Table 1. Got. Further, in the synthesis example of the side chain type liquid crystal polymer A-01, the side chain type liquid crystal polymer A- is the same as the side chain type liquid crystal polymer A-01 except that the liquid crystal monomer is changed as shown in Table 1. 08 was obtained. Table 1 shows the mass average molecular weights (Mw) of the side chain type liquid crystal polymers A-01 to A-08.

  As the polymerizable rod-like liquid crystal compound, compounds of B-01 (the following chemical formula B-01), B-02 (the following chemical formula B-02), and B-03 (the following chemical formula B-03) were prepared.

[Example 1]
(Preparation of polymerizable liquid crystal composition)
A polymerizable liquid crystal composition having the composition shown below was prepared.
-Side chain type liquid crystal polymer A-01: 0.01 part by mass-Polymerizable rod-like liquid crystal compound B-01: 0.09 part by mass-Photopolymerization initiator C-01 (manufactured by BASF, Irgacure 907): 0.005 Parts by mass, cyclohexanone: 0.4 parts by mass

(Formation of horizontal alignment film)
On one side of a PET substrate (Toyobo Co., Ltd., E5100, thickness 38 μm), a rubbing alignment film composition having the following composition was applied by bar coating so that the film thickness after curing would be 10 μm, In an oven for 2 minutes to dry and thermally cure to form a cured film. Thereafter, the surface of the cured film was rubbed with a rubbing cloth to form a horizontal alignment film.
<Composition of composition for rubbing alignment film>
Polyvinyl alcohol (Kuraray, PVA103, saponification degree 98): 0.1 part by mass Glutaraldehyde: 0.01 part by mass Water: 1.3 part by mass Methanol: 1.3 part by mass

(Formation of retardation layer)
The polymerizable liquid crystal composition was applied to the surface of the horizontal alignment film subjected to the rubbing treatment by a die head coating method by adjusting the flow rate during coating so that the film thickness after drying was 1 μm. After drying for 1 minute at a drying temperature of 120 ° C., the retardation film of Example 1 was formed by irradiating ultraviolet rays (UV) with an exposure amount of 300 mJ / cm ² using a high-pressure mercury lamp to form a retardation layer. A laminate for transfer was obtained.

[Examples 2 to 26]
In Example 1, except that the composition of the polymerizable liquid crystal composition was changed as shown in Table 2, the retardation films or transfer laminates of Examples 2 to 26 were obtained in the same manner as in Example 1. .

[Example 27]
In Example 1, the composition of the polymerizable liquid crystal composition was changed as shown in Table 2, and the horizontal alignment film formed by the following method was used as the horizontal alignment film in the same manner as in Example 1, A retardation film or a transfer laminate of Example 27 was obtained.

(Preparation of composition for photo-alignment film)
According to the description in Production Example 1 of Japanese Patent No. 5626493, a copolymer 1 obtained by copolymerizing a photoalignment monomer and hydroxyethyl methacrylate was obtained.
The composition for photo-alignment films having the following composition was prepared.
Copolymer 1: 0.1 part by mass Hexamethoxymethylmelamine (HMM): 0.01 part by mass p-toluenesulfonic acid monohydrate (PTSA): 0.0015 part by mass Propylene glycol monomethyl ether ( PGME): 2.1 parts by mass

(Formation of horizontal alignment film)
On one side of a PET substrate (Toyobo Co., Ltd., E5100, thickness 38 μm), the composition for photo-alignment film was applied by bar coating so that the film thickness after curing was 1.0 μm, and 120 ° C. In an oven for 1 minute to dry and heat cure to form a cured coating. Thereafter, the surface of the cured coating film is irradiated with polarized ultraviolet rays containing a 313 nm emission line in the vertical direction from the substrate normal at an exposure amount of 10 mJ / cm ² using an Hg-Xe lamp and a Grand Taylor prism, thereby forming a horizontal alignment film. Formed.

[Comparative Example 1]
In Example 1, the composition of the polymerizable liquid crystal composition was changed as shown in Table 3, and instead of forming a horizontal alignment film, instead, on a PET substrate (Toyobo Co., Ltd., E5100, thickness 38 μm). A transparent vitreous polymer film is formed by applying an ethyl silicate 2% solution (trade name Colcoat P, manufactured by Colcoat Co., Ltd.) as a sol solution for anchor coating, and placed on the transparent vitreous polymer film. A retardation film or a transfer laminate of Comparative Example 1 was obtained in the same manner as in Example 1 except that the retardation layer was formed.
The transparent vitreous polymer film does not function as a horizontal alignment film.

[Comparative Examples 2 and 3]
In Example 1, the retardation film or transfer laminate of Comparative Examples 2 and 3 was obtained in the same manner as in Example 1 except that the composition of the polymerizable liquid crystal composition was changed as shown in Table 3. .

[Evaluation]
A sample obtained by peeling the PET substrate of the retardation film obtained in each Example and each Comparative Example and transferring the retardation layer and the horizontal alignment film to the glass with adhesive was used. An in-plane phase difference Re (550 nm) with respect to a wavelength of 550 nm is measured by a phase difference measuring device (manufactured by Oji Scientific Instruments Co., Ltd., KOBRA-WR). From the values of nx, ny and nz obtained at that time, the above formula The Nz factor was calculated from (1). The calculation results of each example are shown in Table 2, and the calculation results of each comparative example are shown in Table 3. In the measurement of the in-plane retardation Re (550 nm), specifically, the incident angle dependency is selected as a measurement item, the tilt axis is the slow axis, the incident angle is 40 °, and the film thickness d Was set to 1.0 μm.

The retardation film obtained in each example had a horizontal alignment film, and the retardation layer contained a homeotropic alignment side chain type liquid crystal polymer and a polymerizable rod-shaped liquid crystal compound. The retardation in the film plane and the retardation in the film thickness direction could be controlled so that the characteristics were obtained, and the Nz factor could be in the range of −10 <Nz <1.
Since the retardation film obtained in Comparative Example 1 did not have a horizontal alignment film as in the example of Patent Document 1, the retardation layer was a homeotropic alignment side chain type liquid crystal polymer and polymerizable. Even in the case of containing a rod-like liquid crystal compound, the retardation in the film plane could not be controlled, and the Nz factor was −30.
In the retardation film obtained in Comparative Example 2, since the retardation layer did not contain a polymerizable rod-like liquid crystal compound, the retardation in the film plane could not be controlled, and the Nz factor was −25. It was.
In the retardation film obtained in Comparative Example 3, since the retardation layer does not contain a homeotropic alignment side chain type liquid crystal polymer, the retardation and film in the film surface are obtained so that desired optical characteristics can be obtained. The retardation in the thickness direction could not be controlled, and the Nz factor was 1.1.

DESCRIPTION OF SYMBOLS 10 Retardation film 11 Horizontal alignment film 12 Retardation layer 20, 30 Transfer laminated body 21, 31 Retardation layer 22, 32 Second base material 23, 33 Horizontal alignment film 25, 35 Peelable support 26, 36 Transfer layer 27 including retardation layer used for transfer Interface 37 between second base material and horizontal alignment film Interface 40, 50 between horizontal alignment film and phase difference layer Optical member 41 Optical film 42 Adhesive layer 45 Transfer object

Claims (9)

A horizontal alignment film;
A retardation film having a retardation layer containing a cured product of a polymerizable liquid crystal composition containing a homeotropic alignment side-chain liquid crystal polymer and a polymerizable rod-like liquid crystal compound on the horizontal alignment film. The homeotropic alignment side chain type liquid crystal polymer includes a copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II). The retardation film described in 1.
(In General Formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is represented by — (CH ₂ ) _n —R ³ , or — (C ₂ H ₄ O) _{n ′} -R ^4. R ³ represents a methyl group which may have a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or —OR ⁵ , —O—C (═O) R ⁵ or —C (═O) —OR ⁵ , wherein R ⁴ and R ⁵ each independently have 1 to 10 carbon atoms which may have a substituent. An aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a combination thereof, n is an integer of 2 to 22 and n ′ Is an integer from 1 to 6.
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 ¹ is a direct bond, or —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, — NR ¹⁴ —C (═O) —, —C (═O) —NR ¹⁴ —, —O—C (═O) —NR ¹⁴ —, —NR ¹⁴ —C (═O) —O—, —NR ¹⁴ In the linking group represented by —C (═O) —NR ¹⁴ —, —O—NR ¹⁴ —, or —NR ¹⁴ —O—, Ar ¹ has 6 carbon atoms which may have a substituent. The number of aromatic hydrocarbon groups is 10 or less, and a plurality of L ¹ and Ar ¹ may be the same or different. R ¹³ is —F, —Cl, —CN, —OCF ₃ , —OCF ₂ H, —NCO, —NCS, —NO ₂ , —NHC (═O) —R ¹⁵ , —C (═O) —OR ¹⁵ , —OH, —SH, —CHO, —SO ₃ H, —NR ¹⁵ ₂ , —R ¹⁶ , or —OR ¹⁶ , wherein R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or 1 to 6 carbon atoms. R ¹⁶ represents an alkyl group having 1 to 6 carbon atoms. 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. ) The retardation film of Claim 1 or 2 whose Nz factor (Nz) represented by following formula (1) of the said retardation layer is in the range of -10 <Nz <1.
Formula (1) Nz = (nx−nz) / (nx−ny)
(In formula (1), nx is the in-plane slow axis direction refractive index, ny is the in-plane fast axis direction refractive index, and nz is the thickness direction refractive index.) A support;
On the support, a horizontal alignment film,
A retardation layer containing a cured product of a polymerizable liquid crystal composition containing a homeotropic alignment side-chain liquid crystal polymer and a polymerizable rod-like liquid crystal compound on the horizontal alignment film,
A laminate for transfer used for at least transfer of the retardation layer. The homeotropic alignment side chain type liquid crystal polymer contains a copolymer having a structural unit represented by the following general formula (I) and a structural unit represented by the following general formula (II). The laminate for transfer described in 1.
(In General Formula (I), R ¹ is a hydrogen atom or a methyl group, R ² is represented by — (CH ₂ ) _n —R ³ , or — (C ₂ H ₄ O) _{n ′} -R ^4. R ³ represents a methyl group which may have a substituent, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or —OR ⁵ , —O—C (═O) R ⁵ or —C (═O) —OR ⁵ , wherein R ⁴ and R ⁵ each independently have 1 to 10 carbon atoms which may have a substituent. An aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a combination thereof, n is an integer of 2 to 22 and n ′ Is an integer from 1 to 6.
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 ¹ is a direct bond, or —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C (═O) —O—, — NR ¹⁴ —C (═O) —, —C (═O) —NR ¹⁴ —, —O—C (═O) —NR ¹⁴ —, —NR ¹⁴ —C (═O) —O—, —NR ¹⁴ In the linking group represented by —C (═O) —NR ¹⁴ —, —O—NR ¹⁴ —, or —NR ¹⁴ —O—, Ar ¹ has 6 carbon atoms which may have a substituent. The number of aromatic hydrocarbon groups is 10 or less, and a plurality of L ¹ and Ar ¹ may be the same or different. R ¹³ is —F, —Cl, —CN, —OCF ₃ , —OCF ₂ H, —NCO, —NCS, —NO ₂ , —NHC (═O) —R ¹⁵ , —C (═O) —OR ¹⁵ , —OH, —SH, —CHO, —SO ₃ H, —NR ¹⁵ ₂ , —R ¹⁶ , or —OR ¹⁶ , wherein R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or 1 to 6 carbon atoms. R ¹⁶ represents an alkyl group having 1 to 6 carbon atoms. 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. ) The transfer laminate according to claim 4 or 5, wherein an Nz factor (Nz) represented by the following formula (1) of the retardation layer is in a range of -10 <Nz <1.
Formula (1) Nz = (nx−nz) / (nx−ny)
(In formula (1), nx is the in-plane slow axis direction refractive index, ny is the in-plane fast axis direction refractive index, and nz is the thickness direction refractive index.)   An optical member comprising the retardation film according to any one of claims 1 to 3 and at least one optical film. A transfer laminate preparation step for preparing the transfer laminate according to any one of claims 4 to 6,
A transfer step in which a transfer object including at least one optical film is opposed to the retardation layer of the transfer laminate, and the transfer laminate is transferred onto the transfer object;
And a peeling step of peeling the support or the support and the horizontal alignment film from the transfer laminate transferred onto the transfer target.   A display device comprising the retardation film according to claim 1 or the optical member according to claim 7.