JP2019139219A - Laminate and method for manufacturing the same - Google Patents

Abstract

To provide a laminate in which a vertically aligned liquid crystal cured film can be formed without forming a vertical alignment film, and further a horizontally aligned liquid crystal cured film can be continuously formed via a horizontal alignment film.SOLUTION: A laminate 11 includes a substrate 1, a vertically aligned liquid crystal cured film 2, a horizontal alignment film 3, and a horizontally aligned liquid crystal cured film 4, in this order, where the vertically aligned liquid crystal cured film 2 is a cured product of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in an aligned state in a vertical direction with respect to the plane of the liquid crystal cured film; the horizontally aligned liquid crystal cured film 4 is a cured product of a polymerizable liquid crystal composition in which a polymerizable liquid crystal compound is cured in an aligned state in a horizontal direction with respect to the plane of the liquid crystal cured film; the vertically aligned liquid crystal cured film 2 contains a vertical alignment promoter; the horizontal alignment film is a photo-alignment film formed from a (meth)acrylic polymer; and the total film thickness from a substrate-side surface of the vertically aligned liquid crystal cured film 2 to the surface of the horizontally aligned liquid crystal cured film 4 on an opposite side to the horizontal alignment film is 10 μm or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate including a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film, an elliptically polarizing plate including the laminate, and an organic EL display device. The present invention also relates to a method for manufacturing the laminate.

  An elliptically polarizing plate is an optical member in which a polarizing plate and a retardation plate are laminated. For example, in a device that displays an image in a planar state, such as an organic EL image display device, light reflection at an electrode constituting the device. It is used to prevent In general, a so-called λ / 4 plate is used as a retardation plate constituting the elliptically polarizing plate.

  In view of easily exhibiting uniform retardation performance in a wide wavelength range of visible light, the retardation plate constituting the elliptically polarizing plate is preferably one showing reverse wavelength dispersion. As such a phase difference plate, a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is polymerized and cured in a state where it is aligned in the horizontal direction with respect to the plane of the phase difference plate. A phase difference plate is known. In addition, by incorporating a vertically aligned liquid crystal cured film into an elliptically polarizing plate provided with a horizontally aligned liquid crystal cured film, the oblique hue change during black display when the elliptically polarizing plate is used in an organic EL display device is suppressed. Patent Document 1 describes a laminate including a vertical alignment liquid crystal cured film formed on a vertical alignment film and a horizontal alignment liquid crystal cured film formed on a horizontal alignment film. ing.

JP2015-163935A

  However, a laminate including a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film as described in the above-mentioned patent document has conventionally been produced after independently producing a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film. In many cases, it is produced by pasting them together with an adhesive or the like. Conventionally, a vertical alignment liquid crystal cured film requires a vertical alignment film for aligning a polymerizable liquid crystal compound in the vertical direction, and the vertical alignment film needs to be formed before the vertical alignment liquid crystal cured film is formed. There is. For this reason, the manufacturing process of the conventional laminated body containing a vertical alignment liquid crystal cured film and a horizontal alignment liquid crystal cured film tends to become complicated, and there existed a problem that productivity fell easily.

  Therefore, the present invention provides a novel solution to the above problem, that is, a vertically aligned liquid crystal cured film can be formed without forming a vertical aligned film, and further a horizontally aligned liquid crystal cured film can be continuously formed. It aims at providing a laminated body and its manufacturing method.

  Further, in the examination of the above solution by the present inventors, when a vertically aligned liquid crystal cured film is formed without forming a vertical aligned film, the liquid crystal alignment property tends to be lowered, and When forming a horizontal liquid crystal cured film through a horizontal alignment film, a vertical alignment liquid crystal cured film is compared with a laminate in which a vertical alignment liquid crystal cured film and a horizontal alignment liquid crystal cured film are bonded by an adhesive layer. It was revealed that the adhesion between the liquid crystal cured film and the horizontally aligned liquid crystal cured film tends to decrease.

  Accordingly, the present invention provides a liquid crystal alignment property improved in a laminate including a horizontal alignment liquid crystal cured film laminated on a vertical alignment liquid crystal cured film formed without a vertical alignment film, and a vertical alignment liquid crystal cured film. Another object of the present invention is to improve the adhesion between the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film formed on the vertically aligned liquid crystal cured film via the horizontal aligned film.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, this invention includes the following aspects.
[1] A laminate comprising a substrate, a vertically aligned liquid crystal cured film, a horizontal aligned film and a horizontal aligned liquid crystal cured film in this order,
The vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition that is cured in a state where the polymerizable liquid crystal compound is aligned in a direction perpendicular to the plane of the liquid crystal cured film. Is a cured product of a polymerizable liquid crystal composition cured in a state in which the crystalline liquid crystal compound is aligned in a horizontal direction with respect to the liquid crystal cured film plane,
The vertical alignment liquid crystal cured film contains a vertical alignment accelerator, and the horizontal alignment film is a photo-alignment film formed from a (meth) acrylic polymer,
The laminated body whose total film thickness from the surface by the side of the base material side of the said vertical alignment liquid crystal cured film to the surface on the opposite side to the horizontal alignment film of a horizontal alignment liquid crystal film is 10 micrometers or less.
[2] The laminate according to [1], wherein the substrate is a peelable substrate.
[3] The laminate according to [1] or [2], wherein a substrate, a vertically aligned liquid crystal cured film, a horizontal aligned film, and a horizontally aligned liquid crystal cured film are present adjacent to each other in this order.
[4] The laminate according to any one of [1] to [3], wherein the horizontal alignment film has a thickness of 10 to 5000 nm.
[5] The laminate according to any one of [1] to [4], wherein the horizontal alignment film is a photo-alignment film formed from a polymer having an azo group or a cinnamoyl group.
[6] The laminate according to any one of [1] to [5], wherein the horizontally aligned liquid crystal cured film has at least one maximum absorption between wavelengths of 300 to 400 nm.
[7] The horizontally aligned liquid crystal cured film has the following formula (1):
ReA (450) / ReA (550) ≦ 1 (1)
[In formula (1), ReA (450) represents an in-plane retardation value at a wavelength of 450 nm in the in-plane direction of the horizontally aligned liquid crystal cured film, and ReA (550) represents a wavelength of 550 nm in the in-plane direction of the horizontally aligned liquid crystal cured film. Represents the in-plane retardation value at
The laminated body according to any one of [1] to [6], which satisfies the above.
[8] The laminate according to any one of [1] to [7], wherein the vertically aligned liquid crystal cured film includes a nonionic silane compound as a vertical alignment accelerator.
[9] The cured vertically aligned liquid crystal film includes a nonionic silane compound as a vertical alignment accelerator, and the nonionic silane compound is a silane coupling agent. Laminated body.
[10] The laminate according to any one of [1] to [9], wherein the vertically aligned liquid crystal cured film includes an ionic compound composed of a nonmetal atom as a vertical alignment accelerator.
[11] The above [1] to [10], wherein the vertically aligned liquid crystal cured film contains an ionic compound composed of a non-metal atom as a vertical alignment accelerator, and the molecular weight of the ionic compound is 100 or more and 10,000 or less. The laminated body in any one of.
[12] The laminate according to any one of [1] to [11], wherein the vertically aligned liquid crystal cured film includes a nonionic silane compound and an ionic compound including a nonmetal atom as a vertical alignment accelerator.
[13] A liquid crystal cured film obtained by curing a horizontally aligned liquid crystal cured film having a polymerizable liquid crystal compound having at least one radical polymerizable group aligned horizontally with respect to the in-plane direction of the liquid crystal cured film, The vertically aligned liquid crystal cured film is a cured liquid crystal film obtained by curing a polymerizable liquid crystal compound having at least one radical polymerizable group in a state of being aligned perpendicular to the in-plane direction of the liquid crystal cured film, The laminate according to any one of [1] to [12].
[14] The laminate according to any one of [1] to [13], wherein the vertically aligned liquid crystal cured film has at least one maximum absorption between wavelengths of 300 to 400 nm.
[15] The vertically aligned liquid crystal cured film has the following formula (2):
RthC (450) / RthC (550) ≦ 1 (2)
[In Formula (2), RthC (450) represents the retardation value in the thickness direction at a wavelength of 450 nm of the vertically aligned liquid crystal cured film, and RthC (550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. Represents]
The laminated body according to any one of [1] to [14], which satisfies the above.
[16] An elliptically polarizing plate comprising the laminate according to any one of [1] to [15] and a polarizing film.
[17] An elliptically polarizing plate including a laminate obtained by removing the substrate from the laminate according to any one of [1] to [15] and a polarizing film.
[18] The elliptically polarizing plate according to [16] or [17], wherein an angle formed between the slow axis of the horizontally aligned liquid crystal cured film constituting the laminate and the absorption axis of the polarizing film is 45 ± 5 ° .
[19] An organic EL display device including the elliptically polarizing plate according to any one of [16] to [18].
[20] The method for producing a laminate according to any one of [1] to [15],
Forming a coating film of a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film containing a polymerizable liquid crystal compound, and forming a vertically aligned liquid crystal cured film from the coated film;
Forming a coating film of the composition for forming a horizontal alignment film, and forming a horizontal alignment film from the coating film; and
The manufacturing method including the process of forming the coating film of the polymeric liquid crystal composition for horizontal alignment liquid crystal cured film formation containing a polymeric liquid crystal compound, and forming a horizontal alignment liquid crystal cured film from this coating film in this order.
[21] The manufacturing method according to [20], wherein the step of forming a vertical alignment liquid crystal cured film, the step of forming a horizontal alignment film, and the step of forming a horizontal alignment liquid crystal cured film are successively performed in this order.

  According to the present invention, the vertical alignment liquid crystal cured film is formed without forming the vertical alignment film, and the horizontal alignment liquid crystal cured film is continuously formed on the vertical alignment liquid crystal cured film via the horizontal alignment film. Can be provided, and a method for manufacturing the same. Further, in the laminate, the liquid crystal orientation is improved, and the adhesion between the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film formed on the vertical alignment liquid crystal cured film via the horizontal alignment film Can be improved.

It is a schematic sectional drawing which shows an example of the laminated constitution of the laminated body of this invention. It is a schematic sectional drawing which shows an example of the laminated constitution of the laminated body of this invention. It is a schematic sectional drawing which shows an example of the laminated constitution of the laminated body of this invention.

  The laminate of the present invention includes a substrate, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film in this order. Hereinafter, although an example of the layer structure of the laminated body of this invention is demonstrated based on FIGS. 1-3, the laminated body of this invention is not limited to these aspects.

  A laminate 11 shown in FIG. 1 is formed by laminating a base material 1, a vertical alignment liquid crystal cured film 2, a horizontal alignment film 3 and a horizontal alignment liquid crystal cured film 4 in this order. In the laminate 11 shown in FIG. 1, the vertically aligned liquid crystal cured film 2 is directly formed on the base material 1 without a layer having a vertical alignment regulating force (hereinafter also referred to as “vertical alignment film”). The base material 1 and the vertically aligned liquid crystal cured film 2 are adjacent to each other. In addition to the base material, the vertical alignment liquid crystal cured film, the horizontal alignment film and the horizontal alignment liquid crystal cured film, the laminate of the present invention is configured to include other layers as long as the effects of the present invention are not affected. It may be. Examples of the other layer include a cured resin layer such as a protective layer and a hard coat layer, a further horizontally aligned liquid crystal cured film, and an adhesive layer for bonding the laminate of the present invention to a polarizing film. .

  As a laminated body including other layers, for example, in the laminated body 11 shown in FIG. 2 which is another embodiment of the present invention, the base material 1 and the vertically aligned liquid crystal cured film 2 are interposed via the cured resin layer 5. The horizontal alignment film 3 and the horizontal alignment liquid crystal cured film 4 are laminated on the vertical alignment liquid crystal cured film 2. Furthermore, in the laminated body 11 shown in FIG. 3 which is another embodiment of the present invention, the base material 1 and the vertically aligned liquid crystal cured film 2 are stacked via the cured resin layer 5, and further, the vertically aligned liquid crystal A cured film 2 and a horizontal alignment film 3 are laminated via a cured resin layer 5, and a horizontal alignment liquid crystal cured film 4 is laminated on the horizontal alignment film 3. An elliptically polarizing plate can be obtained by laminating the laminate 11 and the polarizing film through the adhesive layer. At this time, either side of the vertically aligned liquid crystal cured film 2 and the horizontally aligned liquid crystal cured film 4 of the laminate 11 may be bonded to the polarizing film. For example, the substrate 1 of the laminate 11 in FIG. Thereafter, the vertically aligned liquid crystal cured film 2 may be bonded to the polarizing film via an adhesive layer, and the horizontally aligned liquid crystal cured film 4 of the laminate 11 in FIG. You may bond through an adhesive layer. Hereinafter, in the present specification, among the layer configurations of the laminate of the present invention, the minimum layer configuration including the base material, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film in this order is “basic”. Also referred to as “layer structure (I)”. That is, for example, when the laminate of the present invention is composed of a substrate, a vertical alignment liquid crystal cured film, a horizontal alignment film, a first horizontal alignment liquid crystal cured film, and a second horizontal alignment liquid crystal cured film, Up to the horizontally aligned liquid crystal cured film on the substrate side (in this case, the first horizontally aligned liquid crystal cured film) is the basic layer configuration (I) of the laminate of the present invention.

  In the laminate of the present invention, the total film thickness (between a and b in FIGS. 1 to 3) from the substrate-side surface of the vertically aligned liquid crystal cured film to the surface opposite to the horizontal aligned film of the horizontally aligned liquid crystal cured film. The thickness (hereinafter also referred to as “total film thickness T1”) is 10 μm or less. Since the laminate of the present invention can form a horizontal alignment liquid crystal cured film directly on a vertical alignment liquid crystal cured film via a horizontal alignment film, the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film are separately provided. After producing, compared with the conventional laminated body obtained by bonding both with an adhesive or an adhesive agent, total film thickness T1 can be made thin. The reduction in the total thickness T1 of the laminate can contribute to the reduction in the thickness of the entire laminate and the elliptically polarizing plate including the laminate. The total film thickness T1 in the laminate of the present invention is preferably 7 μm or less, more preferably 5 μm or less. The lower limit value of the total film thickness T1 is not particularly limited, and is usually 1 μm or more, for example, 1.5 μm or more. In the case where the laminate of the present invention further comprises a vertical alignment liquid crystal cured film and / or a horizontal alignment liquid crystal cured film on the side opposite to the horizontal alignment film of the horizontal alignment liquid crystal cured film of the basic layer structure (I), The film thickness T1 means the total film thickness from the surface on the substrate side of the vertically aligned liquid crystal cured film constituting the basic layer structure (I) to the surface opposite to the horizontal aligned film of the horizontally aligned liquid crystal cured film.

  In the laminate of the present invention, the vertically aligned liquid crystal cured film can be formed on the substrate or on the layer having no vertical alignment regulating force provided on the substrate without passing through the vertical alignment film. In the laminate of the present invention, the vertically aligned liquid crystal cured film can be formed without the vertical alignment film, so that the number of manufacturing steps of the laminate is reduced and the laminate can be manufactured with high productivity. That is, in one aspect of the laminate of the present invention, the base material and the vertically aligned liquid crystal cured film are stacked without interposing a vertical alignment film. In a more preferable aspect, the laminate of the present invention is a base material, A vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are adjacent to each other in this order. The laminated body of the present invention having such a layer structure can form a vertically aligned liquid crystal cured film on a substrate without a vertical alignment film, and further, via a horizontal alignment film on the vertically aligned liquid crystal cured film. Since the horizontally aligned liquid crystal cured film can be continuously formed, the laminate can be manufactured with higher productivity.

Hereinafter, each structure of the laminated body of this invention is demonstrated in detail.
[Vertical alignment liquid crystal cured film]
The vertically aligned liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymerizable liquid crystal composition that is cured in a state where the polymerizable liquid crystal compound is aligned in a direction perpendicular to the plane of the liquid crystal cured film. In the present invention, the vertically aligned liquid crystal cured film contains a vertical alignment accelerator. That is, in the present invention, the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains a vertical alignment accelerator. In the present invention, the vertical alignment promoter means a material that promotes the liquid crystal alignment of the polymerizable liquid crystal compound in the direction perpendicular to the film plane. When the vertical alignment liquid crystal cured film contains a vertical alignment accelerator, the vertical alignment liquid crystal cured film can be formed without the vertical alignment film. Thereby, in the laminated body of this invention, it is not necessary to form a vertical alignment liquid crystal cured film, the manufacturing process of a laminated body is simplified, and a laminated body can be manufactured with sufficient productivity. In addition, when forming a horizontal alignment film and a horizontal alignment liquid crystal cured film on this vertical alignment liquid crystal cured film, the orientation of a horizontal alignment liquid crystal cured film tends to deteriorate. The reason is not clear, but the surface energy is reduced by additives such as leveling agents contained in the vertically aligned liquid crystal cured film, and the orientation of the liquid crystal compound is liable to be impaired when the horizontal aligned liquid crystal cured film is formed in the upper layer. It is estimated to be. In particular, when a vertical alignment liquid crystal cured film is formed without a vertical alignment film, the influence is more remarkable because an alignment accelerator is further included.

  Examples of the vertical alignment promoter for promoting the vertical alignment of the polymerizable liquid crystal compound include a nonionic silane compound and an ionic compound composed of a nonmetal atom. The vertically aligned liquid crystal cured film preferably contains at least one of a nonionic silane compound and an ionic compound composed of a nonmetallic atom, and includes both a nonionic silane compound and an ionic compound composed of a nonmetallic atom. It is more preferable.

  When the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains a nonionic silane compound, the nonionic silane compound reduces the surface tension of the polymerizable liquid crystal composition and is formed from the polymerizable liquid crystal composition. In the dried coating film, the nonionic silane compound tends to be unevenly distributed at the interface between the dried coating film and the air, and the vertical alignment control force on the polymerizable liquid crystal compound is enhanced. Tends to be oriented in the vertical direction. Thereby, the liquid crystal cured film can be formed while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned.

The nonionic silane compound is a compound that is nonionic and contains Si element. Nonionic silane compounds include, for example, silicon polymers such as polysilanes, silicone resins such as silicone oils and silicone resins, and organic inorganic silane compounds such as silicone oligomers, silses siloxanes and alkoxy silanes (more specifically, Is a silane coupling agent or the like.
These nonionic silane compounds may be used individually by 1 type, or may be used in combination of 2 or more type. Especially, a silane coupling agent is preferable from a viewpoint of improving the adhesiveness with an adjacent layer more.

  The nonionic silane compound may be of a silicone monomer type or a silicone oligomer (polymer) type. When the silicone oligomer is shown in the form of (monomer)-(monomer) copolymer, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercapto Mercaptopropyl group-containing copolymers such as propyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetra Ethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer and mercaptomethyltriethoxysilane-tetrae A copolymer containing a mercaptomethyl group such as a xysilane copolymer; 3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane- Tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyl Oxypropylmethyldiethoxysilane-tetramethoxysilane copolymer And copolymers containing methacryloyloxypropyl groups such as 3-methacryloxyyl propylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane -Tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3- Acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxy Copolymers containing acryloyloxypropyl groups such as propylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane -Tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxy Silane-tetramethoxysilane copolymer and vinylmethyldiethoxysilane-tetrae Vinyl group-containing copolymers such as xysilane copolymers; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymers, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymers, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymers 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetra Amino group-containing copolymers such as methoxysilane copolymer and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer And the like.

  Silane coupling agent is selected from the group consisting of vinyl group, epoxy group, styryl group, methacryl group, acrylic group, amino group, isocyanurate group, ureido group, mercapto group, isocyanate group, carboxyl group, and hydroxyl group at the terminal. A compound containing Si element having at least one functional group and at least one alkoxysilyl group or silanol group. By selecting these functional groups as appropriate, the mechanical strength of the vertically aligned liquid crystal cured film, the surface modification of the vertically aligned liquid crystal cured film, the adhesion between the vertically aligned liquid crystal cured film and the adjacent layer, etc. It becomes possible to give a special effect. From the viewpoint of adhesion, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and another different reactive group (for example, the above functional group). Furthermore, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and a polar group. When the silane coupling agent has at least one alkoxysilyl group and at least one polar group in the molecule, the vertical alignment property of the polymerizable liquid crystal compound is more easily improved, and the vertical alignment promoting effect is remarkably obtained. There is a tendency. Examples of the polar group include an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxyl group, and a hydroxy group. The polar group may have a substituent or a protective group as appropriate in order to control the reactivity of the silane coupling agent.

  Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-glycidoxypropyltri Methoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltri Metoki Silane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane and 3-glycidoxypropylethoxydimethylsilane Can be mentioned.

  Examples of commercially available silane coupling agents include KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, and KBM-403. , KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE Silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. such as -9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007 Is mentioned.

  When the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains a nonionic silane compound, the content is usually preferably 100 parts by weight of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. Is 0.01-5 parts by mass, more preferably 0.05-4 parts by mass, and still more preferably 0.1-3 parts by mass. When the content of the nonionic silane compound is within the above range, it is possible to effectively promote the vertical alignment of the polymerizable liquid crystal compound while maintaining good coating properties of the polymerizable liquid crystal composition.

  When the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains an ionic compound composed of a non-metal atom, the dry coating film formed from the polymerizable liquid crystal composition is polymerizable by electrostatic interaction. The vertical alignment control force with respect to the liquid crystal compound is developed, and the polymerizable liquid crystal compound tends to be aligned in the direction perpendicular to the film plane in the dry coating film. Thereby, the liquid crystal cured film can be formed while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned.

  Examples of ionic compounds composed of nonmetallic atoms include onium salts (more specifically, quaternary ammonium salts, tertiary sulfonium salts in which the nitrogen atom has a positive charge, and phosphorus atoms have a positive charge. And quaternary phosphonium salts. Among these onium salts, a quaternary onium salt is preferable from the viewpoint of further improving the vertical alignment of the polymerizable liquid crystal compound, and from the viewpoint of improving availability and mass productivity, a quaternary phosphonium salt or a quaternary salt. Ammonium salts are more preferred. The onium salt may have two or more quaternary onium salt sites in the molecule, and may be an oligomer or a polymer.

  The molecular weight of the ionic compound comprising a nonmetallic atom is preferably 100 or more and 10,000 or less. When the molecular weight is within the above range, it is easy to improve the vertical alignment property of the polymerizable liquid crystal compound while ensuring the applicability of the polymerizable liquid crystal composition. The molecular weight of the ionic compound comprising a nonmetallic atom is more preferably 5000 or less, and still more preferably 3000 or less.

  Examples of the cation component of the ionic compound composed of a nonmetallic atom include an inorganic cation and an organic cation. Among these, an organic cation is preferable because it hardly causes alignment defects of the polymerizable liquid crystal compound. Examples of the organic cation include an imidazolium cation, a pyridinium cation, an ammonium cation, a sulfonium cation, and a phosphonium cation.

  An ionic compound composed of a nonmetallic atom generally has a counter anion. As an anion component used as the counter ion of the said cation component, an inorganic anion and an organic anion are mentioned, for example. Among these, an organic anion is preferable because it hardly causes alignment defects of the polymerizable liquid crystal compound. The cation and the anion do not necessarily have a one-to-one correspondence.

Specific examples of the anion component include the following.
Chloride anion [Cl ⁻ ],
Bromide anion [Br ⁻ ],
Iodide anion [I ⁻ ],
Tetrachloroaluminate anion [AlCl ₄ ⁻ ],
Heptachlorodialuminate anion [Al ₂ Cl ₇ ⁻ ],
Tetrafluoroborate anion [BF ₄ ⁻ ],
Hexafluorophosphate anion [PF ₆ ⁻ ],
Perchlorate anion [ClO ₄ ⁻ ],
Nitrate anion [NO ₃ ⁻ ],
Acetate anion [CH ₃ COO ⁻ ],
Trifluoroacetate anion [CF ₃ COO ⁻ ],
Fluorosulfonate anion [FSO ₃ ⁻ ],
Methanesulfonate anion [CH ₃ SO ₃ ⁻ ],
Trifluoromethanesulfonate anion [CF ₃ SO ₃ ⁻ ],
p-toluenesulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ⁻ ],
Bis (fluorosulfonyl) imide anion [(FSO ₂ ) ₂ N ⁻ ],
Bis (trifluoromethanesulfonyl) imide anion [(CF ₃ SO ₂ ) ₂ N ⁻ ],
Tris (trifluoromethanesulfonyl) methanide anion [(CF ₃ SO ₂ ) ₃ C ⁻ ],
Hexafluoroarsenate anion [AsF ₆ ⁻ ],
Hexafluoroantimonate anion [SbF ₆ ⁻ ],
Hexafluoroniobate anion [NbF ₆ ⁻ ],
Hexafluorotantalate anion [TaF ₆ ⁻ ],
Dimethyl phosphinate anion [(CH ₃ ) ₂ POO ⁻ ],
(Poly) hydrofluorofluoride anion [F (HF) _n ⁻ ] (for example, n represents an integer of 1 to 3),
Dicyanamide anion [(CN) ₂ N ⁻ ],
Thiocyan anion [SCN ⁻ ],
Perfluorobutanesulfonate anion [C ₄ F ₉ SO ₃ ⁻ ],
Bis (pentafluoroethanesulfonyl) imide anion [(C ₂ F ₅ SO ₂ ) ₂ N ⁻ ],
Perfluorobutanoate anion [C ₃ F ₇ COO ⁻ ], and (trifluoromethanesulfonyl) (trifluoromethanecarbonyl) imide anion [(CF ₃ SO ₂ ) (CF ₃ CO) N ⁻ ].

  Specific examples of the ionic compound composed of a non-metal atom can be appropriately selected from the combination of the cation component and the anion component. Specific examples of the compound that is a combination of a cation component and an anion component include the following.

(Pyridinium salt)
N-hexylpyridinium hexafluorophosphate,
N-octylpyridinium hexafluorophosphate,
N-methyl-4-hexylpyridinium hexafluorophosphate,
N-butyl-4-methylpyridinium hexafluorophosphate,
N-octyl-4-methylpyridinium hexafluorophosphate,
N-hexylpyridinium bis (fluorosulfonyl) imide,
N-octylpyridinium bis (fluorosulfonyl) imide,
N-methyl-4-hexylpyridinium bis (fluorosulfonyl) imide,
N-butyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-octyl-4-methylpyridinium bis (fluorosulfonyl) imide,
N-hexylpyridinium bis (trifluoromethanesulfonyl) imide,
N-octylpyridinium bis (trifluoromethanesulfonyl) imide,
N-methyl-4-hexylpyridinium bis (trifluoromethanesulfonyl) imide,
N-butyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,
N-octyl-4-methylpyridinium bis (trifluoromethanesulfonyl) imide,
N-hexylpyridinium p-toluenesulfonate,
N-octylpyridinium p-toluenesulfonate,
N-methyl-4-hexylpyridinium p-toluenesulfonate,
N-butyl-4-methylpyridinium p-toluenesulfonate, and N-octyl-4-methylpyridinium p-toluenesulfonate.

(Imidazolium salt)
1-ethyl-3-methylimidazolium hexafluorophosphate,
1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide,
1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide,
1-ethyl-3-methylimidazolium p-toluenesulfonate,
1-butyl-3-methylimidazolium methanesulfonate and the like.

(Pyrrolidinium salt)
N-butyl-N-methylpyrrolidinium hexafluorophosphate,
N-butyl-N-methylpyrrolidinium bis (fluorosulfonyl) imide,
N-butyl-N-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide,
N-butyl-N-methylpyrrolidinium p-toluenesulfonate and the like.

(Ammonium salt)
Tetrabutylammonium hexafluorophosphate,
Tetrabutylammonium bis (fluorosulfonyl) imide,
Tetrahexylammonium bis (fluorosulfonyl) imide,
Trioctylmethylammonium bis (fluorosulfonyl) imide,
(2-hydroxyethyl) trimethylammonium bis (fluorosulfonyl) imide,
Tetrabutylammonium bis (trifluoromethanesulfonyl) imide,
Tetrahexylammonium bis (trifluoromethanesulfonyl) imide,
Trioctylmethylammonium bis (trifluoromethanesulfonyl) imide,
(2-hydroxyethyl) trimethylammonium bis (trifluoromethanesulfonyl) imide,
Tetrabutylammonium p-toluenesulfonate,
Tetrahexylammonium p-toluenesulfonate,
Trioctylmethylammonium p-toluenesulfonate,
(2-hydroxyethyl) trimethylammonium p-toluenesulfonate,
(2-hydroxyethyl) trimethylammonium dimethylphosphinate 1- (3-trimethoxysilylpropyl) -1,1,1-tributylammonium bis (trifluoromethanesulfonyl) imide,
1- (3-trimethoxysilylpropyl) -1,1,1-trimethylammonium bis (trifluoromethanesulfonyl) imide,
1- (3-trimethoxysilylbutyl) -1,1,1-tributylammonium bis (trifluoromethanesulfonyl) imide,
1- (3-trimethoxysilylbutyl) -1,1,1-trimethylammonium bis (trifluoromethanesulfonyl) imide,
N-{(3-triethoxysilylpropyl) carbamoyloxyethyl)}-N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide, and N- [2- {3- (3-trimethoxysilylpropylamino) ) -1-Oxopropoxy} ethyl] -N, N, N-trimethylammonium bis (trifluoromethanesulfonyl) imide.

(Phosphonium salt)
Tributyl (2-methoxyethyl) phosphonium bis (trifluoromethanesulfonyl) imide,
Tributylmethylphosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1-[(trimethoxysilyl) methyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1- [2- (trimethoxysilyl) ethyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1- [3- (trimethoxysilyl) propyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-trimethyl-1- [4- (trimethoxysilyl) butyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-tributyl-1-[(trimethoxysilyl) methyl] phosphonium bis (trifluoromethanesulfonyl) imide,
1,1,1-tributyl-1- [2- (trimethoxysilyl) ethyl] phosphonium bis (trifluoromethanesulfonyl) imide, and 1,1,1-tributyl-1- [3- (trimethoxysilyl) propyl] Phosphonium bis (trifluoromethanesulfonyl) imide.
These ionic compounds may be used alone or in combination of two or more. Of these, ionic compounds composed of phosphonium salts, pyridinium salts, and ammonium salts are preferred.

  From the viewpoint of further improving the vertical alignment of the polymerizable liquid crystal compound, the ionic compound composed of a non-metal atom preferably has an Si element and / or an F element in the molecular structure of the cation moiety. When the ionic compound composed of a nonmetallic atom has Si element and / or F element in the molecular structure of the cation moiety, the ionic compound is easily segregated on the surface of the vertically aligned liquid crystal cured film. Among these, the following ionic compounds (i) to (iii) are preferable as the ionic compound in which the constituent elements are all nonmetallic elements.

（イオン性化合物（ｉｉ））

（イオン性化合物（ｉｉｉ））

(Ionic compound (i))

(Ionic compound (ii))

(Ionic compound (iii))

  For example, a method for improving the alignment of liquid crystal by treating the surface of the substrate with a surfactant having an alkyl group having a long chain length (for example, the alignment and physical properties of liquid crystal (Maruzen The vertical alignment property of the polymerizable liquid crystal compound can be further improved by applying the above). That is, the vertical alignment of the polymerizable liquid crystal compound can be effectively improved by treating the substrate surface with an ionic compound having an alkyl group having a long chain length to some extent.

Specifically, it is preferable that an ionic compound composed of a nonmetallic atom satisfies the following formula (3).
5 <M <16 (3)
In formula (3), M is represented by the following formula (4).
M = (the number of covalent bonds from the positively charged atom to the end of the molecular chain of the substituent having the largest number of covalent bonds to the end of the molecular chain among the substituents directly bonded on the positively charged atom ) ÷ (number of positively charged atoms) (4)
When the ionic compound composed of a nonmetallic atom satisfies the above (3), the vertical alignment property of the polymerizable liquid crystal compound can be effectively improved.

  In addition, when there are two or more positively charged atoms in the molecule of an ionic compound composed of a nonmetallic atom, a positive charge considered as a base point for a substituent having two or more positively charged atoms The number of covalent bonds from the atom having the nearest other positively charged atom to the closest positively charged atom is defined as “the number of covalent bonds from the positively charged atom to the end of the molecular chain” described in the definition of M above. Moreover, when the ionic compound which consists of a nonmetallic atom is an oligomer or polymer which has two or more repeating units, a structural unit is considered as one molecule and M is calculated. When an atom having a positive charge is incorporated in a ring structure, the number of covalent bonds leading to the atom having the same positive charge via the ring structure or the end of a substituent bonded to the ring structure Of the number of covalent bonds, the larger number of covalent bonds is defined as “the number of covalent bonds from the positively charged atom to the end of the molecular chain” described in the definition of M above.

  When the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains an ionic compound composed of a nonmetal atom, the content thereof is usually 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. It is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, and still more preferably 0.1 to 3 parts by mass. When the content of the ionic compound composed of a nonmetallic atom is within the above range, it is possible to effectively promote the vertical alignment of the polymerizable liquid crystal compound while maintaining good coating properties of the polymerizable liquid crystal composition. it can.

  From the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film, the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains both a nonionic silane compound and an ionic compound comprising a nonmetallic atom. In the formed dried coating film, the vertical alignment of the polymerizable liquid crystal compound is further promoted by the electrostatic interaction derived from the ionic compound composed of nonmetallic atoms and the surface tension reducing effect derived from the nonionic silane compound. It becomes easy to be done. Thereby, the liquid crystal cured film can be formed while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned more accurately.

  The vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing the above vertical alignment accelerator and at least one polymerizable liquid crystal compound, preferably a polymerizable liquid crystal compound having at least one radical polymerizable group Is a liquid crystal cured film obtained by curing in a state of being aligned perpendicular to the in-plane direction of the liquid crystal cured film. In the present invention, the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film means a liquid crystal compound having a polymerizable group, and in particular, a liquid crystal compound having at least one radical polymerizable group. preferable. The polymerizable liquid crystal compound is not particularly limited, and for example, a conventionally known polymerizable liquid crystal compound can be used in the field of retardation film.

  The polymerizable group refers to a group that can participate in a polymerization reaction by an active radical or an acid generated from a polymerization initiator. Examples of the polymerizable group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group. Among them, a radical polymerizable group is preferable, an acryloyloxy group, a methacryloyloxy group, a vinyl group, and a vinyloxy group are more preferable, and an acryloyloxy group and a methacryloyloxy group are more preferable. When the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film are laminated via the horizontal alignment film, the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film both have at least one radical polymerizable group. In the case of a cured product of a liquid crystal compound, the adhesion between the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film continuously formed through the horizontal photo-aligned film formed from a polymer having a (meth) acryloyl group is Easy to improve.

  The liquid crystal property of the polymerizable liquid crystal compound may be either a thermotropic liquid crystal or a lyotropic liquid crystal, but the thermotropic liquid crystal is preferred in terms of enabling precise film thickness control. The phase order structure in the thermotropic liquid crystal may be a nematic liquid crystal or a smectic liquid crystal. The polymerizable liquid crystal compounds can be used alone or in combination of two or more.

  Examples of the polymerizable liquid crystal compound generally include a polymerizable liquid crystal compound exhibiting positive wavelength dispersion and a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion, and either one of the polymerizable liquid crystal compounds may be used. It is also possible to use a mixture of both types of polymerizable liquid crystal compounds. From the viewpoint of a large effect of suppressing the oblique reflection hue during black display when the vertically aligned liquid crystal cured film is applied to a display device, it is preferable to include a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion.

The polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is preferably a compound having the following characteristics (A) to (D).
(A) A compound capable of forming a nematic phase or a smectic phase.
(B) It has pi electrons on the major axis direction (a) of the polymerizable liquid crystal compound.
(C) It has π electrons on the direction [cross direction (b)] intersecting with the major axis direction (a).
(D) A polymerizable liquid crystal compound defined by the following formula (i) where N (πa) is the total of π electrons present in the major axis direction (a) and N (Aa) is the total molecular weight present in the major axis direction Π electron density in the major axis direction (a):
D (πa) = N (πa) / N (Aa) (i)
A polymerizable liquid crystal compound defined by the following formula (ii) where N (πb) is the total of π electrons present in the cross direction (b) and N (Ab) is the total molecular weight present in the cross direction (b) Π electron density in the cross direction (b) of:
D (πb) = N (πb) / N (Ab) (ii)
And the formula (iii)
0 ≦ [D (πa) / D (πb)] <1 (iii)
[In other words, the π electron density in the cross direction (b) is larger than the π electron density in the major axis direction (a)). Further, as described above, the polymerizable liquid crystal compound having π electrons in the major axis and in the direction intersecting with the major axis has, for example, a T-shaped structure.

In the features (A) to (D) above, the major axis direction (a) and the number of π electrons N are defined as follows.
The major axis direction (a) is the major axis direction of a rod in the case of a compound having a rod-like structure, for example.
The number of π electrons N (πa) existing on the major axis direction (a) does not include π electrons that disappear due to the polymerization reaction.
The number of π electrons N (πa) existing on the major axis direction (a) is the total number of π electrons on the major axis and π electrons conjugated with this, for example, present on the major axis direction (a) And the number of π electrons present in the ring that satisfies the Hückel rule.
The number of π electrons N (πb) existing in the cross direction (b) does not include π electrons that disappear due to the polymerization reaction.
The polymerizable liquid crystal compound satisfying the above has a mesogenic structure in the major axis direction. Due to this mesogenic structure, a liquid crystal phase (nematic phase, smectic phase) is expressed.

  A nematic phase or a smectic phase is formed by applying a polymerizable liquid crystal compound satisfying the above (A) to (D) onto a film (layer) that forms a liquid crystal cured film and heating it to a temperature higher than the phase transition temperature. Is possible. In the nematic phase or smectic phase formed by aligning this polymerizable liquid crystal compound, the major axis directions of the polymerizable liquid crystal compound are usually aligned parallel to each other, and this major axis direction is the alignment direction of the nematic phase. It becomes. When such a polymerizable liquid crystal compound is formed into a film and polymerized in a nematic phase or a smectic phase, a polymer film made of a polymer polymerized in a state of being oriented in the major axis direction (a) can be formed. . This polymer film absorbs ultraviolet rays by π electrons in the major axis direction (a) and π electrons in the cross direction (b). Here, the absorption maximum wavelength of ultraviolet light absorbed by the π electrons in the intersecting direction (b) is λbmax. λbmax is usually 300 nm to 400 nm. The density of π electrons satisfies the above formula (iii), and the π electron density in the cross direction (b) is larger than the π electron density in the major axis direction (a). The absorption of linearly polarized ultraviolet light having a wavelength (λbmax) is larger than that of linearly polarized ultraviolet light having a vibration plane in the major axis direction (a) (wavelength is λbmax). The ratio (ratio of absorbance in the crossing direction (b) of linearly polarized ultraviolet light / absorbance in the long axis direction (a)) is, for example, more than 1.0, preferably 1.2 or more, and usually 30 or less, for example, 10 or less. It is.

In general, the polymerizable liquid crystal compound having the above characteristics often exhibits reverse wavelength dispersion. Specific examples include compounds represented by the following formula (X).

In formula (X), Ar represents a divalent group having an aromatic group which may have a substituent. The aromatic group as used herein means one having [4n + 2] π electrons according to the Huckel rule, and is exemplified by (Ar-1) to (Ar-23) described later. You may have two or more such Ar groups through a bivalent coupling group. Here, n represents an integer. In the case where a ring structure is formed by including a heteroatom such as -N = or -S-, the case where the Huckel's rule is satisfied including the non-covalent electron pair on the heteroatom and the aromatic structure is included is also included. The aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom and a sulfur atom. The divalent group Ar may contain one aromatic group or two or more aromatic groups. When there is one aromatic group, the divalent group Ar may be a divalent aromatic group which may have a substituent. When the divalent group Ar contains two or more aromatic groups, the two or more aromatic groups are bonded to each other by a divalent linking group such as a single bond, —CO—O—, and —O—. It may be.
G ¹ and G ² each independently represents a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or carbon. The carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group which may be substituted with an alkoxy group, cyano group or nitro group of formulas 1 to 4 is an oxygen atom or a sulfur atom Alternatively, it may be substituted with a nitrogen atom.
L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group.
k and l each independently represent an integer of 0 to 3, and satisfy the relationship 1 ≦ k + 1. Here, when 2 ≦ k + 1, B ¹ and B ² , G ¹ and G ² may be the same or different from each other.
E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms, where an alkanediyl group having 4 to 12 carbon atoms is more preferable. Moreover, the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and —CH ₂ — contained in the alkanediyl group is —O—, —S—, —SiH ₂ —, —C It may be substituted with (= O)-.
P ¹ and P ² each independently represent a polymerizable group or a hydrogen atom, and at least one is a polymerizable group.

G ¹ and G ² are each independently preferably a 1,4-phenylenediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms. 1,4-cyclohexanediyl group optionally substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1 substituted with a methyl group , 4-phenylenediyl group, unsubstituted 1,4-phenylenediyl group, or unsubstituted 1,4-trans-cyclohexanediyl group, particularly preferably unsubstituted 1,4-phenylenediyl group or A substituted 1,4-trans-cyclohexanediyl group.
In addition, at least one of a plurality of G ¹ and G ² is preferably a divalent alicyclic hydrocarbon group, and at least one of G ¹ and G ² bonded to L ¹ or L ² More preferably, it is a divalent alicyclic hydrocarbon group.

L ¹ and L ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, —O—, —S—, —R ^a1 OR ^a2 —, —R ^a3 COOR ^a4 —, —R ^a5. OCOR ^a6 —, R ^a7 OC═OOR ^a8 —, —N═N—, —CR ^c = CR ^d —, or —C≡C—. Here, R ^{a1 to} R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and R ^d each represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. L ¹ and L ² are each independently more preferably a single bond, —OR ^a2-1 —, —CH ₂ —, —CH ₂ CH ₂ —, ^{—COOR a4-1} —, or —OCOR ^a6-1 —. is there. Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent a single bond, —CH ₂ —, or —CH ₂ CH ₂ —. L ¹ and L ² are each independently a single bond, —O—, —CH ₂ CH ₂ —, —COO—, —COOCH ₂ CH ₂ —, or —OCO—.

B ¹ and B ² are preferably each independently, preferably a single bond, an alkylene group having 1 to 4 carbon atoms, —O—, —S—, —R ^a9 OR ^a10 —, —R ^a11 COOR ^a12 —, —R ^a13. OCOR ^a14 − or R ^a15 OC═OOR ^a16 —. Here, R ^{a9 to} R ^a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. B ¹ and B ² are each independently more preferably a single bond, —OR ^a10-1 —, —CH ₂ —, —CH ₂ CH ₂ —, ^{—COOR a12-1} —, or OCOR ^a14-1 —. . Here, R ^a10-1 , R ^a12-1 , and R ^a14-1 each independently represent a single bond, —CH ₂ —, or —CH ₂ CH ₂ —. B ¹ and ^{B 2} are each independently more preferably a single _{bond, -O -, - CH 2 CH} 2 -, - COO -, - COOCH 2 CH 2 -, - OCO-, or -OCOCH ₂ CH ₂ - in is there.

  k and l are preferably in the range of 2 ≦ k + l ≦ 6 from the viewpoint of expression of inverse wavelength dispersion, preferably k + l = 4, and more preferably k = 2 and l = 2. It is preferable that k = 2 and l = 2 because a symmetrical structure is obtained.

Examples of the polymerizable group represented by P ¹ or P ² include an epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, and oxiranyl group. And an oxetanyl group. Among these, an acryloyloxy group, a methacryloyloxy group, a vinyl group and a vinyloxy group are preferable, and an acryloyloxy group and a methacryloyloxy group are more preferable.

  Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocycle include furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyrazine ring, pyrimidine ring, triazole ring, triazine ring, pyrroline ring, imidazole ring, pyrazole ring. , Thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, phenanthrolin ring, and the like. Of these, a thiazole ring, a benzothiazole ring, or a benzofuran ring is preferable, and a benzothiazole group is more preferable. In addition, when Ar includes a nitrogen atom, the nitrogen atom preferably has π electrons.

In the formula (X), the total number N of _π electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, particularly Preferably it is 16 or more. Moreover, Preferably it is 30 or less, More preferably, it is 26 or less, More preferably, it is 24 or less.

  Examples of the aromatic group represented by Ar include the following groups.

In formula (Ar-1) to formula (Ar-23), * represents a linking part, and Z ⁰ , Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, or an alkyl having 1 to 12 carbon atoms. Group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, C1-C12 alkylthio group, C1-C12 N-alkylamino group, C2-C12 N, N-dialkylamino group, C1-C12 N-alkylsulfamoyl group or carbon The N, N-dialkylsulfamoyl group represented by Formula 2 to 12 is represented. Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

Q ¹ and Q ² each independently represent —CR ^{2 ′} R ^{3 ′} —, —S—, —NH—, —NR ^{2 ′} —, —CO— or —O—, wherein R ^{2 ′} and R ^{3 '} Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

J ¹ and J ² each independently represent a carbon atom or a nitrogen atom.

Y ¹ , Y ² and Y ³ each independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group.

W ¹ and W ² each independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0 to 6.

Examples of the aromatic hydrocarbon group for Y ¹ , Y ² and Y ³ include an aromatic hydrocarbon group having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and a biphenyl group. A naphthyl group is preferred, and a phenyl group is more preferred. The aromatic heterocyclic group has 4 to 20 carbon atoms and contains at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom such as a furyl group, a pyrrolyl group, a thienyl group, a pyridinyl group, a thiazolyl group, or a benzothiazolyl group. An aromatic heterocyclic group is mentioned, and a furyl group, a thienyl group, a pyridinyl group, a thiazolyl group, and a benzothiazolyl group are preferable.

Y ¹ , Y ² and Y ³ may each independently be an optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from an aggregate of aromatic rings. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.

Z ⁰ , Z ¹ and Z ² are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, or an alkoxy group having 1 to 12 carbon atoms. ⁰ is more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyano group, and Z ¹ and Z ² are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group. Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

Q ¹ and Q ² are preferably —NH—, —S—, —NR ^{2 ′} —, and —O—, and R ^{2 ′} is preferably a hydrogen atom. Among them, -S-, -O-, and -NH- are particularly preferable.

  Among formulas (Ar-1) to (Ar-23), formula (Ar-6) and formula (Ar-7) are preferable from the viewpoint of molecular stability.

In formulas (Ar-16) to (Ar-23), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . Examples of the aromatic heterocyclic group include those described above as the aromatic heterocyclic ring that Ar may have, for example, pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyrazine ring, pyrimidine ring, indole Ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring and the like. This aromatic heterocyclic group may have a substituent. Y ¹ may be the above-described optionally substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring, etc. are mentioned.

  Moreover, as a polymerizable liquid crystal compound for forming a vertically aligned liquid crystal cured film in the present invention, for example, a compound containing a group represented by the following formula (Y) (hereinafter also referred to as “polymerizable liquid crystal compound (Y)”). It may be used. The polymerizable liquid crystal compound (Y) generally tends to exhibit positive wavelength dispersion. The polymerizable liquid crystal compounds can be used alone or in combination of two or more.

P11-B11-E11-B12-A11-B13- (Y)
[In formula (Y), P11 represents a polymerizable group.
A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and divalent aromatic hydrocarbon group is a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a nitro group. The hydrogen atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom.
B11 is —O—, —S—, —CO—O—, —O—CO—, —O—CO—O—, —CO—NR ¹⁶ —, —NR ¹⁶ —CO—, —CO—, — CS- or a single bond is represented. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B12 and B13 are each _{independently, -C≡C -, - CH = CH} -, - CH 2 -CH 2 -, - O -, - S -, - C (= O) -, - C (= O ) -O-, -OC (= O)-, -O-C (= O) -O-, -CH = N-, -N = CH-, -N = N-, -C (= O ) —NR ¹⁶ —, —NR ¹⁶ —C (═O) —, —OCH ₂ —, —OCF ₂ —, —CH ₂ O—, —CF ₂ O—, —CH═CH—C (═O) — O—, —O—C (═O) —CH═CH— or a single bond is represented.
E11 represents an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atom contained in the alkoxy group May be substituted with a halogen atom. In addition, —CH ₂ — constituting the alkanediyl group may be replaced by —O— or —CO—. ]

  The number of carbon atoms of the aromatic hydrocarbon group and alicyclic hydrocarbon group of A11 is preferably in the range of 3-18, more preferably in the range of 5-12, and particularly preferably 5 or 6. preferable. A11 is preferably a cyclohexane-1,4-diyl group or a 1,4-phenylene group.

E11 is preferably a linear alkanediyl group having 1 to 12 carbon atoms. —CH ₂ — constituting the alkanediyl group may be replaced by —O—.
Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane -1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group and dodecane-1,12- A linear alkanediyl group having 1 to 12 carbon atoms such as a diyl group; —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —, —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —O—; CH ₂ —CH ₂ — and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —O—CH ₂ —CH ₂ — and the like can be mentioned.
B11 is preferably —O—, —S—, —CO—O—, or —O—CO—, and more preferably —CO—O—.
B12 and B13 are each independently —O—, —S—, —C (═O) —, —C (═O) —O—, —O—C (═O) —, —O—C. (═O) —O— is preferable, and —O— or —O—C (═O) —O— is more preferable.

［式（Ｐ−１１）〜（Ｐ−１５）中、
Ｒ^１７〜Ｒ^２１はそれぞれ独立に、炭素数１〜６のアルキル基または水素原子を表わす。］ The polymerizable group represented by P11 is preferably a radical polymerizable group or a cationic polymerizable group in view of high polymerization reactivity, particularly photopolymerization reactivity, and is easy to handle and easy to produce a liquid crystal compound. Therefore, the polymerizable group is preferably a group represented by the following formula (P-11) to formula (P-15).

[In the formulas (P-11) to (P-15),
R ^{17 to} R ²¹ each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. ]

Specific examples of the groups represented by formula (P-11) to formula (P-15) include groups represented by the following formula (P-16) to formula (P-20).

P11 is preferably a group represented by Formula (P-14) to Formula (P-20), and more preferably a vinyl group, a p-stilbene group, an epoxy group, or an oxetanyl group.
More preferably, the group represented by P11-B11- is an acryloyloxy group or a methacryloyloxy group.

Examples of the polymerizable liquid crystal compound (Y) include compounds represented by the formula (I), the formula (II), the formula (III), the formula (IV), the formula (V), or the formula (VI).
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-B16-E12-B17-P12 (I)
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-F11 (II)
P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-E12-B17-P12 (III)
P11-B11-E11-B12-A11-B13-A12-B14-A13-F11 (IV)
P11-B11-E11-B12-A11-B13-A12-B14-E12-B17-P12 (V)
P11-B11-E11-B12-A11-B13-A12-F11 (VI)
(Where
A12 to A14 are independently synonymous with A11, B14 to B16 are independently synonymous with B12, B17 is synonymous with B11, and E12 is synonymous with E11.
F11 is a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxy group, a methylol group, a formyl group, and a sulfo group. (—SO ₃ H), a carboxyl group, an alkoxycarbonyl group having 1 to 10 carbon atoms or a halogen atom, —CH ₂ — constituting the alkyl group and alkoxy group may be replaced by —O—. Good. )

  As a specific example of the polymerizable liquid crystal compound (Y), “3.8.6 Network (fully crosslinked type)” of Liquid Crystal Handbook (Edited by Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000) Among the compounds described in "6.5. 1 Liquid crystal material b. Polymerizable nematic liquid crystal material", JP 2010-31223 A, JP 2010-270108 A, JP Examples thereof include polymerizable liquid crystals described in JP2011-6360A and JP2011-207765A.

  Specific examples of the polymerizable liquid crystal compound (Y) include the following formulas (I-1) to (I-4), formulas (II-1) to (II-4), and formulas (III-1) to (III). (III-26), Formula (IV-1) to Formula (IV-26), Formula (V-1) to Formula (V-2), and Formula (VI-1) to Formula (VI-6). Compounds. In the following formulae, k1 and k2 each independently represent an integer of 2 to 12. These polymerizable liquid crystal compounds (Y) are preferable from the viewpoint of easy synthesis or availability.

  By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity, a vertically aligned liquid crystal cured film having a high degree of alignment order can be formed. In the present invention, when a polymerizable liquid crystal compound exhibiting a smectic liquid crystal property is used as the polymerizable liquid crystal compound for forming a vertically aligned liquid crystal cured film, the polymerizable liquid crystal compound has a higher order from the viewpoint of achieving a higher degree of alignment order. The smectic phase (higher order smectic liquid crystal state) is more preferable. Here, the higher-order smectic phase means a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, and a smectic L phase. This means that among these, the smectic B phase, the smectic F phase, and the smectic I phase are more preferable. The thermic liquid crystal may be either a thermotropic liquid crystal or a lyotropic liquid crystal, but the thermotropic liquid crystal is preferred in terms of enabling precise film thickness control. The polymerizable liquid crystal compound exhibiting smectic liquid crystallinity may be a monomer, but may be an oligomer or a polymer in which a polymerizable group is polymerized.

  The polymerizable liquid crystal compound exhibiting smectic liquid crystallinity is a liquid crystal compound having at least one polymerizable group, and is a liquid crystal compound having two or more polymerizable groups from the viewpoint of improving the heat resistance of the vertically aligned liquid crystal cured film. It is preferable. Examples of the polymerizable group include (meth) acryloyloxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, oxiranyl group, oxetanyl group, etc. The heat resistance of the vertically aligned liquid crystal cured film is easily improved, the adhesion between the vertically aligned liquid crystal cured film and the horizontal alignment film formed from the polymer having a (meth) acryloyl group, and further the horizontal alignment A (meth) acryloyloxy group is preferably included because it is easy to adjust and improve the adhesion to the horizontally aligned liquid crystal cured film through the film.

Examples of the polymerizable liquid crystal compound exhibiting smectic liquid crystallinity include a compound represented by the following formula (Z) (hereinafter sometimes referred to as “polymerizable liquid crystal compound (Z)”).
^{U 1z -V 1z -W 1z - (} X 1z -Y 1z -) nz -X 2z -W 2z -V 2z -U 2z (Z)
[In formula (Z), X ^1z and X ^2z each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group, wherein the divalent aromatic group or 2 The hydrogen atom contained in the valent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, or a nitro group. A carbon atom constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or a nitrogen atom. However, at least one of X ^1z and X ^2z is a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent.
Y ^1z is a single bond or a divalent linking group.
nz is 1 to 3, and when nz is 2 or more, the plurality of X ^1z may be the same or different. X ^2z may be the same as or different from any or all of the plurality of X ^1z . When nz is 2 or more, the plurality of Y ^1z may be the same as or different from each other. From the viewpoint of liquid crystallinity, nz is preferably 2 or more.
U ^1z represents a hydrogen atom or a (meth) acryloyloxy group.
U ^2z represents a polymerizable group.
W ^1z and W ^2z are each independently a single bond or a divalent linking group.
V ^1z and V ^2z each independently represent an ^optionally substituted alkanediyl group having 1 to 20 carbon atoms, and —CH ₂ — constituting the alkanediyl group is —O—, -CO-, -S- or NH- may be substituted. ]

In the polymerizable liquid crystal compound (Z), X ^1z and X ^2z are preferably independently of each other, preferably a 1,4-phenylene group which may have a substituent, or a substituent. It is a good cyclohexane-1,4-diyl group, and at least one of X ^1z and X ^2z has a 1,4-phenylene group which may have a substituent, or a substituent. A cyclohexane-1,4-diyl group, preferably a trans-cyclohexane-1,4-diyl group. Examples of the substituent that the optionally substituted 1,4-phenylene group or optionally substituted cyclohexane-1,4-diyl group includes a methyl group, ethyl Group, a C1-C4 alkyl group such as a butyl group, a cyano group, and a halogen atom such as a chlorine atom and a fluorine atom. Preferably it is unsubstituted.

The polymerizable liquid crystal compound (Z) is represented by the formula (Z1):
_{^{- (X 1z -Y 1z -)}} nz -X 2z - (Z1)
[ ^Wherein , X ^1z , Y ^1z , X ^2z and nz each have the same meaning as described above. ]
[Hereinafter referred to as a partial structure (Z1). ] Is preferably an asymmetric structure in that it easily exhibits smectic liquid crystallinity.
Examples of the polymerizable liquid crystal compound (Z) in which the partial structure (Z1) is an asymmetric structure include a polymerizable liquid crystal compound (Z) in which nz is 1 and one X ^1z and X ^2z are different from each other. Can be mentioned. Further, nz is 2 and two Y ^1z have the same structure, two X ^1z have the same structure, and one X ^2z has a structure different from these two X ^1z the polymerizable liquid crystal compound (Z), ^{X 1z} that binds to ^{W 1z} of the two ^{X 1z} is, the other of ^{X 1z} and ^{X 2z} are different structures, the other of ^{X 1z} and ^{X 2z} mutually the same structure The polymerizable liquid crystal compound (Z) which is is also mentioned. Further, ^{polymerization} in which nz is 3 and three Y ^1z have the same structure as each other, and any one of three X ^1z and one X ^{2z has} a structure different from all the other three Liquid crystal compound (Z).

Y ^1z _{is, -CH 2 CH 2 -, -} CH 2 O -, - CH 2 CH 2 O -, - COO -, - OCOO-, a single ^{bond, -N = N -, - CR} az = CR bz -, —C≡C—, —CR ^az ═N— or —CO—NR ^az — is preferable. R ^az and R ^bz each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ^1z _is, -CH ₂ CH 2 -, - more preferably COO- or a single bond, when a plurality of ^{Y 1z} is ^{present, Y 1z} that binds ^{X 2z} is, _-CH 2 CH ₂ - or CH ₂ O- is more preferable. When X ^1z and X ^2z all have the same structure, it is preferable that two or more Y ^1z having different bonding methods exist. In the case where a plurality of Y ^1z having different coupling methods are present, an asymmetric structure is formed, and thus smectic liquid crystal properties tend to be easily exhibited.

U ^2z is the aforementioned polymerizable group. U ^1z is a hydrogen atom or a polymerizable group. Since it is easy to manufacture, the heat resistance of the vertically aligned liquid crystal cured film is easily improved, and the adhesion between the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film is easily adjusted and improved, the polymerizable group is ( It is preferably a (meth) acryloyloxy group. The polymerizable group may be in a polymerized state or an unpolymerized state, but is preferably in an unpolymerized state.

^{Examples of the} alkanediyl group represented by V ^1z and V ^2z include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, and a pentane- 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl Group and icosane-1,20-diyl group and the like. V ^1z and V ^2z are preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.

  Examples of the substituent that the alkanediyl group optionally has include a cyano group and a halogen atom. The alkanediyl group is preferably unsubstituted, and is an unsubstituted linear alkanediyl group. Is more preferable.

W ^1z and W ^2z are each independently preferably a single bond, —O—, —S—, —COO— or OCOO—, and more preferably a single bond or —O—.

  The polymerizable liquid crystal compound (Z) preferably has an asymmetric molecular structure in the molecular structure, and specifically is a polymerizable liquid crystal compound having the following partial structures (Aa) to (Ai). More preferably. From the viewpoint of easily exhibiting high-order smectic liquid crystallinity, it is more preferable to have a partial structure of (Aa), (Ab) or (Ac). In the following (Aa) to (Ai), * represents a bond (single bond).

  Specific examples of the polymerizable liquid crystal compound (Z) include compounds represented by formulas (A-1) to (A-25). When the polymerizable liquid crystal compound (Z) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans isomer.

  Among these, Formula (A-2), Formula (A-3), Formula (A-4), Formula (A-5), Formula (A-6), Formula (A-7), Formula (A- 8) at least one selected from the group consisting of compounds represented by formula (A-13), formula (A-14), formula (A-15), formula (A-16) and formula (A-17) Species are preferred. As the polymerizable liquid crystal compound (Z), one type may be used alone, or two or more types may be used in combination.

  The polymerizable liquid crystal compound (Z) is described in, for example, Lub et al., Recl. Trav. Chim. It can be produced by a known method described in Pays-Bas, 115, 321-328 (1996), or Japanese Patent No. 4719156.

  In the present invention, the vertically aligned liquid crystal cured film preferably has at least one maximum absorption between wavelengths of 300 to 400 nm, and the polymerizable liquid crystal compound forming the vertically aligned liquid crystal cured film has a maximum between wavelengths of 300 to 400 nm. A polymerizable liquid crystal compound having an absorption wavelength is preferred. When the polymerizable liquid crystal composition contains a photopolymerization initiator, the polymerization reaction and gelation of the polymerizable liquid crystal compound may proceed during long-term storage. However, if the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm, the generation of reactive species from the photopolymerization initiator and the polymerization of the polymerizable liquid crystal compound due to the reactive species will occur even when ultraviolet light is exposed during storage. The progress of polymerization reaction and gelation can be effectively suppressed. Therefore, it is advantageous in terms of long-term stability of the polymerizable liquid crystal composition, and the orientation and film thickness uniformity of the obtained liquid crystal cured film can be improved. Note that the maximum absorption wavelength of the polymerizable liquid crystal compound can be measured in a solvent using an ultraviolet-visible spectrophotometer. The solvent is a solvent that can dissolve the polymerizable liquid crystal compound, and examples thereof include chloroform.

  In a laminate in which a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film are bonded with an adhesive layer, from the viewpoint of reducing the thickness of the laminate and improving the flexibility, the pressure sensitive adhesive and In comparison, an energy ray curable adhesive is considered to be advantageous. However, when the vertically aligned liquid crystal cured film is formed from a polymerizable liquid crystal composition including a polymerizable liquid crystal compound having a maximum absorption wavelength between wavelengths of 300 to 400 nm, formation of a laminate including the vertically aligned liquid crystal cured film In the above, the vertically aligned liquid crystal cured film shows absorption in the above wavelength range, and therefore the vertically aligned liquid crystal cured film is cured by using an ultraviolet curable adhesive that is cured by light in the above wavelength range (ultraviolet light). It is difficult to laminate with other layers such as a film with high adhesion. In the present invention, the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film can be continuously formed without interposing an adhesive layer. Since it is possible to use a polymerizable liquid crystal compound having a maximum absorption in a wavelength region of 300 to 400 nm without exhibiting the above-mentioned problem relating to the property, and exhibiting so-called reverse wavelength dispersibility, in the structure of the laminate, it is high. This is also advantageous in that a thin laminate having optical properties can be obtained.

  The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film is, for example, 70 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. Preferably it is 80-99 mass parts, More preferably, it is 85-98 mass parts, More preferably, it is 90-95 mass parts. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film. In the present invention, the solid content of the polymerizable liquid crystal composition means all components excluding volatile components such as organic solvents from the polymerizable liquid crystal composition.

  In addition to the vertical alignment accelerator and the polymerizable liquid crystal compound, the polymerizable liquid crystal composition used for forming the vertically aligned liquid crystal cured film includes additives such as a solvent, a polymerization initiator, a leveling agent, an antioxidant, and a photosensitizer. May further be included. Each of these components may be used alone or in combination of two or more.

  Since the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film is usually applied to a substrate or the like in a state dissolved in a solvent, it preferably contains a solvent. As the solvent, a solvent capable of dissolving the polymerizable liquid crystal compound is preferable, and a solvent inert to the polymerization reaction of the polymerizable liquid crystal compound is preferable. Examples of the solvent include alcohols such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether. Solvents; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone, etc. Ketone solvent; aliphatic hydrocarbon solvent such as pentane, hexane and heptane; ethylcyclohexa Aliphatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-containing solvents such as chloroform and chlorobenzene; Dimethylacetamide, dimethylformi Examples include amide solvents such as amide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used alone or in combination of two or more. Among these, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are preferable.

  The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by weight, more preferably 70 to 95 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal composition. Accordingly, the solid content in 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition becomes low, so that the thickness of the film becomes substantially uniform and unevenness tends not to occur. The solid content can be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.

  The polymerization initiator is a compound capable of generating a reactive species by the contribution of heat or light and initiating a polymerization reaction such as a polymerizable liquid crystal compound. Examples of reactive species include active species such as radicals, cations, and anions. Among these, from the viewpoint of easy reaction control, a photopolymerization initiator that generates radicals by light irradiation is preferable.

  Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, oxime compounds, triazine compounds, iodonium salts, and sulfonium salts. Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (Inc. ), Sequol BZ, Sequol Z, Sequol BEE (manufactured by Seiko Chemical Co., Ltd.), kayacure BP100 (Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (Dow), Adeka optomer SP- 152, Adekaoptomer SP-170, Adekaoptomer N-1717, Adekaoptomer N-1919, Adeka Arcles NCI-831, Adeka Arcles NC -930 (manufactured by KK ADEKA), TAZ-A, TAZ-PP (or, Nippon SiberHegner KK) (manufactured by Sanwa Chemical Co.) and TAZ-104 and the like.

  The photopolymerization initiator can sufficiently utilize the energy emitted from the light source and is excellent in productivity. Therefore, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and among them, α-acetophenone series A polymerization initiator and an oxime photopolymerization initiator are preferred.

  Examples of the α-acetophenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1 -One and 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, and the like, more preferably 2-methyl-2-morpholino-1- ( 4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one. Examples of commercially available products of α-acetophenone compounds include Irgacure 369, 379EG, 907 (above, manufactured by BASF Japan Ltd.), Sequol BEE (manufactured by Seiko Chemical Co., Ltd.), and the like.

  The oxime photopolymerization initiator generates radicals such as phenyl radicals and methyl radicals when irradiated with light. Polymerization of the polymerizable liquid crystal compound proceeds favorably by this radical, and among them, an oxime photopolymerization initiator that generates a methyl radical is preferable in terms of high polymerization reaction initiation efficiency. From the viewpoint of allowing the polymerization reaction to proceed more efficiently, it is preferable to use a photopolymerization initiator that can efficiently use ultraviolet rays having a wavelength of 350 nm or more. As a photopolymerization initiator capable of efficiently using ultraviolet rays having a wavelength of 350 nm or more, a triazine compound or a carbazole compound containing an oxime structure is preferable, and a carbazole compound containing an oxime ester structure is more preferable from the viewpoint of sensitivity. Examples of the carbazole compound containing an oxime structure include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. Commercially available oxime ester photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (manufactured by BASF Japan Ltd.), Adekaoptomer N-1919, Adeka Arcles NCI-831. (Above, manufactured by ADEKA Corporation).

  Content of a photoinitiator is 0.1-30 mass parts normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 1-20 mass parts, More preferably, it is 1-15 mass parts. It is. If it is in the said range, reaction of a polymeric group will fully advance and it will be hard to disturb the orientation of a polymeric liquid crystal compound.

  The leveling agent is an additive having a function of adjusting the fluidity of the polymerizable liquid crystal composition and flattening the coating film obtained by applying the composition. Fluoroalkyl leveling agents can be mentioned. Commercially available products may be used as the leveling agent, specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Toray Dow Corning Co., Ltd.) , KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4446, TSF-4442, TSF4442, TSF4460 (All of the above are made by Momentive Performance Materials Japan GK), Fluorinert (registered trademark) FC-72, FC-4 FC-43, FC-3283 (all of which are manufactured by Sumitomo 3M Co., Ltd.), MegaFace (registered trademark) R-08, R-30, R-90, F-410, F- 411, F-443, F-445, F-470, F-477, F-479, F-482, F-483, F-556 (all of which are DIC Corporation) Manufactured), F-top (trade name) EF301, EF303, EF351, EF351, EF352 (all manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.), Surflon (registered trademark) S-381, S-382, S- 383, S-393, SC-101, SC-105, KH-40, SA-100 (all of which are manufactured by AGC Seimi Chemical Co., Ltd.), trade names E1830, E5844 (Daikin Fine Chemical Co., Ltd.) Manufactured , BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (both trade name: BM Chemie Co., Ltd.), and the like. Leveling agents can be used alone or in combination of two or more.

  0.01-5 mass parts is preferable with respect to 100 mass parts of polymerizable liquid crystal compounds, and, as for content of a leveling agent, 0.05-3 mass parts is more preferable. It is preferable for the content of the leveling agent to be within the above-mentioned range since it is easy to align the polymerizable liquid crystal compound and the obtained liquid crystal cured film tends to be smoother.

  By blending the antioxidant, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. The antioxidant may be a primary antioxidant selected from phenolic antioxidants, amine antioxidants, quinone antioxidants, nitroso antioxidants, phosphorus antioxidants and sulfur. It may be a secondary antioxidant selected from system antioxidants. In order to polymerize the polymerizable liquid crystal compound without disturbing the alignment of the polymerizable liquid crystal compound, the content of the antioxidant is usually 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. Yes, preferably 0.1-5 parts by mass, more preferably 0.1-3 parts by mass. Antioxidants can be used alone or in combination of two or more.

  Further, by using a photosensitizer, the photopolymerization initiator can be made highly sensitive. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; anthracene having a substituent such as anthracene and alkyl ether; phenothiazine; and rubrene. A photosensitizer can be used individually or in combination of 2 or more types. Content of a photosensitizer is 0.01-10 mass parts normally with respect to 100 mass parts of polymeric liquid crystal compounds, Preferably it is 0.05-5 mass parts, More preferably, it is 0.1-10 mass parts. 3 parts by mass.

  A polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film comprises a vertical alignment accelerator and a polymerizable liquid crystal compound, and components other than the vertical alignment accelerator such as a solvent and a photopolymerization initiator and the polymerizable liquid crystal compound at a predetermined temperature. Can be obtained by stirring or the like.

In the present invention, the vertically aligned liquid crystal cured film preferably satisfies the following formula (2).
RthC (450) / RthC (550) ≦ 1 (2)
[In Formula (2), RthC (450) represents the retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the position in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. Represents the phase difference value. ]
By satisfying the above formula (2), it is possible to suppress a decrease in ellipticity on the short wavelength side in the laminated body including the vertically aligned liquid crystal cured film, and black when the vertically aligned liquid crystal cured film is applied to a display device. The oblique reflection hue at the time of display can be improved. The value of RthC (450) / RthC (550) in the vertically aligned liquid crystal cured film is more preferably 0.95 or less, further preferably 0.92 or less, particularly preferably 0.9 or less, and preferably Is 0.7 or more, more preferably 0.75 or more, and still more preferably 0.8 or more.

The retardation value RthC (λ) in the film thickness direction of the vertically aligned liquid crystal cured film can be adjusted by the thickness dC of the vertically aligned liquid crystal cured film. The in-plane retardation value is expressed by the following formula:
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2−nzC (λ)) × dC
(Where nxC (λ) is the in-plane main refractive index of the vertically aligned liquid crystal cured film at wavelength λnm, and nyC (λ) is the refraction in the direction orthogonal to nxC (λ) at wavelength λnm. Ratio, nzC (λ) represents the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of λnm. When nxC (λ) = nyC (λ), nxC (λ) is arbitrary in the film plane. The refractive index in the direction can be set, and dC represents the thickness of the vertically aligned liquid crystal cured film)
Therefore, in order to obtain a desired retardation value RthC (λ) in the film thickness direction, the three-dimensional refractive index and the film thickness dC may be adjusted. The three-dimensional refractive index depends on the molecular structure and orientation state of the polymerizable liquid crystal compound described above.

In the present invention, the vertically aligned liquid crystal cured film is preferably aligned with a high degree of order in the vertical direction of the liquid crystal cured film. In the vertically aligned liquid crystal cured film, when the polymerizable liquid crystal compound is aligned with a high degree of order, when the laminate including the vertically aligned liquid crystal cured film is incorporated in an organic EL display device, the oblique direction during black display It tends to be excellent in the effect of suppressing changes in the reflected hue. The vertically aligned liquid crystal cured film satisfies the following formula (5) as an index indicating the degree of oblique optical compensation effect at the time of black display, indicating the high alignment state of the polymerizable liquid crystal compound in the vertically aligned liquid crystal cured film. preferable.
−120 nm ≦ RthC (550) ≦ −30 nm (5)
In formula (5), RthC (550) has the same meaning as described above. From the viewpoint of further improving the oblique reflection hue at the time of black display, the retardation value RthC (550) in the film thickness direction of the vertically aligned liquid crystal cured film is more preferably −100 nm or more, further preferably −90 nm or more, particularly Preferably it is -80 nm or more, More preferably, it is -40 nm or less, More preferably, it is -50 nm or less.

[Horizontal alignment liquid crystal cured film]
The horizontally aligned liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymerizable liquid crystal composition cured in a state where the polymerizable liquid crystal compound is aligned in the horizontal direction with respect to the liquid crystal cured film plane, preferably A liquid crystal cured film obtained by curing a polymerizable liquid crystal compound having at least one radical polymerizable group in a state of being aligned horizontally with respect to the in-plane direction of the liquid crystal cured film. In the present invention, the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition forming the horizontally aligned liquid crystal cured film means a liquid crystal compound having a polymerizable group, and in particular, a liquid crystal compound having at least one radical polymerizable group. preferable. When the horizontally aligned liquid crystal cured film is laminated on the vertically aligned liquid crystal cured film via a horizontal photo alignment film formed from a polymer having a (meth) acryloyl group, the vertically aligned liquid crystal cured film and the horizontal aligned liquid crystal cured film are When both are cured products of a polymerizable liquid crystal compound having at least one radical polymerizable group, the adhesion between the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film continuously formed through the horizontal aligned film is improved. It's easy to do. In particular, since the adhesion between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film tends to be further increased, the polymerizable liquid crystal compound constituting the horizontally aligned liquid crystal cured film and the polymerizable liquid crystal compound constituting the vertically aligned liquid crystal cured film And a polymer group that is similar to or the same as the polymerizable group of the polymer that forms the horizontal alignment film, and both the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film have a (meth) acryloyl group More preferably, it is composed of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound.

  The polymerizable liquid crystal compound constituting the horizontally aligned liquid crystal cured film is not particularly limited, and for example, a conventionally known polymerizable liquid crystal compound can be used in the field of retardation film. Specifically, compounds represented by the formula (X), (Y) or (Z) exemplified as polymerizable liquid crystal compounds that can be used for forming a vertically aligned liquid crystal cured film can be used. A polymerizable liquid crystal compound exhibiting wavelength dispersion is preferred, and for example, a compound represented by the above formula (X) can be suitably used. In the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film, the polymerizable liquid crystal compounds can be used alone or in combination of two or more.

  The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition used for forming the horizontally aligned liquid crystal cured film is, for example, 70 to 99.5 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. , Preferably it is 80-99 mass parts, More preferably, it is 85-98 mass parts, More preferably, it is 90-95 mass parts. If the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film.

  The polymerizable liquid crystal composition used for forming the horizontally aligned liquid crystal cured film further contains additives such as a solvent, a polymerization initiator, a leveling agent, an antioxidant, and a photosensitizer in addition to the polymerizable liquid crystal compound. Also good. Examples of these components include the same components as those exemplified above as components that can be used in the vertically aligned liquid crystal cured film. Each of these components may be used alone or in combination of two or more. .

  The polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film can be obtained by stirring the polymerizable liquid crystal compound and components other than the polymerizable liquid crystal compound such as a solvent and a photopolymerization initiator at a predetermined temperature. .

  In the present invention, the horizontally aligned liquid crystal cured film has a wavelength of 300 to 400 nm for the same reason as that when the vertically aligned liquid crystal cured film has at least one maximum absorption between wavelengths of 300 to 400 nm. It is preferred to have at least one maximum absorption in between. In a preferred embodiment of the present invention, both the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film have at least one maximum absorption between wavelengths of 300 to 400 nm.

In the present invention, the horizontally aligned liquid crystal cured film preferably satisfies the following formula (1).
ReA (450) / ReA (550) ≦ 1 (1)
[In the formula (1), ReA (λ) represents the in-plane retardation value of the horizontally aligned liquid crystal cured film at the wavelength λnm, and ReA (λ) = (nxA (λ) −nyA (λ)) × dA ( In the formula, nxA (λ) represents a main refractive index at a wavelength λnm in the horizontally aligned liquid crystal cured film surface, and nyA (λ) is a wavelength λnm in a direction orthogonal to the direction of nxA in the same plane as nxA. DA represents the thickness of the horizontally aligned liquid crystal cured film)]

  When the horizontally aligned liquid crystal cured film satisfies the formula (1), the horizontally aligned liquid crystal cured film has a so-called reverse wavelength dispersion in which an in-plane retardation value at a short wavelength is smaller than an in-plane retardation value at a long wavelength. Showing gender. By combining such a horizontally aligned liquid crystal cured film with the above vertically aligned liquid crystal cured film, it is possible to obtain a laminate that is excellent in improving the front and oblique reflection hues during black display when incorporated in an organic EL display device. it can. ReA (450) / ReA (550) is preferably 0.70 or more, more preferably because reverse wavelength dispersion is improved and the effect of improving the reflection hue in the front direction of the horizontally aligned liquid crystal cured film can be further enhanced. Is 0.78 or more, preferably 0.95 or less, more preferably 0.92 or less.

  The in-plane retardation value can be adjusted by the thickness dA of the horizontally aligned liquid crystal cured film. Since the in-plane retardation value is determined by the above formula ReA (λ) = (nxA (λ) −nyA (λ)) × dA, a desired in-plane retardation value (ReA (λ): wavelength λ ( In order to obtain the in-plane retardation value of the horizontally aligned liquid crystal cured film in nm), the three-dimensional refractive index and the film thickness dA may be adjusted.

Moreover, it is preferable that a horizontal alignment liquid crystal cured film satisfy | fills following formula (6).
120 nm ≦ ReA (550) ≦ 170 nm (6)
[In formula (6), ReA (λ) has the same meaning as above]
When the in-plane retardation ReA (550) of the horizontally aligned liquid crystal cured film is within the range of the formula (6), a laminate (elliptical polarizing plate) including the horizontally aligned liquid crystal cured film is applied to an organic EL display device. The effect of improving the front reflection hue during black display becomes remarkable. A more preferable range of the in-plane retardation value is 130 nm ≦ ReA (550) ≦ 150 nm.

[Horizontal alignment film]
The horizontal alignment film constituting the laminate of the present invention is a photo-alignment film formed from a polymer having a (meth) acryloyl group. The horizontal alignment film has a horizontal alignment regulating force for aligning the polymerizable liquid crystal compound in the horizontal direction with respect to the coating plane. The alignment regulating force can be arbitrarily adjusted according to the type of alignment film, the surface state, rubbing conditions, etc., and in the case of a photo-alignment film formed from a photo-alignable polymer, it is arbitrarily adjusted according to the polarization irradiation conditions, etc. It is possible. In the present invention, a vertical alignment liquid crystal cured film is formed on a substrate, and further a horizontal alignment film is formed thereon, and a horizontal alignment liquid crystal cured film is formed thereon. The orientation tends to deteriorate. The reason is not clear, but the surface energy is reduced by additives such as leveling agents contained in the vertically aligned liquid crystal cured film, and the orientation of the liquid crystal compound is liable to be impaired when the horizontal aligned liquid crystal cured film is formed in the upper layer. It is estimated to be. In particular, when a vertical alignment liquid crystal cured film is formed without a vertical alignment film, the influence is more remarkable because an alignment accelerator is further included. For this reason, the liquid crystal alignment at the time of forming the vertical alignment liquid crystal cured film is easily affected by the type and thickness of the horizontal alignment film.

  When the horizontal alignment film has a polymerizable group similar to or the same as the polymerizable liquid crystal compound constituting the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film, the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal are interposed through the horizontal alignment film. Since the adhesion to the cured film tends to increase, the horizontal alignment film is formed from a polymer having a (meth) acryloyl group, and both the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film have a (meth) acryloyl group. It is preferably formed from a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound.

  The photo-alignment film is usually obtained by applying a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter also referred to as “photo-alignment film-forming composition”) to a substrate, removing the solvent, and then polarizing the photo-alignment film. It is obtained by irradiating (preferably polarized UV). The photo-alignment film is advantageous in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.

  The photoreactive group refers to a group that generates liquid crystal alignment ability when irradiated with light. Specific examples include groups involved in photoreactions that are the origin of liquid crystal alignment ability such as molecular orientation induction or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction caused by light irradiation. Among them, a group involved in the dimerization reaction or the photocrosslinking reaction is preferable in terms of excellent orientation. As the photoreactive group, an unsaturated bond, particularly a group having a double bond is preferable, and a carbon-carbon double bond (C═C bond), a carbon-nitrogen double bond (C═N bond), or a nitrogen-nitrogen two bond. A group having at least one selected from the group consisting of a heavy bond (N═N bond) and a carbon-oxygen double bond (C═O bond) is particularly preferred.

  Examples of the photoreactive group having a C═C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group. Examples of the photoreactive group having a C═N bond include groups having a structure such as an aromatic Schiff base and an aromatic hydrazone. Examples of the photoreactive group having an N = N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and a group having an azoxybenzene structure. Examples of the photoreactive group having a C═O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

  Among them, a photoreactive group involved in the photodimerization reaction is preferable, the amount of polarized light irradiation necessary for photoalignment is relatively small, and a photoalignment film excellent in thermal stability and temporal stability can be easily obtained. An azo group, a cinnamoyl group and a chalcone group are preferred. As the polymer having a photoreactive group, a polymer having an azo group or a cinnamoyl group is preferable. This is particularly preferable from the viewpoint of improving the adhesion between the cured film and the horizontally aligned liquid crystal cured film.

  Examples of the solvent that can be included in the composition for forming a photoalignment film include the same solvents as those exemplified above as the solvent that can be used in the polymerizable liquid crystal composition, and the solubility of the polymer or monomer having a photoreactive group. It can be selected as appropriate according to the conditions.

  The content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment film can be appropriately adjusted depending on the type of the polymer or monomer and the thickness of the desired photoalignment film. The mass is preferably at least 0.2 mass%, more preferably in the range of 0.3-10 mass%. As long as the characteristics of the photo-alignment film are not significantly impaired, the composition for forming a photo-alignment film may contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer.

  The thickness of the horizontal alignment film (photo-alignment film) is usually 10 to 5000 nm, preferably 100 to 1000 nm, more preferably 100 to 500 nm, still more preferably 100 to 300 nm, and particularly preferably 100 to 250 nm. When the thickness of the alignment film is within the above range, it has a sufficient horizontal alignment regulating force and hardly causes cohesive failure in the alignment film in the laminate.

〔Base material〕
As a base material which comprises the laminated body of this invention, although a glass base material, a film base material, etc. are mentioned, a resin film base material is preferable from a viewpoint of workability. Examples of the resin constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylic acid esters; polyacrylic acid esters; Examples include cellulose esters such as diacetylcellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; and plastics such as polyphenylene sulfide and polyphenylene oxide. Such a resin can be formed into a substrate by a known method such as a solvent casting method or a melt extrusion method. The substrate surface may be subjected to a surface treatment such as a mold release treatment such as a silicone treatment, a corona treatment, or a plasma treatment.

  A commercially available product may be used as the substrate. As a commercially available cellulose ester base material, for example, a cellulose ester base material manufactured by Fuji Photo Film Co., Ltd. such as Fujitac Film; manufactured by Konica Minolta Opto Co., Ltd. such as “KC8UX2M”, “KC8UY”, and “KC4UY” And cellulose ester base materials. Examples of commercially available cyclic olefin resins include cyclic olefin resins manufactured by Ticona (Germany) such as “Topas (registered trademark); cyclic olefins manufactured by JSR Corporation such as“ Arton (registered trademark) ”. -Type resin; cyclic olefin resin made by ZEON Corporation such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)"; Mitsui like "APEL" (registered trademark) Examples include cyclic olefin-based resins manufactured by Chemical Co., Ltd. Commercially available cyclic olefin resin base materials can also be used. Examples of commercially available cyclic olefin resin substrates include cyclic olefin resin substrates manufactured by Sekisui Chemical Co., Ltd., such as “ESCINA (registered trademark)” and “SCA40 (registered trademark)”; “ZEONOR FILM (registered trademark)”. And the cyclic olefin resin substrate made by JSR Corporation such as “Arton Film (registered trademark)”.

  In this invention, it is preferable that a base material is finally peelable from the laminated body of this invention, for example, the vertical alignment liquid crystal cured film of the laminated body after peeling a base material is used as an adhesive layer. An elliptically polarizing plate can be obtained by laminating with a polarizing film through a film.

  From the viewpoint of thinning the laminate, easy peeling of the base material, handling property of the base material, and the like, the thickness of the base material is usually 5 to 300 μm, preferably 10 to 150 μm.

  The laminated body of the present invention may include layers other than the base material, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film as long as the effect of the present invention is not affected. As such other layers, for example, a cured resin layer, a hard coat layer for the purpose of improving the solvent resistance of the substrate, increasing the mechanical strength of the liquid crystal cured film, or reinforcing, Examples include a primer layer. For example, the base material and the vertical alignment liquid crystal cured film may be laminated via a layer having no vertical alignment regulating force, and the vertical alignment liquid crystal cured film and the horizontal alignment film are layers having no vertical alignment regulating force ( It may be laminated via a non-adhesive layer).

  The cured resin layer can be formed of, for example, an acrylic resin, a methacrylic resin, an epoxy resin, an oxetane resin, a urethane resin, a melamine resin, or the like. By providing a cured resin layer, the solvent resistance of the substrate is improved, or even if the vertically aligned liquid crystal cured film formed adjacent to the cured resin layer is a thin film, the cured resin layer serves as a protective layer or a reinforcing layer. The strength of the vertically aligned liquid crystal cured film can be sufficiently supplemented.

  When the laminate of the present invention includes other layers such as the cured resin layer, the thickness of the other layers may be appropriately determined depending on the purpose and type of the layer to be provided, but preferably 0.1 to 10 0.0 μm, more preferably 0.3 to 5.0 μm.

[Method for producing laminate]
The laminate of the present invention is, for example,
A step of forming a coating film of a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film containing a polymerizable liquid crystal compound, and forming a vertically aligned liquid crystal cured film from the coating film (hereinafter referred to as “vertical aligned liquid crystal cured film forming step”). Also called)
Forming a coating film of the composition for forming a horizontal alignment film, forming a horizontal alignment film from the coating film (hereinafter, also referred to as “horizontal alignment film forming process”), and
A step of forming a coating film of a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film containing a polymerizable liquid crystal compound, and forming a horizontally aligned liquid crystal cured film from the coated film (hereinafter referred to as “horizontal aligned liquid crystal cured film forming step”). (Also called)
In this order. In the laminate of the present invention, when the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film are adjacent to each other, the vertical alignment liquid crystal cured film forming process, the horizontal alignment film forming process, and the vertical alignment liquid crystal cured film formation are performed. It is preferable that a process is continuously performed in this order.

In the vertical alignment liquid crystal cured film forming step, the vertical alignment liquid crystal cured film is, for example,
Applying a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film on a substrate to obtain a coating film;
Drying the coating film to form a dry coating film; and
It can be produced by a method including a step of irradiating a dry coating film with active energy rays to form a vertically aligned liquid crystal cured film.

  Formation of the coating film of the polymerizable liquid crystal composition is, for example, a vertically aligned liquid crystal cured film on a base material or another layer such as a cured resin layer having no vertical alignment regulating force provided on the base material. It can be performed by applying a polymerizable liquid crystal composition for formation.

  As a method for applying the polymerizable liquid crystal composition to a substrate or the like, a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, a coating method such as an applicator method, or a printing method such as a flexo method. Known methods such as

Next, a dry coating film is formed by removing the solvent by drying or the like. Examples of drying methods include natural drying, ventilation drying, heat drying, and reduced pressure drying. At this time, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent can be removed from the coating film by drying, and the polymerizable liquid crystal compound can be aligned in a direction perpendicular to the coating film plane. The heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used and the material such as the base material on which the coating film is formed. In order to cause the polymerizable liquid crystal compound to transition to the liquid crystal phase, liquid crystal It is usually necessary that the temperature be higher than the phase transition temperature. In order to bring the polymerizable liquid crystal compound into a vertically aligned state while removing the solvent contained in the polymerizable liquid crystal composition, for example, the liquid crystal phase transition temperature (smectic phase transition of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition). It can be heated to a temperature equal to or higher than the temperature or nematic phase transition temperature.
The liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature adjustment stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like. When two or more kinds of polymerizable liquid crystal compounds are used in combination, the phase transition temperature is a polymerization in which all polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition are mixed in the same ratio as the composition in the polymerizable liquid crystal composition. Means a temperature measured in the same manner as in the case of using one kind of polymerizable liquid crystal compound by using a mixture of polymerizable liquid crystal compounds. In general, it is known that the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition may be lower than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound alone.

  The heating time can be appropriately determined according to the heating temperature, the type of polymerizable liquid crystal compound to be used, the type of solvent, the boiling point and the amount thereof, and is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.

  Removal of the solvent from the coating film may be performed simultaneously with heating to a temperature higher than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound, or may be performed separately, but is preferably performed simultaneously from the viewpoint of improving productivity. Before heating the polymerizable liquid crystal compound to a temperature above the liquid crystal phase transition temperature, the solvent in the coating film is appropriately adjusted under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize. You may provide the preliminary drying process for making it remove. Examples of the drying method in the preliminary drying step include a natural drying method, a ventilation drying method, a heating drying method and a drying method under reduced pressure. The drying temperature (heating temperature) in the drying step is the kind of the polymerizable liquid crystal compound to be used, the solvent It can be appropriately determined according to the type, the boiling point and the amount thereof.

  Next, in the obtained dried coating film, the vertically aligned liquid crystal cured film is formed by polymerizing the polymerizable liquid crystal compound while maintaining the vertically aligned state of the polymerizable liquid crystal compound. Examples of the polymerization method include a thermal polymerization method and a photopolymerization method, and the photopolymerization method is preferable from the viewpoint of easily controlling the polymerization reaction. In the photopolymerization, the light applied to the dried coating film includes the type of polymerization initiator contained in the dried coating film, the type of polymerizable liquid crystal compound (particularly the type of polymerizable group possessed by the polymerizable liquid crystal compound), and It is suitably selected according to the amount. Specific examples thereof include one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α rays, β rays, and γ rays, and active electron beams. Among them, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction, and that widely used in the field as a photopolymerization apparatus can be used. It is preferable to select the kind of the polymerizable liquid crystal compound and the polymerization initiator contained in the polymerizable liquid crystal composition. Moreover, at the time of superposition | polymerization, superposition | polymerization temperature can also be controlled by irradiating light, cooling a dry coating film with a suitable cooling means. By adopting such a cooling means, if a polymerizable liquid crystal compound is polymerized at a lower temperature, a vertically aligned liquid crystal cured film can be appropriately formed even if a substrate having relatively low heat resistance is used. In addition, the polymerization reaction can be promoted by increasing the polymerization temperature within a range that does not cause problems due to heat during light irradiation (such as deformation due to heat of the base material). In photopolymerization, a patterned cured film can be obtained by masking or developing.

  Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, and a wavelength range. Examples include LED light sources that emit light of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW / cm ² . The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating the photopolymerization initiator. The time for irradiating light is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and further preferably 0.1 second to 1 minute. is there. When irradiating once or a plurality of times with such ultraviolet irradiation intensity, the integrated light amount is 10 to 3,000 mJ / cm ² , preferably 50 to 2,000 mJ / cm ² , more preferably 100 to 1,000 mJ / cm ² . ² .

  The thickness of the vertically aligned liquid crystal cured film can be appropriately selected depending on the display device to be applied, and is preferably 0.2 to 3 μm, more preferably 0.2 to 2 μm. When the vertically aligned liquid crystal cured film is positive wavelength dispersive, it is more preferably 0.2 to 1 μm, and when it is reverse wavelength dispersive, 0.4 to 2 μm is more preferable.

  In the horizontal alignment film forming step, the photo-alignment film is obtained, for example, by applying a composition for forming a photo-alignment film on the vertically aligned liquid crystal cured film and irradiating with polarized light (preferably polarized UV) after removing the solvent. It is done.

  Examples of the method for applying the composition for forming a photo-alignment film on the vertically aligned liquid crystal cured film include the same method as the method for applying the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film to a substrate or the like. Examples of the method for removing the solvent from the applied composition for forming a photo-alignment film include a natural drying method, a ventilation drying method, a heat drying method and a vacuum drying method.

In order to irradiate the polarized light, the polarized light is irradiated from the vertically aligned liquid crystal cured film side (base material side) even in the form of directly irradiating the polarized UV to the film obtained by removing the solvent from the coating film of the composition for forming a photo-alignment film. Alternatively, the polarized light may be transmitted for irradiation. The polarized light is particularly preferably substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in a wavelength region in which the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength in the range of 250 to 400 nm is particularly preferable. Examples of the light source used for the polarized light irradiation include xenon lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and high pressure mercury lamps, ultra high pressure mercury lamps and metal halide lamps. preferable. Among these, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide lamp are preferable because of high emission intensity of ultraviolet rays having a wavelength of 313 nm. By irradiating light from the light source through an appropriate polarizer, polarized UV light can be irradiated. As such a polarizer, a polarizing prism such as a polarizing filter, Glan Thompson, or Grand Taylor, or a wire grid type polarizer can be used.
Note that a plurality of regions (patterns) having different liquid crystal alignment directions can be formed by performing masking during polarized light irradiation.

In the horizontal alignment liquid crystal cured film forming step, the horizontal alignment liquid crystal cured film is, for example,
Applying a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film on the horizontal alignment film to obtain a coating film;
Drying the coating film to form a dry coating film; and
The dry coating film can be produced by a method including a step of irradiating an active energy ray to form a horizontally aligned liquid crystal cured film.

  The coating film of the polymerizable liquid crystal composition can be formed, for example, by applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on the horizontal alignment film. Examples of the method for applying the polymerizable liquid crystal composition include the same methods as those that can be employed in the method for producing a vertically aligned liquid crystal cured film.

  Next, a dry coating film is formed by removing the solvent by drying or the like. Examples of drying methods include natural drying, ventilation drying, heat drying, and reduced pressure drying. From the viewpoint of productivity, heat drying is preferable. In this case, the heating temperature is preferably equal to or higher than the phase transition temperature of the polymerizable liquid crystal compound so that the solvent can be removed. The procedures and conditions in this step are the same as those that can be adopted in the method for producing a vertically aligned liquid crystal cured film.

  The obtained dried coating film is irradiated with active energy rays (more specifically, ultraviolet rays or the like), and the polymerizable liquid crystal compound is maintained in a state where the polymerizable liquid crystal compound is oriented in the horizontal direction with respect to the coating plane. By polymerizing, a horizontally aligned liquid crystal cured film is formed. Examples of the polymerization method include the same methods as those that can be employed in the method for producing a vertically aligned liquid crystal cured film.

  The thickness of the horizontally aligned liquid crystal cured film can be appropriately selected depending on the display device to be applied, and is preferably 0.2 to 5 μm, more preferably 0.2 to 4 μm, and further preferably 0.2 to 3 μm. .

  In the present invention, the vertically aligned liquid crystal cured film is formed from a polymerizable liquid crystal composition containing a vertical alignment accelerator, whereby a vertically aligned liquid crystal cured film having no or few alignment defects can be obtained without using the vertical alignment film. . The laminate of the present invention including such a vertically aligned liquid crystal cured film in combination with a horizontally aligned liquid crystal cured film tends to have excellent optical characteristics, and particularly when applied to an organic EL display device, the front and oblique directions when displaying black Excellent suppression effect of reflected hue. Further, since a process for forming a vertical alignment film is not required, it is advantageous in terms of production efficiency and production cost.

[Elliptically polarizing plate]
The present invention includes an elliptically polarizing plate including the laminate of the present invention and a polarizing film.
The polarizing film is a film having a polarizing function, and examples thereof include a stretched film in which a dye having absorption anisotropy is adsorbed and a film including a film coated with a dye having absorption anisotropy as a polarizer. Examples of the dye having absorption anisotropy include a dichroic dye.

  A film containing a stretched film adsorbed with a dye having absorption anisotropy as a polarizer is usually a step of uniaxially stretching a polyvinyl alcohol resin film, by dyeing the polyvinyl alcohol resin film with a dichroic dye, At least a polarizer produced through a step of adsorbing a dichroic dye, a step of treating a polyvinyl alcohol resin film adsorbed with a dichroic dye with an aqueous boric acid solution, and a step of washing with water after the treatment with the aqueous boric acid solution It is produced by sandwiching it with a transparent protective film via an adhesive on one surface.

  The polyvinyl alcohol resin can be obtained by saponifying a polyvinyl acetate resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith are used. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

  The saponification degree of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol resin is usually about 1,000 to 10,000, preferably in the range of 1,500 to 5,000.

  What formed such a polyvinyl alcohol-type resin into a film is used as a raw film of a polarizing film. The method for forming a polyvinyl alcohol-based resin is not particularly limited, and can be formed by a known method. The film thickness of a polyvinyl alcohol-type raw fabric film can be about 10-150 micrometers, for example.

  Uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with the dichroic dye, simultaneously with dyeing, or after dyeing. When uniaxial stretching is performed after dyeing, the uniaxial stretching may be performed before boric acid treatment or during boric acid treatment. Moreover, it is also possible to perform uniaxial stretching in these several steps. In uniaxial stretching, it may be uniaxially stretched between rolls having different peripheral speeds, or may be uniaxially stretched using a hot roll. Further, the uniaxial stretching may be dry stretching in which stretching is performed in the air, or may be wet stretching in which stretching is performed in a state where a solvent is used and a polyvinyl alcohol-based resin film is swollen. The draw ratio is usually about 3 to 8 times.

  The polyvinyl alcohol resin film is dyed with a dichroic dye by, for example, a method of immersing the polyvinyl alcohol resin film in an aqueous solution containing the dichroic dye.

  Specifically, iodine or a dichroic organic dye is used as the dichroic dye. Examples of dichroic organic dyes include C.I. I. Examples include dichroic direct dyes composed of disazo compounds such as DIRECT RED 39, and dichroic direct dyes composed of compounds such as trisazo and tetrakisazo. The polyvinyl alcohol-based resin film is preferably subjected to an immersion treatment in water before the dyeing treatment.

  When iodine is used as the dichroic dye, a method of dyeing a polyvinyl alcohol resin film by dipping it in an aqueous solution containing iodine and potassium iodide is usually employed. The content of iodine in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water. Moreover, content of potassium iodide is about 0.5-20 mass parts normally per 100 mass parts of water. The temperature of the aqueous solution used for dyeing is usually about 20 to 40 ° C. Moreover, the immersion time (dyeing time) in this aqueous solution is usually about 20 to 1,800 seconds.

On the other hand, when a dichroic organic dye is used as the dichroic dye, a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is usually employed. The content of the dichroic organic dye in this aqueous solution is usually about 1 × 10 ⁻⁴ to 10 parts by mass, preferably 1 × 10 ⁻³ to 1 part by mass, more preferably 100 parts by mass of water. Is 1 × 10 ⁻³ to 1 × 10 ⁻² parts by mass. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing assistant. The temperature of the aqueous dichroic dye solution used for dyeing is usually about 20 to 80 ° C. Moreover, the immersion time (dyeing time) in this aqueous solution is usually about 10 to 1,800 seconds.

  The boric acid treatment after dyeing with a dichroic dye can be usually performed by a method of immersing a dyed polyvinyl alcohol resin film in an aqueous boric acid solution. The boric acid content in this boric acid aqueous solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass per 100 parts by mass of water. When iodine is used as the dichroic dye, this aqueous boric acid solution preferably contains potassium iodide. In this case, the content of potassium iodide is usually 0.1 to 100 parts by mass of water. About 15 parts by mass, preferably 5 to 12 parts by mass. The immersion time in the boric acid aqueous solution is usually about 60 to 1,200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of boric acid treatment is usually 50 ° C. or higher, preferably 50 to 85 ° C., more preferably 60 to 80 ° C.

  The polyvinyl alcohol resin film after the boric acid treatment is usually washed with water. The water washing treatment can be performed, for example, by a method of immersing a boric acid-treated polyvinyl alcohol resin film in water. The temperature of water in the water washing treatment is usually about 5 to 40 ° C. The immersion time is usually about 1 to 120 seconds.

  A drying process is performed after water washing, and a polarizer is obtained. The drying process can be performed using, for example, a hot air dryer or a far infrared heater. The temperature of a drying process is about 30-100 degreeC normally, Preferably it is 50-80 degreeC. The drying time is usually about 60 to 600 seconds, preferably 120 to 600 seconds. By the drying treatment, the moisture content of the polarizer is reduced to a practical level. The moisture content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. When the moisture content is less than 5% by mass, the flexibility of the polarizer is lost, and the polarizer may be damaged or broken after drying. On the other hand, if the moisture content exceeds 20% by mass, the thermal stability of the polarizer may be deteriorated.

  Thus, the thickness of the polarizer obtained by uniaxially stretching, dyeing with a dichroic dye, boric acid treatment, washing with water and drying on a polyvinyl alcohol resin film is preferably 5 to 40 μm.

  Examples of the film coated with a dye having absorption anisotropy include a composition containing a dichroic dye having liquid crystallinity or a film obtained by applying a composition containing a dichroic dye and a polymerizable liquid crystal. Can be mentioned. The film preferably has a protective film on one side or both sides. As the said protective film, the same thing as the resin film illustrated previously as a base material which can be used for manufacture of a vertical alignment liquid crystal cured film is mentioned.

  The film coated with the pigment having absorption anisotropy is preferably thin, but if it is too thin, the strength is lowered and the processability tends to be inferior. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

  Specific examples of the film coated with the pigment having absorption anisotropy include films described in JP 2012-33249 A.

  A transparent protective film may be laminated on, for example, an adhesive layer on at least one surface of the polarizer thus obtained. As a transparent protective film, the transparent film similar to the resin film illustrated previously as a base material which can be used for manufacture of a vertical alignment liquid crystal cured film can be used.

  The elliptically polarizing plate of the present invention comprises the laminate of the present invention, or a laminate obtained by removing the substrate from the laminate of the present invention and a polarizing film, for example, the laminate of the present invention. And the polarizing film are laminated via an adhesive layer or the like, the elliptically polarizing plate of the present invention can be obtained. Moreover, the elliptically polarizing plate of this invention can be obtained by bonding the laminated body which removed the base material from the laminated body of this invention, and a polarizing film.

  In one embodiment of the present invention, when the laminate of the present invention and the polarizing film are laminated, the slow axis (optical axis) of the horizontally aligned liquid crystal cured film constituting the laminate and the absorption axis of the polarizing film. Lamination is preferably performed so that the angle formed is 45 ± 5 °.

  The elliptically polarizing plate of the present invention may have a configuration as provided in a conventional general elliptically polarizing plate, or a polarizing film and a retardation film. As such a configuration, for example, it is used for the purpose of protecting the surface of an adhesive layer (sheet) for bonding an elliptical polarizing plate to a display element such as organic EL, a polarizing film or a liquid crystal cured film from scratches and dirt A protective film.

The laminate and the elliptically polarizing plate of the present invention can be used for various display devices.
A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light-emitting source. As the display device, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, a field emission display device (FED), a surface field emission display device) (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device (eg, grating light valve (GLV) display device, display device having digital micromirror device (DMD)) The liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, and a projection liquid crystal display device. These display devices include a table for displaying a two-dimensional image. The device may be a three-dimensional display device that displays a three-dimensional image, and in particular, the elliptically polarizing plate of the present invention is notable for its effect, so that it is an organic electroluminescence (EL) display device. The laminate of the present invention can be suitably used for a liquid crystal display device and a touch panel display device, and the display device can be thinned by using the laminate or the elliptically polarizing plate of the present invention. Therefore, it is possible to obtain a display device that is easy to perform, has excellent optical characteristics, and can exhibit good image display characteristics.

  Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, “%” and “part” mean mass% and mass part, respectively, unless otherwise specified.

1. Example 1
(1) Preparation of composition for forming horizontal alignment film 5 parts by mass (weight average molecular weight: 30000) of photoalignment material having the following structure and 95 parts by mass of cyclopentanone (solvent) were mixed as components, and the resulting mixture was obtained. Was stirred at 80 ° C. for 1 hour to obtain a composition for forming a horizontal alignment film.

(2) Preparation of polymerizable liquid crystal compound A polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (X2) having the following molecular structures were respectively prepared. The polymerizable liquid crystal compound (X1) was produced according to the method described in JP 2010-31223 A. The polymerizable liquid crystal compound (X2) was produced according to the method described in JP2009-173893A.

Polymerizable liquid crystal compound (X1)

Polymerizable liquid crystal compound (X2)

1 mg of the polymerizable liquid crystal compound (X1) was dissolved in 50 mL of tetrahydrofuran to obtain a solution. The solution obtained as a measurement sample is put in a measurement cell having an optical path length of 1 cm, the measurement sample is set in an ultraviolet-visible spectrophotometer (“UV-2450” manufactured by Shimadzu Corporation), and an absorption spectrum is measured. When the wavelength at which the maximum absorption was obtained was read from the obtained absorption spectrum, the maximum absorption wavelength λ _max in the wavelength range of 300 to 400 nm was 350 nm.

(3) Preparation of polymerizable liquid crystal composition for forming horizontally aligned liquid crystal cured film A leveling agent ("F-" manufactured by DIC Co., Ltd.) is used with respect to polymerizable liquid crystal compound LC242 represented by the following formula (LC242): Paliocolor LC242 (registered trademark of BASF). 556 ") 0.1 parts by weight and 3 parts by weight of polymerization initiator Irg369. Furthermore, cyclopentanone was added so that the solid content concentration would be 13%, and these were mixed to obtain a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film.

LC242: Paliocolor LC242 (registered trademark of BASF)

(4) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film 0.25 parts by mass of leveling agent “F-556” (manufactured by DIC) per 100 parts by mass of liquid crystal compound (X2), Japanese Patent Application No. 2016 -Ionic compound A (molecular weight: 645) 2.0 parts by weight prepared with reference to JP-514802, silane coupling agent “KBE-9103” (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by weight, photopolymerization As an initiator, 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Ltd.) was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. This mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.

Ionic compound A:

(5) Preparation of base material 50 parts by mass of dipentaerythritol hexaacrylate (Aronix M-403, polyfunctional acrylate manufactured by Toagosei Co., Ltd.), 50 parts by mass of acrylate resin (Eveacryl 4858 manufactured by Daicel UCB Co., Ltd.), 2-methyl- A solution of 3 parts by mass of 1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907; manufactured by Ciba Specialty Chemicals) in 250 parts by mass of isopropanol was prepared, and the acrylate compound was contained. A composition for forming a cured resin layer was obtained.
Then, the composition for cured resin layer formation was apply | coated with the bar coater on the TAC film (KC4UY) by Konica Minolta, Inc., and it dried at 50 degreeC for 1 minute. Then, a cured resin is obtained by irradiating with ultraviolet rays (integrated light quantity at a wavelength of 365 nm: 400 mJ / cm ² in a nitrogen atmosphere) using a high-pressure mercury lamp (“UNICURE VB-15201BY-A”, manufactured by USHIO INC.). A layer was formed. It was 2.0 micrometers when the film thickness of the obtained cured resin layer was measured with the contact-type film thickness meter. At this time, after measuring the retardation value Re550 of the laminate of the TAC film and the cured resin layer using “KOBRA-WPR” manufactured by Oji Scientific Instruments, the TAC film-derived retardation value Re550 was subtracted. It was confirmed that the phase difference value was 3 nm or less and was optically isotropic.

(6) Preparation of vertically aligned liquid crystal cured film A polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was applied to the cured resin layer on the substrate prepared as described above using a bar coater, and the temperature was 60 at 120 ° C. Heated for 2 seconds. Then, using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) while being heated to 120 ° C., ultraviolet light is applied from the surface where the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film is applied. Is irradiated (accumulated light quantity at a wavelength of 365 nm in a nitrogen atmosphere: 500 mJ / cm ² ) to form a vertically aligned liquid crystal cured film, and a substrate, a cured resin layer, and a vertically aligned liquid crystal cured film are laminated adjacently in this order. A laminated body was obtained. It was 0.6 micrometer when the film thickness of the obtained vertical alignment liquid crystal cured film was measured with the ellipsometer (M-220 by JASCO Corporation).

<Measurement of retardation value of vertical alignment liquid crystal cured film>
The vertically aligned liquid crystal cured film surface of the laminate composed of the base material, the cured resin layer and the vertically aligned liquid crystal cured film prepared in the above procedure is subjected to corona treatment and attached to glass via a 25 μm pressure sensitive adhesive made by Lintec. After combining, the TAC film and the cured resin layer were peeled off. About the obtained laminate made of glass, adhesive, and vertically aligned liquid crystal cured film, the front phase difference is obtained by changing the incident angle of light to the sample for optical property measurement using KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd. And the phase difference value when tilted by 40 ° about the fast axis.
The average refractive index at each wavelength was measured using an ellipsometer M-220 manufactured by JASCO Corporation. The film thickness was measured using an Optical NanoGauge film thickness meter C12562-01 manufactured by Hamamatsu Photonics Co., Ltd. From the above-mentioned front phase difference value, phase difference value when tilted by 40 ° about the fast axis, average refractive index, and film thickness value, the technical data of Oji Measuring Instruments (http://www.oji-keisoku.co .Jp / products / kobra / reference.html) to calculate a three-dimensional refractive index. From the obtained three-dimensional refractive index, the optical properties of the vertically aligned liquid crystal cured film are calculated according to the following formula, and the values of Rth (450), Rth (550), αth = Rth (450) / Rth (550) are calculated. did. The results are shown in Table 1.
RthC (λ) = ((nxC (λ) + nyC (λ)) / 2−nzC (λ)) × dC
RthC (λ) represents the retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at the wavelength λnm. Further, nxC (λ) is the in-plane main refractive index of the vertically aligned liquid crystal cured film at the wavelength λnm, nyC (λ) is the refractive index in the direction orthogonal to nxC (λ) at the wavelength λnm, nzC ( λ) indicates the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at the wavelength λnm. When nxC (λ) = nyC (λ), nxC (λ) is the refractive index in an arbitrary direction within the film plane. DC represents the thickness of the vertically aligned liquid crystal cured film.

(7) Production of horizontal alignment liquid crystal cured film Corona treatment was performed on the vertical alignment liquid crystal cured film surface of the laminate composed of the base material (TAC film), the cured resin layer and the vertical alignment liquid crystal cured film manufactured by the method described above. The composition for forming a horizontal alignment film was applied using a bar coater and dried at 80 ° C. for 1 minute. Subsequently, using a polarized UV irradiation apparatus (SPOT CURE SP-9; manufactured by USHIO INC.), Polarized UV exposure was performed with an integrated light amount at a wavelength of 313 nm: 100 mJ / cm ² to obtain a horizontal alignment film. It was 200 nm when the film thickness of the obtained horizontal alignment film was measured with the ellipsometer.
Subsequently, a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film is applied on the horizontal alignment film, heated at 120 ° C. for 60 seconds, and then a high pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). Is used to form a horizontally aligned liquid crystal cured film by irradiating ultraviolet rays from the surface coated with the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film (integrated light quantity at a wavelength of 365 nm: 500 mJ / cm ² ) in a nitrogen atmosphere. And the laminated body which laminated | stacked the base material, the cured resin layer, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film adjacently in this order was obtained. The film thickness of the obtained horizontally aligned liquid crystal cured film was measured by an ellipsometer and found to be 1.1 μm. In this laminate, the total film thickness T1 from the surface on the substrate side of the vertically aligned liquid crystal cured film to the surface opposite to the horizontal aligned film of the horizontal aligned liquid crystal cured film was 1.9 μm.
The laminate obtained in Example 1 is a laminate having a configuration of base material (TAC film) / cured resin layer / vertical alignment liquid crystal cured film / horizontal alignment film / horizontal alignment liquid crystal cured film.

<Measurement of retardation value of horizontal alignment liquid crystal cured film>
A 25 μm pressure-sensitive adhesive made by Lintec Co., Ltd. was subjected to corona treatment on the horizontally aligned liquid crystal cured film surface of the laminate comprising the substrate, cured resin layer, vertically aligned liquid crystal cured film, horizontal aligned film, and horizontally aligned liquid crystal cured film. Then, the TAC film and the cured resin layer were peeled off. Re (450), Re measured using the KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd. for the laminate composed of the obtained glass, adhesive, vertical alignment liquid crystal cured film, horizontal alignment film, horizontal alignment liquid crystal cured film. From the value of (550), Re (450) and Re (550) of the vertically aligned liquid crystal cured film previously measured by the above-described method are subtracted, and ReA (450) and ReA (550) of the horizontally aligned liquid crystal cured film are subtracted. Further, αA = ReA (450) / ReA (550) was calculated. The results are shown in Table 1.

(8) Evaluation of laminate <Evaluation of orientation of laminate>
The obtained laminate was bonded to 5 × 5 cm × 0.7 mm thick glass via a Lintec pressure sensitive adhesive (25 μm), and only the substrate was peeled off. The obtained sample was observed under a condition of 200 times magnification using a polarizing microscope (“BX-51” manufactured by Olympus Corporation), and the number of alignment defects in a visual field of 480 μm × 320 μm was counted. Here, as the number of alignment defects, only the alignment defects caused by the measurement sample were counted, and the number of defects caused by environmental foreign matters other than the sample were excluded and not counted. From the observation result with a polarizing microscope, the orientation of the laminate was evaluated based on the following evaluation criteria. If it was (circle), it was judged that it was excellent in orientation, and if it was (triangle | delta), it judged that it was the orientation of the grade which does not affect an optical characteristic. The results are shown in Table 1.
Evaluation criteria:
○ (very good): The number of alignment defects is 0 or more and 5 or less.
Δ (good): The number of alignment defects is 6 or more and 20 or less.
X (Poor): The number of orientation defects is 21 or more, or no orientation at all.

<Adhesion test of laminate>
The adhesion test of the laminate was conducted as follows with reference to the adhesion test (cross-cut method) of JIS K5600-5-6. First, the horizontally aligned liquid crystal cured film side of the laminate and a glass of 5 × 5 cm × 0.7 mm thickness were bonded via a pressure sensitive adhesive (25 μm) manufactured by Lintec, and only the substrate was peeled from the laminate. . 100 mm of cuts of 1 mm □ were made on the laminate side of the obtained sample with a cutter. Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.) is pasted on the obtained notch of 100 squares, peeled off the cellophane tape, and then confirmed the number of squares peeled between the layers in the laminate. The adhesion was judged. The results are shown in Table 1.
Evaluation criteria:
◯: After peeling of the tape, the mass peeled between the layers in the laminate is less than 30 squares.
(Triangle | delta): The mass which peeled between the layers in a laminated body after cellophane peeling is 30 squares or more and 59 squares or less.
X: The mass which peeled between the layers in a laminated body after cellophane peeling is 60 squares or more.

2. Example 2
Except that the preparation of the polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film and the formation of the horizontal alignment liquid crystal cured film were changed as follows, the substrate, the cured resin layer, and the vertical alignment liquid crystal were the same as in Example 1. The laminated body which laminated | stacked the cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film adjacently in this order was produced, and adhesiveness and orientation evaluation of the laminated body were implemented. Table 1 shows the results.

(1) Preparation of polymerizable liquid crystal composition for forming horizontally aligned liquid crystal cured film Polymerizable liquid crystal compound (X1) and polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. For 100 parts by mass of the obtained mixture, 0.1 part by mass of a leveling agent “BYK-361N” (manufactured by BM Chemie) and 2-dimethylamino-2-benzyl-1- (4- 6 parts by mass of morpholinophenyl) butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Ltd.) was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. This mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film.

(2) Formation of horizontal alignment liquid crystal cured film Corona treatment on the vertical alignment liquid crystal cured film surface of the laminate composed of the base material (TAC film), the cured resin layer, and the vertical alignment liquid crystal cured film prepared in the same procedure as in Example 1. The composition for forming a horizontal alignment film was applied using a bar coater and dried at 80 ° C. for 1 minute. Subsequently, using a polarized UV irradiation apparatus (SPOT CURE SP-9; manufactured by USHIO INC.), Polarized UV exposure was performed with an integrated light amount at a wavelength of 313 nm: 100 mJ / cm ² to obtain a horizontal alignment film. It was 200 nm when the film thickness of the obtained horizontal alignment film was measured with the ellipsometer.
Subsequently, a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film is applied on the horizontal alignment film, heated at 120 ° C. for 60 seconds, and then a high pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). Is used to form a horizontally aligned liquid crystal cured film by irradiating ultraviolet rays from the surface coated with the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film (integrated light quantity at a wavelength of 365 nm: 500 mJ / cm ² ) in a nitrogen atmosphere. And the laminated body which laminated | stacked the base material, the cured resin layer, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film adjacently in this order was obtained. The thickness of the obtained horizontally aligned liquid crystal cured film was measured with an ellipsometer and found to be 2.2 μm.

3. Example 3
Except that the preparation of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film and the formation of the vertically aligned liquid crystal cured film were changed as follows, the substrate, the cured resin layer, and the vertically aligned liquid crystal cured were the same as in Example 2. A laminate was prepared by laminating a film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film adjacent to each other in this order, and the adhesion and orientation of the laminate were evaluated. Table 1 shows the results.

(1) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film Polymerizable liquid crystal compound (X1) and polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. The ionic compound A (molecular weight: 645) prepared with reference to 0.25 parts by mass of the leveling agent “F-556” (manufactured by DIC) and Japanese Patent Application No. 2006-514802 with respect to 100 parts by mass of the obtained mixture. ) 2.0 parts by mass, 0.5 parts by mass of silane coupling agent “KBE-9103” (manufactured by Shin-Etsu Chemical Co., Ltd.), 2-dimethylamino-2-benzyl-1- (4-morpholino as a photopolymerization initiator) 6 parts by mass of phenyl) butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Ltd.) was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. This mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.

(2) Preparation of vertically aligned liquid crystal cured film A polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was applied to the cured resin layer on the substrate prepared in the same procedure as in Example 1 using a bar coater. After heating at 120 ° C. for 60 seconds, ultraviolet rays were applied from the surface coated with the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film using a high pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). A vertically aligned liquid crystal cured film was formed by irradiation (integrated light quantity at a wavelength of 365 nm: 500 mJ / cm ² ) in a nitrogen atmosphere. It was 1.2 micrometers when the film thickness of the obtained vertical alignment liquid crystal cured film was measured with the ellipsometer (M-220 by JASCO Corporation).

4). Example 4
A substrate, a cured resin layer, a vertical alignment liquid crystal cured film, a cured resin layer, a horizontal alignment film, and a horizontal alignment liquid crystal cured film are the same as in Example 3 except that the formation of the horizontal alignment liquid crystal cured film is changed as follows. Were laminated adjacently in this order, and the adhesion and orientation of the laminate were evaluated. Table 1 shows the results.

(1) Formation of horizontally aligned liquid crystal cured film 50 parts by mass of dipentaerythritol hexaacrylate (Aronix M-403, polyfunctional acrylate manufactured by Toagosei Co., Ltd.), 50 parts by mass of acrylate resin (Evecril 4858 manufactured by Daicel UC Corporation), 2 -A solution in which 3 parts by mass of methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907; manufactured by Ciba Specialty Chemicals) was dissolved in 250 parts by mass of isopropanol was prepared, and acrylate A composition for forming a cured resin layer comprising a compound was obtained.
Subsequently, corona treatment was performed on the surface of the laminate of the substrate (TAC film), the cured resin layer, and the vertically aligned liquid crystal cured film, and the cured resin layer forming composition was applied with a bar coater. And dried at 50 ° C. for 1 minute. Then, a cured resin is obtained by irradiating with ultraviolet rays (integrated light quantity at a wavelength of 365 nm: 400 mJ / cm ² in a nitrogen atmosphere) using a high-pressure mercury lamp (“UNICURE VB-15201BY-A”, manufactured by USHIO INC.). A layer was formed. It was 2.0 micrometers when the film thickness of the obtained cured resin layer was measured with the contact-type film thickness meter.
Next, corona treatment is performed on the surface of the cured resin layer, which is the outermost layer of the laminate composed of the base material (TAC film), cured resin layer, vertically aligned liquid crystal cured film, and cured resin layer prepared by the above-described method. The composition for forming an alignment film was applied using a bar coater and dried at 80 ° C. for 1 minute. Subsequently, using a polarized UV irradiation apparatus (SPOT CURE SP-9; manufactured by USHIO INC.), Polarized UV exposure was performed with an integrated light amount at a wavelength of 313 nm: 100 mJ / cm ² to obtain a horizontal alignment film. It was 200 nm when the film thickness of the obtained horizontal alignment film was measured with the ellipsometer.
Subsequently, a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film is applied on the horizontal alignment film, heated at 120 ° C. for 60 seconds, and then a high pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). Is used to form a horizontally aligned liquid crystal cured film by irradiating ultraviolet rays from the surface coated with the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film (integrated light quantity at a wavelength of 365 nm: 500 mJ / cm ² ) in a nitrogen atmosphere. And the laminated body which laminated | stacked the base material, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film adjacently in this order was obtained. The thickness of the obtained horizontally aligned liquid crystal cured film was measured with an ellipsometer and found to be 2.2 μm.

5). Example 5
A substrate, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film are laminated adjacently in this order in the same manner as in Example 3 except that the method for producing the vertical alignment liquid crystal cured film was changed as follows. The laminated body which produced was manufactured, and adhesiveness and orientation evaluation of the laminated body were implemented. Table 1 shows the results.

(1) Production of vertically aligned liquid crystal cured film:
After performing a corona treatment on a COP film (ZF14-23) manufactured by Nippon Zeon Co., Ltd., a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was applied using a bar coater and heated at 120 ° C. for 60 seconds. Then, using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) while being heated to 120 ° C., ultraviolet light is applied from the surface where the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film is applied. Is irradiated (under a nitrogen atmosphere, integrated light quantity at a wavelength of 365 nm: 500 mJ / cm ² ) to form a vertically aligned liquid crystal cured film, and a laminate in which a base material and a vertically aligned liquid crystal cured film are stacked adjacent to each other in this order. Obtained. It was 1.2 micrometers when the film thickness of the obtained vertical alignment liquid crystal cured film was measured with the ellipsometer (M-220 by JASCO Corporation).

6). Example 6
A substrate, a cured resin layer, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film are laminated adjacently in this order in the same manner as in Example 3 except that the preparation of the base material is changed as follows. The laminated body which produced was manufactured, and adhesiveness and orientation evaluation of the laminated body were implemented. Table 1 shows the results.

(1) Preparation of base material 50 parts by mass of dipentaerythritol hexaacrylate (Aronix M-403, polyfunctional acrylate manufactured by Toagosei Co., Ltd.), 50 parts by mass of acrylate resin (Evecril 4858 manufactured by Daicel UC Corporation), 2-methyl- A solution of 3 parts by mass of 1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one (Irgacure 907; manufactured by Ciba Specialty Chemicals) in 250 parts by mass of isopropanol was prepared, and the acrylate compound was contained. A composition for forming a cured resin layer was obtained.
Subsequently, the cured resin layer forming composition was applied on a PET film (Diafoil T140E25) manufactured by Mitsubishi Plastics Co., Ltd. with a bar coater, dried at 50 ° C. for 1 minute, and then a high-pressure mercury lamp (“UNICURE VB-15201BY”). The cured resin layer was formed by irradiating with ultraviolet rays (accumulated light amount at a wavelength of 365 nm: 400 mJ / cm ² ) using “-A”, manufactured by USHIO INC. It was 2.0 micrometers when the film thickness of the obtained cured resin layer was measured with the contact-type film thickness meter.

7). Example 7
A laminate in which a base material, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film are laminated adjacently in this order in the same manner as in Example 5 except that the film thickness of the horizontal alignment film is changed to 30 nm. Was prepared, and the adhesion and orientation of the laminate were evaluated. Table 1 shows the results.

8). Example 8
A laminate in which a base material, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film are laminated adjacently in this order in the same manner as in Example 5 except that the film thickness of the horizontal alignment film is changed to 500 nm. Was prepared, and the adhesion and orientation of the laminate were evaluated. Table 1 shows the results.

9. Example 9
A substrate, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film were prepared in the same manner as in Example 5 except that the preparation of the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film was changed as follows. A laminated body laminated adjacently in this order was produced, and the adhesion and orientation of the laminated body were evaluated. Table 1 shows the results.

(1) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film Polymerizable liquid crystal compound (X1) and polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. The ionic compound A (molecular weight: 645) prepared with reference to 0.25 parts by mass of the leveling agent “F-556” (manufactured by DIC) and Japanese Patent Application No. 2006-514802 with respect to 100 parts by mass of the obtained mixture. ) 2.0 parts by mass, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (BASF Japan Ltd. “Irgacure (registered trademark) 369 (Irg369) as a photopolymerization initiator” ]) 6 parts by weight were added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. This mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.

10. Example 10
A substrate, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film were prepared in the same manner as in Example 5 except that the preparation of the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film was changed as follows. A laminated body laminated adjacently in this order was produced, and the adhesion and orientation of the laminated body were evaluated. Table 1 shows the results.

(1) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film Polymerizable liquid crystal compound (X1) and polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. For 100 parts by mass of the obtained mixture, leveling agent “F-556” (manufactured by DIC) 0.25 part by mass, silane coupling agent “KBE-9103” (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 mass Part, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Ltd.) as a photopolymerization initiator 6 parts by mass Was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. This mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.

11. Comparative Example 1
A substrate, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film were prepared in the same manner as in Example 5 except that the preparation of the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film was changed as follows. A laminated body laminated adjacently in this order was produced, and the adhesion and orientation of the laminated body were evaluated. Table 1 shows the results.

(1) Preparation of polymerizable liquid crystal composition for forming vertically aligned liquid crystal cured film Polymerizable liquid crystal compound (X1) and polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. Leveling agent “F-556” (manufactured by DIC) 0.25 part by mass with respect to 100 parts by mass of the obtained mixture, and 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) as a photopolymerization initiator ) Butan-1-one ("Irgacure (registered trademark) 369 (Irg369)" manufactured by BASF Japan Ltd.) 6 parts by mass was added. Further, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. This mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film.

12 Comparative Example 2
A substrate, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film are laminated adjacently in this order in the same manner as in Example 5 except that the manufacturing process of the horizontal alignment liquid crystal cured film is changed as follows. The laminated body which produced was manufactured, and adhesiveness and orientation evaluation of the laminated body were implemented. Table 1 shows the results.

(1) Preparation of polymerizable liquid crystal composition for forming horizontally aligned liquid crystal cured film Polymerizable liquid crystal compound (X1) and polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. For 100 parts by mass of the obtained mixture, 0.1 part by mass of a leveling agent “BYK-361N” (manufactured by BM Chemie) and 2-dimethylamino-2-benzyl-1- (4- 6 parts by mass of morpholinophenyl) butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Ltd.) was added. Further, cyclopentanone was added so that the solid content concentration was 13%. This mixture was stirred at 80 ° C. for 1 hour to obtain a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film.

(2) Formation of horizontally aligned liquid crystal cured film Corona treatment was performed on the vertically aligned liquid crystal cured film of the laminate composed of the base material and the vertically aligned liquid crystal cured film produced by the method described above. Subsequently, a 4% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied, and after drying, a film having a thickness of 0.2 μm was formed. Subsequently, the surface of the obtained film was rubbed to obtain a horizontal alignment film. The rubbing process uses a semi-automatic rubbing apparatus (trade name: LQ-008, manufactured by Joyo Engineering Co., Ltd.) and a push-in amount of 0.15 mm using a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.). , Under the conditions of 500 rpm and 16.7 mm / s.
Subsequently, a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film is applied on the horizontal alignment film, heated at 120 ° C. for 60 seconds, and then a high pressure mercury lamp (Unicure VB-15201BY-A, manufactured by USHIO INC.). Is used to form a horizontally aligned liquid crystal cured film by irradiating ultraviolet rays from the surface coated with the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film (integrated light quantity at a wavelength of 365 nm: 500 mJ / cm ² ) in a nitrogen atmosphere. And the laminated body which laminated | stacked the base material, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film adjacently in this order was obtained. The thickness of the obtained horizontally aligned liquid crystal cured film was measured with an ellipsometer and found to be 2.2 μm.

  According to the present invention, it was confirmed that a vertically aligned liquid crystal cured film can be produced without forming a vertically aligned film, and the liquid crystal alignment and adhesion can be improved at the same time (Examples 1 to 10). On the other hand, when a polymerizable liquid crystal composition containing no vertical alignment accelerator is used, a vertical alignment liquid crystal cured film cannot be obtained without forming a vertical alignment film. The retardation value of the cured film could not be calculated (Comparative Example 1). Furthermore, in Comparative Example 2 where the horizontal alignment film was not a photo-alignment film, the adhesion between the vertically aligned liquid crystal cured film and the horizontal aligned liquid crystal cured film was inferior.

1: substrate 2: vertically aligned liquid crystal cured film 3: horizontal aligned film 4: horizontal aligned liquid crystal cured film 5: cured resin layer 11: laminate

Claims (21)

A laminate including a base material, a vertical alignment liquid crystal cured film, a horizontal alignment film and a horizontal alignment liquid crystal cured film in this order,
The vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition that is cured in a state where the polymerizable liquid crystal compound is aligned in a direction perpendicular to the plane of the liquid crystal cured film. Is a cured product of a polymerizable liquid crystal composition cured in a state in which the crystalline liquid crystal compound is aligned in a horizontal direction with respect to the liquid crystal cured film plane,
The vertical alignment liquid crystal cured film contains a vertical alignment accelerator, and the horizontal alignment film is a photo-alignment film formed from a polymer having a (meth) acryloyl group,
The laminated body whose total film thickness from the surface by the side of the base material side of the said vertical alignment liquid crystal cured film to the surface on the opposite side to the horizontal alignment film of a horizontal alignment liquid crystal film is 10 micrometers or less.   The laminate according to claim 1, wherein the substrate is a peelable substrate.   The laminated body of Claim 1 or 2 with which a base material, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film exist adjacent in this order.   The laminated body in any one of Claims 1-3 whose film thickness of a horizontal alignment film is 10-5000 nm.   The laminate according to any one of claims 1 to 4, wherein the horizontal alignment film is a photo-alignment film formed from a polymer having an azo group or a cinnamoyl group.   The laminated body in any one of Claims 1-5 in which a horizontal alignment liquid crystal cured film has at least 1 or more maximum absorption between wavelengths 300-400 nm. The horizontally aligned liquid crystal cured film has the following formula (1):
ReA (450) / ReA (550) ≦ 1 (1)
[In formula (1), ReA (450) represents an in-plane retardation value at a wavelength of 450 nm in the in-plane direction of the horizontally aligned liquid crystal cured film, and ReA (550) represents a wavelength of 550 nm in the in-plane direction of the horizontally aligned liquid crystal cured film. Represents the in-plane retardation value at
The laminated body in any one of Claims 1-6 which satisfy | fills.   The laminated body in any one of Claims 1-7 in which a vertical alignment liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter.   The laminate according to any one of claims 1 to 8, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound as a vertical alignment accelerator, and the nonionic silane compound is a silane coupling agent.   The laminated body in any one of Claims 1-9 in which a vertical alignment liquid crystal cured film contains the ionic compound which consists of a nonmetallic atom as a vertical alignment promoter.   The vertical alignment liquid crystal cured film contains an ionic compound composed of a nonmetal atom as a vertical alignment accelerator, and the molecular weight of the ionic compound is 100 or more and 10,000 or less. Laminated body.   The laminated body in any one of Claims 1-11 in which a vertical alignment liquid crystal cured film contains the ionic compound which consists of a nonionic silane compound and a nonmetallic atom as a vertical alignment promoter.   The horizontally aligned liquid crystal cured film is a liquid crystal cured film obtained by curing a polymerizable liquid crystal compound having at least one radical polymerizable group in a state of being aligned horizontally with respect to the in-plane direction of the liquid crystal cured film, and is vertical. The alignment liquid crystal cured film is a liquid crystal cured film formed by curing in a state in which the polymerizable liquid crystal compound having at least one radical polymerizable group is aligned perpendicular to the in-plane direction of the liquid crystal cured film. The laminate according to any one of 12 above.   The laminate according to any one of claims 1 to 13, wherein the vertically aligned liquid crystal cured film has at least one maximum absorption between wavelengths of 300 to 400 nm. The vertically aligned liquid crystal cured film has the following formula (2):
RthC (450) / RthC (550) ≦ 1 (2)
[In Formula (2), RthC (450) represents the retardation value in the thickness direction at a wavelength of 450 nm of the vertically aligned liquid crystal cured film, and RthC (550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. Represents]
The laminated body in any one of Claims 1-14 which satisfy | fills.   The elliptically polarizing plate containing the laminated body in any one of Claims 1-15, and a polarizing film.   The elliptically polarizing plate containing the laminated body which removed the base material from the laminated body in any one of Claims 1-15, and a polarizing film.   The elliptically polarizing plate according to claim 16 or 17, wherein an angle formed by the slow axis of the horizontally aligned liquid crystal cured film constituting the laminate and the absorption axis of the polarizing film is 45 ± 5 °.   The organic electroluminescence display containing the elliptically polarizing plate in any one of Claims 16-18. It is a manufacturing method of the layered product according to any one of claims 1 to 15,
Forming a coating film of a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film containing a polymerizable liquid crystal compound, and forming a vertically aligned liquid crystal cured film from the coated film;
Forming a coating film of the composition for forming a horizontal alignment film, and forming a horizontal alignment film from the coating film; and
The manufacturing method including the process of forming the coating film of the polymeric liquid crystal composition for horizontal alignment liquid crystal cured film formation containing a polymeric liquid crystal compound, and forming a horizontal alignment liquid crystal cured film from this coating film in this order.   21. The manufacturing method according to claim 20, wherein the step of forming the vertical alignment liquid crystal cured film, the step of forming the horizontal alignment film, and the step of forming the horizontal alignment liquid crystal cured film are successively performed in this order.

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