TWI808127B - Laminated body and manufacturing method thereof - Google Patents

Abstract

The laminated system of the present invention comprises a substrate, a vertically aligned liquid crystal cured film, a horizontally aligned liquid crystal cured film, and a horizontally aligned liquid crystal cured film in the following order, The vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition formed by curing a polymerizable liquid crystal compound in a state aligned vertically relative to the plane of the liquid crystal cured film, and the horizontally aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition formed by curing a polymerizable liquid crystal compound in a state aligned horizontally relative to the plane of the liquid crystal cured film, The vertical alignment liquid crystal cured film contains a vertical alignment accelerator, the horizontal alignment film is a photo-alignment film formed of a (meth)acrylic polymer, and The total film thickness from the substrate-side surface of the vertical alignment cured liquid crystal film to the surface of the horizontal alignment cured liquid crystal film opposite to the horizontal alignment film is 10 μm or less.

Description

Laminated body and manufacturing method thereof

The present invention relates to a laminate comprising a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film, an elliptical polarizer comprising the above laminate, and an organic EL display device. Moreover, this invention also relates to the manufacturing method of the said laminated body.

An elliptical polarizer is an optical member formed by laminating a polarizer and a retardation plate. For example, in a device that displays images in a flat state, such as an organic EL image display device, it is used to prevent light reflection on the electrodes constituting the device. As a retardation plate constituting the elliptically polarizing plate, a so-called λ/4 plate is generally used.

In terms of easily exhibiting uniform retardation performance in a wide wavelength range of visible light, as a retardation plate constituting an elliptically polarizing plate, one showing reverse wavelength dispersion is preferable. As such a retardation plate, there is known a retardation plate including a horizontally aligned liquid crystal cured film obtained by polymerizing and curing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion in a state aligned in a direction horizontal to the plane of the retardation plate. Furthermore, it is known that by further incorporating a vertically aligned liquid crystal cured film into an elliptical polarizing plate having a horizontally aligned liquid crystal cured film, it is possible to suppress oblique hue changes during black display when the elliptical polarizing plate is used in an organic EL display device. Patent Document 1 describes a laminate comprising a vertically aligned liquid crystal cured film formed on a vertically aligned film and a horizontally aligned liquid crystal cured film formed on a horizontally aligned film. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-163935

[Problem to be solved by the invention]

However, the laminates including the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film described in the above-mentioned patent documents are usually manufactured by the following method: After the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film are independently produced, the two are bonded together with an adhesive or the like. In addition, in the manufacture of the vertically aligned liquid crystal cured film, a vertically aligned film for aligning the polymerizable liquid crystal compound in the vertical direction is required, and the vertically aligned film needs to be formed before the formation of the vertically aligned liquid crystal cured film. Therefore, the manufacturing steps of the conventional laminate including the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film tend to become complicated, and productivity tends to decrease.

Therefore, the purpose of the present invention is to provide a novel solution to the above problems, that is, to form a vertically aligned liquid crystal cured film without forming a vertically aligned film, and to continuously form a laminate of horizontally aligned liquid crystal cured films, and its manufacturing method.

Furthermore, in the study of the above-mentioned solution by the present inventors, it has been clarified that when a vertically aligned liquid crystal cured film is formed without forming a vertically aligned film, its liquid crystal alignment is likely to decrease; and when a horizontally aligned liquid crystal cured film is formed on a vertically aligned liquid crystal cured film via a horizontally aligned film, the adhesion between the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film is likely to decrease compared with a laminate formed by bonding the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film through an adhesive layer.

Therefore, the present invention also aims to improve the alignment of liquid crystals in a laminate including a horizontally aligned liquid crystal cured film laminated on a vertically aligned liquid crystal cured film formed without a vertically aligned liquid crystal film; and 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 a horizontal alignment film. [Technical means to solve the problem]

The inventors of the present invention conducted earnest research to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention includes the following aspects. [1] A laminate comprising a substrate, a vertically aligned liquid crystal cured film, a horizontally aligned liquid crystal cured film, and a horizontally aligned liquid crystal cured film in the following order, The vertically aligned liquid crystal curable film is a cured product of a polymerizable liquid crystal composition cured in a state where a polymerizable liquid crystal compound is aligned perpendicular to the plane of the liquid crystal cured film, and the horizontally aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition that is cured in a state where a polymerizable liquid crystal compound is aligned horizontally with respect to the plane of the liquid crystal cured film, The vertical alignment liquid crystal cured film contains a vertical alignment promoter, and the horizontal alignment film is a photo-alignment film formed of (meth)acrylic polymer, The total film thickness from the substrate-side surface of the vertical alignment cured liquid crystal film to the surface of the horizontal alignment cured liquid crystal film opposite to the horizontal alignment film is 10 μm or less. [2] The laminate as described in [1] above, wherein the substrate is a peelable substrate. [3] The laminate described in [1] or [2] above, wherein the substrate, the vertically aligned liquid crystal cured film, the horizontally aligned liquid crystal cured film, and the horizontally aligned liquid crystal cured film are present adjacent to each other in this order. [4] The laminate according to any one of the above [1] to [3], wherein the film thickness of the horizontal alignment film is 10 to 5000 nm. [5] The laminate according to any one of [1] to [4] above, wherein the horizontal alignment film is a photo-alignment film formed of a polymer having an azo group or a cinnamonyl group. [6] The laminate according to any one of [1] to [5] above, wherein the horizontally aligned liquid crystal cured film has at least one maximum absorption at a wavelength of 300 to 400 nm. [7] The laminate described in any one of [1] to [6] above, wherein the horizontally aligned liquid crystal cured film satisfies the following formula (1): ReA(450)/ReA(550)≦1 (1) [In the formula (1), ReA(450) represents the in-plane retardation value under the wavelength 450 nm in the in-plane direction of the horizontally aligned liquid crystal cured film, and ReA(550) represents the in-plane retardation value under the wavelength 550 nm in the in-plane direction of the horizontally aligned liquid crystal cured film]. [8] The laminate according to any one of the above [1] to [7], wherein the vertical alignment liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter. [9] The laminate according to any one of [1] to [8] above, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter, and the nonionic silane compound is a silane coupling agent. [10] The laminate according to any one of [1] to [9] above, wherein the vertically aligned liquid crystal cured film contains an ionic compound containing a non-metal atom as a vertical alignment accelerator. [11] The laminate according to any one of [1] to [10] above, wherein the vertically aligned liquid crystal cured film contains an ionic compound containing non-metal atoms as a vertical alignment promoter, and the molecular weight of the ionic compound is 100 to 10,000. [12] The laminate according to any one of [1] to [11] above, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound and an ionic compound containing a nonmetal atom as a vertical alignment accelerator. [13] The laminate according to any one of [1] to [12] above, wherein the horizontally aligned liquid crystal cured film is a cured liquid crystal film formed by curing a polymerizable liquid crystal compound having at least one radically polymerizable group in a state aligned horizontally with respect to the in-plane direction of the liquid crystal cured film, and the vertically aligned liquid crystal cured film is a cured liquid crystal film formed by curing a polymerizable liquid crystal compound having at least one radically polymerizable group in a state aligned vertically with respect to the in-plane direction of the liquid crystal cured film. [14] The laminate according to any one of [1] to [13] above, wherein the vertically aligned liquid crystal cured film has at least one absorption maximum at a wavelength of 300 to 400 nm. [15] The laminate described in any one of [1] to [14] above, wherein the vertically aligned liquid crystal cured film satisfies the following formula (2): RthC(450)/RthC(550)≦1 (2) [In formula (2), RthC(450) represents the retardation value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 450 nm, and RthC(550) represents the retardation value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550 nm]. [16] An elliptically polarizing plate comprising the laminate described in any one of [1] to [15] above and a polarizing film. [17] An elliptically polarizing plate comprising a laminate obtained by removing a substrate from the laminate described in any one of [1] to [15] above, and a polarizing film. [18] The elliptically polarizing plate described in [16] or [17] above, wherein the 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°. [19] An organic EL display device comprising the elliptically polarizing plate according to any one of the above-mentioned [16] to [18]. [20] A method for manufacturing the laminate described in any one of the above [1] to [15], which includes the following steps in the following order: Forming a coating film of a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film containing a polymerizable liquid crystal compound, and forming a vertical alignment liquid crystal cured film from the coating 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 A coating film of a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film containing a polymerizable liquid crystal compound is formed, and a horizontal alignment liquid crystal cured film is formed from the coating film. [21] The production method described in [20] above, wherein the step of forming a vertically aligned liquid crystal cured film, the step of forming a horizontally aligned liquid crystal film, and the step of forming a horizontally aligned liquid crystal cured film are continuously performed in the following order. [Effect of Invention]

According to the present invention, it is possible to provide a laminate capable of forming a vertically aligned liquid crystal cured film without forming a vertically aligned liquid crystal film, and further forming a horizontally aligned liquid crystal cured film on the vertically aligned liquid crystal cured film via a horizontal alignment film, and a manufacturing method thereof. Furthermore, the above-mentioned laminate can improve the liquid crystal alignment; and can 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 horizontally aligned film.

The laminate of the present invention comprises a base material, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film in the following order. Hereinafter, an example of the layer configuration of the laminate of the present invention will be described based on FIGS. 1 to 3 , but the laminate of the present invention is not limited to these aspects.

The laminate 11 shown in FIG. 1 is formed by sequentially laminating a substrate 1 , a vertically aligned liquid crystal cured film 2 , a horizontally aligned liquid crystal cured film 3 , and a horizontally aligned liquid crystal cured film 4 . In the laminated body 11 shown in FIG. 1 , the vertical alignment liquid crystal cured film 2 is directly formed on the substrate 1 without interposing a layer having a vertical alignment restriction force (hereinafter, also referred to as “vertical alignment film”), and the substrate 1 and the vertical alignment liquid crystal cured film 2 exist adjacently. In addition to the substrate, the vertically aligned liquid crystal cured film, the horizontally aligned liquid crystal cured film, and the horizontally aligned liquid crystal cured film, the laminate of the present invention may further include other layers within the range that does not affect the effect of the present invention. Examples of other layers include a cured resin layer such as a protective layer or a hard coat layer, and an adhesive layer for bonding a horizontally aligned liquid crystal cured film, the laminate of the present invention, and a polarizing film.

As a laminate including other layers, for example, a laminate 11 shown in FIG. 2 as another aspect of the present invention is formed by laminating a substrate 1 and a vertical alignment liquid crystal cured film 2 through a cured resin layer 5, and laminating a horizontal alignment film 3 and a horizontal alignment liquid crystal cured film 4 on the vertical alignment liquid crystal cured film 2. Furthermore, as another aspect of the present invention, the laminated body 11 shown in FIG. 3 is formed by laminating the base material 1 and the vertically aligned liquid crystal cured film 2 via the cured resin layer 5 , further laminating the above-mentioned vertically aligned liquid crystal cured film 2 and the horizontal alignment film 3 via the cured resin layer 5 , and laminating the horizontally aligned liquid crystal cured film 4 on the horizontally aligned film 3 . An elliptically polarizing plate can be obtained by bonding the laminate 11 and a polarizing film through an 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 can also be attached to the polarizing film. For example, after the substrate 1 of the laminated body 11 in FIG. Furthermore, hereinafter, in this specification, the minimum layer configuration including a base material, a vertical alignment liquid crystal cured film, a horizontal alignment film, and a horizontal alignment liquid crystal cured film in the following order among the layer configurations of the laminate of the present invention is referred to as "basic layer configuration (I)". That is, for example, when the laminate of the present invention is composed of a substrate, a vertically aligned liquid crystal cured film, a horizontally aligned film, a first horizontally aligned liquid crystal cured film, and a second horizontally aligned liquid crystal cured film, the horizontally aligned liquid crystal cured film (in this case, the first horizontally aligned liquid crystal cured film) from the substrate to the side farthest from the substrate becomes the basic layer configuration (I) of the laminate of the present invention.

In the laminate of the present invention, the total film thickness from the substrate-side surface of the vertically aligned liquid crystal cured film to the surface of the horizontally aligned liquid crystal cured film opposite to the horizontal alignment film (thickness between a-b in FIGS. Since the laminate of the present invention can directly form a horizontal alignment cured film on the vertical alignment cured film via a horizontal alignment film, it can make the total film thickness T1 thinner compared with the previous laminate obtained by separately manufacturing the vertical alignment cured film and the horizontal alignment cured film and laminating them together with an adhesive or an adhesive. The thinning of the total film thickness T1 of the laminate also contributes to the thinning of the entire laminate and the elliptically polarizing plate including the laminate. The above-mentioned total film thickness T1 of the laminate of the present invention is preferably 7 μm or less, more preferably 5 μm or less. The lower limit of the above-mentioned total film thickness T1 is not particularly limited, and may generally be greater than 1 μm, for example, greater than 1.5 μm. Furthermore, when the layered body of the present invention has a vertically aligned liquid crystal cured film and/or a horizontally aligned liquid crystal cured film on the opposite side of the horizontally aligned liquid crystal cured film of the basic layer configuration (I), the above-mentioned total 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 constituted (I) to the surface of the horizontally aligned liquid crystal cured film on the opposite side to the horizontal alignment film.

In the laminate of the present invention, the vertically aligned liquid crystal cured film may be formed on the substrate without intervening the vertical alignment film or on a layer having no vertical alignment restriction force on the substrate. In the laminate of the present invention, since the vertical alignment liquid crystal cured film can be formed without the vertical alignment film, the number of manufacturing steps of the laminate is reduced, and the laminate can be manufactured with good productivity. That is, in one aspect of the laminated body of the present invention, the base material and the vertical alignment liquid crystal cured film are laminated without intervening the vertical alignment film. In a more preferable aspect, the laminate system substrate of the present invention, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film are adjacently present in this order. The laminate of the present invention having such a layer structure can form a vertically aligned cured liquid crystal film on the substrate without a vertically aligned film, and can further form a horizontally aligned cured liquid crystal film on the vertically aligned liquid crystal cured film via a horizontally aligned film. Therefore, it becomes a laminate that can be manufactured with better productivity.

Hereinafter, each structure of the laminated body of this invention is demonstrated in detail. [Vertical Alignment Liquid Crystal Curing Film] The vertical alignment liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymeric liquid crystal composition formed by curing a polymerizable liquid crystal compound in a state of being aligned in a vertical direction with respect to the plane of the liquid crystal cured film. In this invention, a vertical alignment liquid crystal cured film contains a vertical alignment promoter. That is, in this invention, the polymeric liquid crystal composition which forms a vertical alignment liquid crystal cured film contains a vertical alignment promoter. In the present invention, the vertical alignment promoter means a material that promotes the liquid crystal alignment of the polymerizable liquid crystal compound in a direction perpendicular to the film plane. By making a vertical alignment liquid crystal cured film contain a vertical alignment promoter, a vertical alignment liquid crystal cured film can be formed without a 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 good productivity. Furthermore, when a horizontal alignment film and a horizontal alignment cured liquid crystal film are formed on this vertical alignment liquid crystal cured film, the orientation of the horizontal alignment liquid crystal cured film tends to deteriorate easily. The reason has not been determined, but it is speculated that the surface energy decreases due to additives such as leveling agents contained in the vertically aligned liquid crystal cured film, and the alignment of the liquid crystal compound is easily damaged when the horizontally aligned liquid crystal cured film is formed on the upper layer. In particular, when forming a vertically aligned liquid crystal cured film without a vertically aligned film, since an alignment promoter is further contained, the influence becomes more remarkable.

Examples of the vertical alignment promoter that promotes the alignment of the polymerizable liquid crystal compound in the vertical direction include nonionic silane compounds and ionic compounds containing nonmetal atoms. The vertical alignment liquid crystal cured film preferably contains at least one of a nonionic silane compound and an ionic compound containing a nonmetal atom, and more preferably contains both a nonionic silane compound and an ionic compound containing a nonmetal atom.

If 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 the dry coating film formed by the polymerizable liquid crystal composition tends to concentrate the nonionic silane compound at the interface between the dry coating film and the air, and increases the vertical alignment restriction force for the polymerizable liquid crystal compound, so that the polymerizable liquid crystal compound in the dry coating film tends to be aligned in a direction perpendicular to the film plane. Thereby, the state of vertical alignment of the polymerizable liquid crystal compound can be maintained to form a liquid crystal cured film.

The nonionic silane compound is a nonionic compound containing Si element. Examples of nonionic silane compounds include silicone polymers such as polysilanes, silicone resins such as silicone oils and silicone resins, organoinorganic silane compounds such as polysiloxane oligomers, silsesquioxanes, and alkoxysilanes (more specifically, silane coupling agents, etc.). These nonionic silane compounds may be used alone or in combination of two or more. Among them, a silane coupling agent is preferable from the viewpoint of further improving the adhesiveness with the adjacent layer.

The nonionic silane compound can be polysiloxane monomer type or polysiloxane oligomer (polymer) type. If polysiloxane oligomers are expressed in the form of (monomer)-(monomer) copolymers, examples include: 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer containing mercaptopropyl groups; Silane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane-tetramethoxysilane copolymer and mercaptomethyltriethoxysilane-tetraethoxysilane copolymer, such as mercaptomethyl-containing copolymers; 3-methacryloxypropyl trimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropyl trimethoxysilane-tetraethoxysilane copolymer, Tetramethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer Copolymers containing methacryloxypropyl groups such as alkane copolymers; 3-acryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer Oxysilane copolymer, 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer containing acryloxypropyl group; vinyltrimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane Alkane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxysilane copolymer and vinylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltrimethyl Oxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer Amino group-containing copolymers such as ethoxysilane copolymers, etc.

The silane coupling agent is a compound containing Si element having at least one functional group selected from the group consisting of vinyl group, epoxy group, styryl group, methacryl group, acryl group, amine group, isocyanurate group, urea group, mercapto group, isocyanate group, carboxyl group, and hydroxyl group at the end, and at least one alkoxysilyl group or silanol group. By properly selecting these functional groups, it is possible to provide special effects such as improving the mechanical strength of the vertically aligned cured liquid crystal film, modifying the surface of the vertically aligned liquid crystal cured film, and improving the adhesion to the layer adjacent to the vertically aligned cured liquid crystal film. 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-mentioned functional group). Furthermore, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and a polar group. If the silane coupling agent has at least one alkoxysilyl group and at least one polar group in its molecule, the vertical alignment of the polymerizable liquid crystal compound is more likely to be improved, and the vertical alignment promotion effect tends to be significantly obtained. As a polar group, an epoxy group, an amino group, an isocyanuric acid group, a mercapto group, a carboxyl group, and a hydroxyl group are mentioned, for example. Furthermore, the polar group may have an appropriate substituent or protecting group in order to control the reactivity of the silane coupling agent.

Examples of silane coupling agents 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-butylene) Propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidyl Oxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane.

In addition, 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, 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-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE- Silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. such as 846 and KBE-9007.

When the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film contains a nonionic silane compound, its content is usually 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 relative to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. When the content of the nonionic silane compound is within the above range, the vertical alignment of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coating properties of the polymerizable liquid crystal composition.

If the polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains an ionic compound containing non-metal atoms, then in the dry coating film formed by the polymerizable liquid crystal composition, the vertical alignment restriction force for the polymerizable liquid crystal compound is expressed by electrostatic interaction, and the polymerizable liquid crystal compound tends to align in the direction perpendicular to the film plane in the dry coating film. Thereby, the state of vertical alignment of the polymerizable liquid crystal compound can be maintained to form a liquid crystal cured film.

Examples of ionic compounds containing nonmetal atoms include onium salts (more specifically, quaternary ammonium salts having a positive charge on a nitrogen atom, tertiary permeic acid salts, and quaternary phosphonium salts having a positive charge on a phosphorus atom). Among these onium salts, quaternary onium salts are preferable from the viewpoint of improving the vertical alignment of the polymerizable liquid crystal compound, and quaternary phosphonium salts or quaternary ammonium salts are more preferable from the viewpoint of improving availability and mass production. The onium salt may have two or more quaternary onium salt sites in the molecule, and may also be an oligomer or a polymer.

The molecular weight of the ionic compound containing nonmetal atoms is preferably from 100 to 10,000. When the molecular weight is within the above range, it is easy to improve the vertical alignment of the polymerizable liquid crystal compound while ensuring the applicability of the polymerizable liquid crystal composition. The molecular weight of the ionic compound containing a nonmetal atom is more preferably 5,000 or less, further preferably 3,000 or less.

As a cation component of the ionic compound containing a nonmetal atom, an inorganic cation and an organic cation are mentioned, for example. Among them, organic cations are preferred in terms of less likely to cause alignment defects of the polymerizable liquid crystal compound. Examples of organic cations include imidazolium cations, pyridinium cations, ammonium cations, percite cations, and phosphonium cations.

Ionic compounds comprising non-metal atoms generally have a counteranion. As an anion component used as a counter ion of the said cation component, an inorganic anion and an organic anion are mentioned, for example. Among these, organic anions are preferred in terms of the difficulty in generating alignment defects of the polymerizable liquid crystal compound. Furthermore, cations and anions do not have to be in one-to-one correspondence.

As an anion component, specifically, the following are mentioned, for example.氯陰離子[Cl ^- ]、 溴陰離子[Br ^- ]、 碘陰離子[I ^- ]、 四氯鋁酸根陰離子[AlCl ₄ ^- ]、 七氯二鋁酸根陰離子[Al ₂ Cl ₇ ^- ]、 四氟硼酸根陰離子[BF ₄ ^- ]、 六氟磷酸根陰離子[PF ₆ ^- ]、 過氯酸根陰離子[ClO ₄ ^- ]、 硝酸根陰離子[NO ₃ ^- ]、 乙酸根陰離子[CH ₃ COO ^- ]、 三氟乙酸根陰離子[CF ₃ COO ^- ]、 氟磺酸根陰離子[FSO ₃ ^- ]、 甲磺酸根陰離子[CH ₃ SO ₃ ^- ]、 三氟甲磺酸根陰離子[CF ₃ SO ₃ ^- ]、 對甲苯磺酸根陰離子[p-CH ₃ C ₆ H ₄ SO ₃ ^- ]、 雙(氟磺醯)亞胺陰離子[(FSO ₂ ) ₂ N ^- ]、 雙(三氟甲磺醯)亞胺陰離子[(CF ₃ SO ₂ ) ₂ N ^- ]、 三(三氟甲磺醯)甲烷陰離子[(CF ₃ SO ₂ ) ₃ C ^- ]、 六氟砷酸根陰離子[AsF ₆ ^- ]、 六氟銻酸根陰離子[SbF ₆ ^- ]、 六氟鈮酸根陰離子[NbF ₆ ^- ]、 六氟鉭酸根陰離子[TaF ₆ ^- ]、 二甲基次膦酸根陰離子[(CH ₃ ) ₂ POO ^- ]、 (聚)氫氟氟化物陰離子[F(HF) _n ^- ](例如，n表示1～3之整數)、 二氰亞胺陰離子[(CN) ₂ N ^- ]、 硫氰化物陰離子[SCN ^- ]、 全氟丁磺酸根陰離子[C ₄ F ₉ SO ₃ ^- ]、 雙(五氟乙磺醯)亞胺陰離子[(C ₂ F ₅ SO ₂ ) ₂ N ^- ]、 全氟丁酸根陰離子[C ₃ F ₇ COO ^- ]、及(三氟甲磺醯基)(三氟甲烷羰基)醯亞胺陰離子[(CF ₃ SO ₂ )(CF ₃ CO)N ^- ]。

Specific examples of the ionic compound containing a nonmetal atom can be appropriately selected from combinations of the aforementioned cationic components and anionic components. About the compound which is a combination of a specific cationic component and an anionic component, the following are mentioned, for example.

(pyridinium salt) N-hexylpyridinium hexafluorophosphate, N-octylpyridinium hexafluorophosphate, N-methyl-4-hexylpyridinium hexafluorophosphate, N-butyl-4-methylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, Bis(fluorosulfonyl)imide 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(trifluoromethanesulfonyl)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, 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, Bis(fluorosulfonyl)imide 1-ethyl-3-methylimidazolium, Bis(trifluoromethanesulfonyl)imide 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-butyl-3-methylimidazolium methanesulfonate, etc.

(pyrrolidinium salt) N-butyl-N-methylpyrrolidinium hexafluorophosphate, Bis(fluorosulfonyl)imide N-butyl-N-methylpyrrolidinium, Bis(trifluoromethanesulfonyl)imide N-butyl-N-methylpyrrolidinium, N-butyl-N-methylpyrrolidinium p-toluenesulfonate, etc.

(ammonium salt) Tetrabutylammonium hexafluorophosphate, Tetrabutylammonium bis(fluorosulfonyl)imide, Bis(fluorosulfonyl)imide tetrahexylammonium, bis(fluorosulfonyl)imide trioctylmethylammonium, Bis(fluorosulfonyl)imide (2-hydroxyethyl)trimethylammonium, Tetrabutylammonium bis(trifluoromethanesulfonyl)imide, Tetrahexylammonium bis(trifluoromethanesulfonyl)imide, bis(trifluoromethanesulfonyl)imide trioctylmethylammonium, bis(trifluoromethanesulfonyl)imide(2-hydroxyethyl)trimethylammonium, Tetrabutylammonium p-toluenesulfonate, Tetrahexylammonium p-toluenesulfonate, Trioctylmethylammonium p-toluenesulfonate, (2-Hydroxyethyl)trimethylammonium p-toluenesulfonate, (2-Hydroxyethyl)trimethylammonium dimethylphosphonous acid, Bis(trifluoromethanesulfonyl)imide 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)aminoformyloxyethyl)}-N,N,N-trimethylammonium, and Bis(trifluoromethanesulfonyl)imide N-[2-{3-(3-trimethoxysilylpropylamino)-1-oxopropoxy}ethyl]-N,N,N-trimethylammonium.

(phosphonium salt) Bis(trifluoromethanesulfonyl)imide 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, 1,1,1-tributyl-1-[2-(trimethoxysilyl)ethyl]phosphonium bis(trifluoromethanesulfonyl)imide, and Bis(trifluoromethanesulfonyl)imide 1,1,1-tributyl-1-[3-(trimethoxysilyl)propyl]phosphonium. These ionic compounds may be used alone, respectively, or may be used in combination of two or more. Among them, ionic compounds containing phosphonium salts, pyridinium salts, and ammonium salts are preferred.

The ionic compound containing nonmetal atoms preferably has Si element and/or F element in the molecular structure of the cation site from the viewpoint of further improving the vertical alignment of the polymerizable liquid crystal compound. If the ionic compound containing non-metal atoms has Si element and/or F element in the molecular structure of the cationic part, the ionic compound is easily segregated to the surface of the vertically aligned liquid crystal cured film. Among these, the ionic compounds in which all the constituent elements are nonmetallic elements are preferably the following ionic compounds (i) to (iii) and the like.

(ionic compound (i)) [Chem. 1] (ionic compound (ii)) [Chem. 2] (ionic compound (iii)) [Chem. 3]

For example, it is possible to apply a method of treating the surface of the substrate with a surfactant having an alkyl group with a certain length of chain to improve the alignment of the liquid crystal (for example, refer to Chapter 2 "Alignment and Physical Properties of Liquid Crystals" in "Liquid Crystal Handbook" (issued by Maruzen Co., Ltd.), etc.), to further improve the vertical alignment of the polymerizable liquid crystal compound. That is, the vertical alignment of the polymerizable liquid crystal compound can be effectively improved by treating the surface of the substrate with an ionic compound having an alkyl group having a certain length of chain.

Specifically, the ionic compound containing a nonmetal atom preferably satisfies the following formula (3). 5<M<16 (3) In formula (3), M is represented by the following formula (4). M=(among substituents directly bonded to atoms with positive charge, the number of covalent bonds from the atom with positive charge to the end of the molecular chain of the substituent with the largest number of covalent bonds to the end of the molecular chain)÷(number of atoms with positive charge) (4) By making the ionic compound containing a nonmetal atom satisfy the above (3), the vertical alignment of the polymerizable liquid crystal compound can be effectively improved.

Furthermore, when there are two or more positively charged atoms in the molecule of an ionic compound containing nonmetal atoms, regarding a substituent having two or more positively charged atoms, the number of covalent bonds from the positively charged atom regarded as the base point to the nearest other positively charged atom is taken 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 containing a nonmetal atom is an oligomer or a polymer having 2 or more repeating units, the structural unit is regarded as one molecule, and the above-mentioned M is calculated. When an atom with a positive charge is incorporated into a ring structure, the number of covalent bonds to the atom with a positive charge via the ring structure, or the number of covalent bonds to the end of a substituent bonded to the ring structure, whichever has the greater number of covalent bonds, is taken as the "number of covalent bonds from the atom with a positive charge to the end of the molecular chain" described in the definition of M above.

When the polymerizable liquid crystal composition forming a vertically aligned liquid crystal cured film contains an ionic compound containing a non-metal atom, the content thereof is usually 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 relative to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. If the content of the ionic compound containing non-metal atoms is within the above range, the good coatability of the polymerizable liquid crystal composition can be maintained, and the vertical alignment of the polymerizable liquid crystal compound can be effectively promoted.

By making the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film contain both a nonionic silane compound and an ionic compound containing a non-metal atom, in a dry coating film formed from a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film, the vertical alignment of the polymerizable liquid crystal compound can be further facilitated by the electrostatic interaction from the ionic compound containing a nonmetal atom and the surface tension reduction effect from the nonionic silane compound. Thereby, it is possible to form a cured liquid crystal film while maintaining a state where the polymerizable liquid crystal compound is vertically aligned with higher precision.

The vertically aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing the above-mentioned vertical alignment promoter and at least one polymerizable liquid crystal compound, preferably a cured liquid crystal film formed by curing a polymerizable liquid crystal compound having at least one radically polymerizable group in a state of vertical alignment relative 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 for forming a vertically aligned liquid crystal cured film means a liquid crystal compound having a polymerizable group, especially a liquid crystal compound having at least one radically polymerizable group. The polymerizable liquid crystal compound is not particularly limited, and for example, previously known polymerizable liquid crystal compounds in the field of retardation films can be used.

The polymerizable group refers to an active radical generated from a polymerization initiator or a group that can participate in a polymerization reaction by an acid or the like. Examples of the polymerizable group include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxiranyl, oxetanyl and the like. Among them, a radical polymerizable group is preferable, an acryloxy group, a methacryloxy group, a vinyl group, and a vinyloxy group are more preferable, and an acryloxy group and a methacryloxy group are still more preferable. When the vertical alignment cured liquid crystal film and the horizontal alignment cured liquid crystal film are laminated via the horizontal alignment film, when both the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film are cured products of a polymerizable liquid crystal compound having at least one radical polymerizable group, the adhesion between the vertical alignment liquid crystal cured film and the horizontal alignment cured liquid crystal film formed continuously through the horizontal photo-alignment film formed from a polymer having a (meth)acryl group is easy to improve.

The liquid crystallinity exhibited by the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, and a thermotropic liquid crystal is preferable in terms of being able to control fine film thickness. In addition, as the phase order structure in the thermotropic liquid crystal, it may be a nematic liquid crystal or a smectic liquid crystal. A polymeric liquid crystal compound can be used individually or in combination of 2 or more types.

The polymerizable liquid crystal compound generally includes: a polymerizable liquid crystal compound exhibiting positive wavelength dispersion and a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion. Only one of the polymerizable liquid crystal compounds may be used, or two polymerizable liquid crystal compounds may be used in combination. It is preferable to contain a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion from the viewpoint that the suppressing effect of oblique reflection hue at the time of black display when the vertically aligned liquid crystal cured film is applied to a display device is large.

As the polymerizable liquid crystal compound showing reverse wavelength dispersibility, compounds having the characteristics of the following (A) to (D) are preferred. (A) A compound capable of forming a nematic phase or a smectic phase. (B) It has π electrons in the long-axis direction (a) of the polymerizable liquid crystal compound. (C) There are π-electrons in a direction intersecting with the major axis direction (a) [intersecting direction (b)]. (D) Assuming that the total of π electrons present in the major axis direction (a) is N(πa), and the total of molecular weights present in the major axis direction is N(Aa), the π electron density of the polymerizable liquid crystal compound in the major axis direction (a) defined by the following formula (i): D(πa)=N(πa)/N(Aa) (i); Assuming that the total of π electrons present in the crossing direction (b) is N(πb), and the sum of the molecular weights present in the crossing direction (b) is N(Ab), the π electron density in the crossing direction (b) of the polymerizable liquid crystal compound defined by the following formula (ii): D(πb)=N(πb)/N(Ab) (ii) in formula (iii) 0≦[D(πa)/D(πb)]<1 (iii) The relationship [that is, the π-electron density in the cross direction (b) is greater than the π-electron density in the long-axis direction (a)]. Also, as described above, the polymerizable liquid crystal compound having π electrons in the long axis and the direction intersecting it has, for example, a T-shaped structure.

Among the features (A) to (D) above, the major axis direction (a) and the number N of π electrons are defined as follows. ・As for the major axis direction (a), for example, in the case of a compound having a rod-like structure, it is the rod-like major axis direction. ・Number of π electrons N(πa) present in the major axis direction (a) does not include π electrons that disappear by polymerization reaction. ・The number N(πa) of π electrons present in the major axis direction (a) is the total number of π electrons on the major axis and their conjugated π electrons, including, for example, the number of π electrons present on rings that exist in the major axis direction (a) and satisfy Huckel's law. ・Number of π electrons N(πb) present in the crossing direction (b) does not include π electrons that disappear by polymerization reaction. The polymerizable liquid crystal compound satisfying the above has a mesogenic structure in the long axis direction. With this mesogen structure, a liquid crystal phase (nematic phase, smectic phase) is expressed.

Apply the polymerizable liquid crystal compound satisfying the above (A) to (D) on the film (layer) forming the liquid crystal cured film, and heat it above the phase transition temperature to form a nematic phase or a smectic phase. In the nematic phase or smectic phase formed by the alignment of the polymerizable liquid crystal compound, the polymerizable liquid crystal compound is usually aligned so that the long-axis directions of the polymerizable liquid crystal compound become parallel to each other, and the long-axis direction becomes the alignment direction of the nematic phase. When such a polymerizable liquid crystal compound is formed into a film and polymerized in a state of a nematic phase or a smectic phase, a polymer film containing a polymer polymerized in a state aligned in the major axis direction (a) can be formed. The polymer film absorbs ultraviolet rays through π electrons in the long axis direction (a) and π electrons in the cross direction (b). Here, let the absorption maximum wavelength of the ultraviolet rays absorbed by the π electrons in the intersecting direction (b) be λbmax. λbmax is usually 300 nm to 400 nm. Since the density of π electrons satisfies the above formula (iii), and the π electron density in the crossing direction (b) is greater than the π electron density in the major axis direction (a), the absorption of linearly polarized ultraviolet light (wavelength λbmax) with a vibrating plane in the crossing direction (b) is greater than the absorption of linearly polarized ultraviolet light (wavelength λbmax) with a vibrating plane in the major axis direction (a). The ratio (absorbance in the cross direction (b) of linearly polarized ultraviolet light/absorbance in the major 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.

Polymerizable liquid crystal compounds having the above characteristics generally exhibit reverse wavelength dispersion in many cases. Specifically, for example, a compound represented by the following formula (X) is exemplified. [chemical 4]

In formula (X), Ar represents a divalent group having an aromatic group which may have a substituent. The term "aromatic group" here means that the number of π electrons in the ring structure is [4n+2] according to Huckel's law. For example, it may have two or more Ar groups as exemplified in (Ar-1) to (Ar-23) below via a divalent linking group. Here n represents an integer. In the case of forming a ring structure including heteroatoms such as -N= or -S-, it also includes the non-covalent bond electron pairs on these heteroatoms that satisfy Huckel's law and have aromaticity. In this aromatic group, it is preferable to contain at least one or more of a nitrogen atom, an oxygen atom, and a sulfur atom. The aromatic group included in the divalent group Ar may be one, or two or more. 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 may be bonded to each other by a single bond, -CO-O-, -O-, or other divalent bonding groups. G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may also be substituted by a halogen atom, an alkyl group having 1 to 4 carbons, a fluoroalkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, a cyano group or a nitro group, and the carbon atoms constituting the divalent aromatic group or alicyclic hydrocarbon group may be replaced by an oxygen atom, a sulfur atom or 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 of 1≦k+l. Here, in the case of 2≦k+l, B ¹ and B ² , G ¹ and G ² are the same as or different from each other. E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms, and here, more preferably an alkanediyl group having 4 to 12 carbon atoms. Also, the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and the -CH ₂ - contained in the alkanediyl group may be substituted with -O-, -S-, -SiH ₂ -, -C(=O)-. ^P1 and ^P2 independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

^G1 and ^G2 are independent, preferably 1,4-phenylenediyl which may be substituted by at least one substituent selected from the group consisting of halogen atoms and alkyl groups having 1 to 4 carbons, 1,4-cyclohexanediyl which may be substituted by at least one substituent selected from the group consisting of halogen atoms and alkyls having 1 to 4 carbons, more preferably methyl-substituted 1,4-phenylenediyl, unsubstituted 1,4-phenylenediyl, or unsubstituted 1,4 - trans-cyclohexanediyl, especially unsubstituted 1,4-phenylenediyl or unsubstituted 1,4-trans-cyclohexanediyl. Also, it is preferable that at least one of the plural G ¹ and G ² is a divalent alicyclic hydrocarbon group, and more preferably at least one of the G ¹ and G ² bonded to L ¹ or L ² 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 carbons, and R ^c and R ^d represent an alkyl group having 1 to 4 carbons 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 -. Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent any of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. L ¹ and L ² are each independently, and are further preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or -OCO-.

B ¹ and B ² are 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 any of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. B ¹ and B ² are each independently, and are further preferably a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, -OCO-, or -OCOCH ₂ CH ₂ -.

From the viewpoint of expressing inverse wavelength dispersion, k and l are preferably in the range of 2≦k+l≦6, preferably k+l=4, more preferably k=2 and l=2. If k=2 and l=2, since it becomes a symmetrical structure, it is preferable.

Examples of the polymerizable group represented by ^P1 or ^P2 include epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloxy group, methacryloxy group, oxiranyl group, and oxetanyl group. Among them, acryloxy, methacryloxy, vinyl and vinyloxy are preferred, and acryloxy and methacryloxy are more preferred.

Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and the like, preferably a benzene ring and a naphthalene ring. Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyridine ring, a pyrimidine ring, a triazole ring, a triazole ring, a pyrroline ring, an imidazole ring, a pyrazole ring, a thiazole ring, a benzothiazole ring, a thienothiazole ring, a oxazole ring, a benzoxazole ring, and a morpholine ring. Among them, it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazolyl group. Also, when Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

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

As an aromatic group represented by Ar, the following groups are mentioned, for example.

[chemical 5]

式(Ar-1)～式(Ar-23)中，*印表示連結部，Z ⁰ 、Z ¹及Z ²分別獨立地表示氫原子、鹵素原子、碳數1～12之烷基、氰基、硝基、碳數1～12之烷基亞磺醯基、碳數1～12之烷基磺醯基、羧基、碳數1～12之氟烷基、碳數1～12之烷氧基、碳數1～12之烷硫基、碳數1～12之N-烷基胺基、碳數2～12之N,N-二烷基胺基、碳數1～12之N-烷基胺磺醯基或碳數2～12之N,N-二烷基胺磺醯基。 In addition, 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-, R ^2' and R ^3' each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbons.

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

Y ¹ , Y ² and Y ³ each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may be substituted.

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 0-6.

The aromatic hydrocarbon groups in Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms such as phenyl, naphthyl, anthracenyl, phenanthrenyl, and biphenyl, preferably phenyl and naphthyl, more preferably phenyl. Examples of the aromatic heterocyclic group include: furyl, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl and other aromatic heterocyclic groups with 4 to 20 carbon atoms containing at least one heteroatom such as nitrogen atom, oxygen atom, sulfur atom, etc., preferably furyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl.

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

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

Q ¹ and Q ² are preferably -NH-, -S-, -NR ^2' -, -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 the 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 heterocycle that Ar may have, for example, a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyrroline ring, a pyrimidine ring, an indole ring, a quinoline ring, an isoquinoline ring, a purine ring, and a pyrrolidine ring. This aromatic heterocyclic group may have a substituent. In addition, Y ¹ may be the above-mentioned 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.

In addition, in the present invention, as the polymerizable liquid crystal compound forming the vertically aligned liquid crystal cured film, for example, a compound containing a group represented by the following formula (Y) (hereinafter also referred to as "polymerizable liquid crystal compound (Y)") can also be used. The polymerizable liquid crystal compound (Y) generally has a tendency to exhibit positive wavelength dispersion. A polymeric liquid crystal compound can be used individually or in combination of 2 or more types.

P11-B11-E11-B12-A11-B13- (Y) [式(Y)中，P11表示聚合性基； A11表示2價脂環式烴基或2價芳香族烴基；該2價脂環式烴基及2價芳香族烴基所含有之氫原子可被取代為鹵素原子、碳數1～6之烷基、碳數1～6之烷氧基、氰基或硝基，該碳數1～6之烷基及該碳數1～6之烷氧基所含有之氫原子可被取代為氟原子； B11表示-O-、-S-、-CO-O-、-O-CO-、-O-CO-O-、-CO-NR ¹⁶ -、-NR ¹⁶ -CO-、-CO-、-CS-或單鍵。 R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbons. B12及B13分別獨立地表示-C≡C-、-CH=CH-、-CH ₂ -CH ₂ -、-O-、-S-、-C(=O)-、-C(=O)-O-、-OC(=O)-、-OC(=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-、-OC(=O)-CH=CH-或單鍵； E11表示碳數1～12之烷二基，該烷二基所含有之氫原子亦可被取代為碳數1～5之烷氧基，該烷氧基所含有之氫原子亦可被取代為鹵素原子；又，構成該烷二基之-CH ₂ -亦可被取代為-O-或-CO-]。

The carbon number 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, especially preferably 5 or 6. A11 is preferably cyclohexane-1,4-diyl or 1,4-phenylene.

E11 is preferably a linear C 1-12 alkanediyl group. -CH ₂ - constituting the alkanediyl group may be substituted with -O-.具體而言，可列舉：亞甲基、伸乙基、丙烷-1,3-二基、丁烷-1,4-二基、戊烷-1,5-二基、己烷-1,6-二基、庚烷-1,7-二基、辛烷-1,8-二基、壬烷-1,9-二基、癸烷-1,10-二基、十一烷-1,11-二基及十二烷-1,12-二基等碳數1～12之直鏈狀烷二基；-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -、-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -及-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -等。 As B11, -O-, -S-, -CO-O-, -O-CO- are preferable, and -CO-O- is more preferable among them. B12 and B13 are preferably independently -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, and among them, -O- or -OC(=O)-O- are more preferable.

The polymerizable group represented by P11 is preferably a radically polymerizable group or a cationic polymerizable group in terms of high polymerization reactivity, especially photopolymerization reactivity, and is preferably a group represented by the following formulas (P-11) to formula (P-15) in terms of ease of handling and easy production of liquid crystal compounds. [chemical 6] [In the formulas (P-11) to (P-15), R ¹⁷ to R ²¹ each independently represent an alkyl group having 1 to 6 carbon atoms or a hydrogen atom].

Specific examples of the groups represented by the formulas (P-11) to (P-15) include groups represented by the following formulas (P-16) to (P-20). [chemical 7]

P11 is preferably a group represented by formula (P-14) to formula (P-20), more preferably vinyl group, p-stilbene group, epoxy group or oxetanyl group. Further preferably, the group represented by P11-B11- is acryloxy or methacryloxy.

Examples of the polymerizable liquid crystal compound (Y) include compounds represented by formula (I), formula (II), formula (III), formula (IV), formula (V) or 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) (式中， A12～A14分別獨立地與與A11含義相同，B14～B16分別獨立地與B12含義相同，B17與B11含義相同，E12與E11含義相同； F11表示氫原子、碳數1～13之烷基、碳數1～13之烷氧基、氰基、硝基、三氟甲基、二甲胺基、羥基、羥甲基、甲醯基、磺基(-SO ₃ H)、羧基、碳數1～10之烷氧基羰基或鹵素原子，構成該烷基及烷氧基之-CH ₂ -亦可被取代為-O-)。

Specific examples of the polymerizable liquid crystal compound (Y) include compounds having a polymerizable group among the compounds described in "3.8.6 Network (Completely Crosslinked Type)" in Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000), "6.5.1 Liquid Crystal Material b. Polymerizable liquid crystals described in Gazette No. 70108, JP-A-2011-6360 and JP-A-2011-207765.

Specific examples of the polymerizable liquid crystal compound (Y) include compounds represented by the following formula (I-1) to formula (I-4), formula (II-1) to formula (II-4), formula (III-1) to formula (III-26), formula (IV-1) to formula (IV-26), formula (V-1) to formula (V-2), and formula (VI-1) to formula (VI-6). In addition, in the following formula, k1 and k2 each independently represent the integer of 2-12. These polymerizable liquid crystal compounds (Y) are preferred in terms of ease of synthesis or ease of acquisition.

[chemical 8]

[chemical 9]

[chemical 10]

[chemical 11]

[chemical 12]

[chemical 13]

[chemical 14]

[chemical 15]

[chemical 16]

By using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity, a vertically aligned liquid crystal cured film with a high degree of alignment order can be formed. In the case of using a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity as the polymerizable liquid crystal compound forming a vertically aligned liquid crystal cured film in the present invention, the polymerizable liquid crystal compound is more preferably a higher order smectic phase (higher order smectic liquid crystal state) from the viewpoint of realizing a higher degree of alignment order. Here, the so-called high-order smectic phase means smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, smectic J phase, smectic K phase, and smectic L phase, and among them, smectic B phase, smectic F phase, and smectic I phase are more preferable. The liquid crystallinity may be a thermotropic liquid crystal or a lyotropic liquid crystal, and a thermotropic liquid crystal is preferable at the point that a fine film thickness can be controlled. In addition, the polymerizable liquid crystal compound exhibiting smectic liquid crystallinity may be a monomer, an oligomer obtained by polymerizing a polymerizable group, or a polymer.

The polymerizable liquid crystal compound exhibiting smectic liquid crystallinity is a liquid crystal compound having at least one polymerizable group, and is preferably a liquid crystal compound having two or more polymerizable groups from the viewpoint of improving the heat resistance of a vertically aligned liquid crystal cured film. Examples of polymerizable groups include: (meth)acryloxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, oxiranyl, oxetanyl, and the like. Among them, it is easy to manufacture; the heat resistance of the vertical alignment cured liquid crystal film is easy to improve; In terms of binding properties, it is preferable to contain a (meth)acryloyloxy group.

Examples of the polymerizable liquid crystal compound exhibiting smectic liquid crystallinity include compounds 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) [式(Z)中，X ^1z及X ^2z相互獨立地表示2價芳香族基或2價脂環式烴基，此處，該2價芳香族基或2價脂環式烴基所含有之氫原子可被取代為鹵素原子、碳數1～4之烷基、碳數1～4之氟烷基、碳數1～4之烷氧基、氰基或硝基，構成該2價芳香族基或2價脂環式烴基之碳原子亦可被取代為氧原子或硫原子或氮原子；其中，X ^1z及X ^2z中之至少1個為可具有取代基之1,4-伸苯基或可具有取代基之環己烷-1,4-二基； Y ^1z為單鍵或二價連結基； nz為1～3，於nz為2以上之情形時，複數個X ^1z相互可相同亦可不同。 X ^2z may be the same as any or all of the plurality of X ^1z , or may be different; and when nz is 2 or more, the plurality of Y ^1z may be the same 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 independently a single bond or a divalent linking group; V ^1z and V ^2z independently represent an alkanediyl group having 1 to 20 carbon atoms that may have a substituent, and the -CH ₂ - constituting the alkanediyl group may also be substituted with -O-, -CO-, -S- or NH-].

In the polymerizable liquid crystal compound (Z), X ^1z and X ^2z are preferably independently substituted 1,4-phenylene or substituted cyclohexane-1,4-diyl, and at least one of X ^1z and X ^2z is substituted 1,4-phenylene or substituted cyclohexane-1,4-diyl, preferably trans-cyclohexane-1,4-diyl. Examples of substituents that optionally substituted 1,4-phenylene groups or optionally substituted cyclohexane-1,4-diyl groups include alkyl groups having 1 to 4 carbon atoms such as methyl groups, ethyl groups, and butyl groups, cyano groups, and halogen atoms such as chlorine atoms and fluorine atoms. Preferably it is unsubstituted.

In addition, in the polymerizable liquid crystal compound (Z)-based formula (Z), the formula (Z1): -(X ^1z -Y ^1z -) _nz -X ^2z - (Z1) [wherein X ^1z , Y ^1z , X ^2z and nz have the same meanings as above] [hereinafter referred to as partial structure (Z1)] is an asymmetric structure, which is preferable in terms of easily expressing smectic liquid crystallinity. The polymerizable liquid crystal compound (Z) whose partial structure (Z1) is an asymmetric structure includes, for example, a polymerizable liquid crystal compound (Z) in which nz is 1 and one X ^1z and X ^2z are mutually different structures. In addition, polymerizable liquid crystal compounds (Z) in which nz is 2, two Y ^1z have the same structure, and two X ^1z have the same structure, one X ^2z and the two X ^1z have different structures; X ^1z bonded to W ^1z among the two X ^1z have a different structure from the other X ^1z and X ^2z , and the other X ^1z and X ^2z have the same structure. . Furthermore, a polymerizable liquid crystal compound (Z) in which nz is 3, three Y ^1z have the same structure as each other, and any one of three X ^1z and one X ^2z is a structure different from the other three is exemplified.

Y ^1z is preferably -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 -. R ^az and R ^bz independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Y ^1z is more preferably -CH ₂ CH ₂ -, -COO- or a single bond, and when there are multiple Y ^1z , Y ^1z bonded to X ^2z is more preferably -CH ₂ CH ₂ - or CH ₂ O-. When all of X ^1z and X ^2z have the same structure, it is preferable that two or more Y ^1z exist in mutually different bonding modes. When there are a plurality of Y ^1z having mutually different bonding methods, since it becomes an asymmetric structure, smectic liquid crystallinity tends to be easily expressed.

U ^2z is the aforementioned polymerizable group. U ^1z is a hydrogen atom or a polymerizable group. The polymerizable group is preferably a (meth)acryloxyl group in terms of ease of manufacture; easy improvement of heat resistance of the vertically aligned liquid crystal cured film; and easy adjustment and improvement of the adhesion between the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film. The polymerizable group may be in a polymerized state or an unpolymerized state, preferably an unpolymerized state.

As the alkanediyl group represented by ^V1z and ^V2z , methylene, ethylidene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,10-diyl, tetradecane-1,14-diyl and eicosane- 1,20-Dibase etc. V ^1z and V ^2z are preferably an alkanediyl group having 2 to 12 carbons, more preferably an alkanediyl group having 6 to 12 carbons.

A cyano group, a halogen atom, etc. are mentioned as a substituent which this alkanediyl group arbitrarily has, and this alkanediyl group is preferably an unsubstituted, more preferably an unsubstituted linear alkanediyl group.

W ^1z and W ^2z are independent of each other, and are preferably a single bond, -O-, -S-, -COO- or OCOO-, more preferably a single bond or -O-.

The polymerizable liquid crystal compound (Z) is preferably a molecular structure having an asymmetric molecular structure, specifically, a polymerizable liquid crystal compound having the following partial structures (A-a) to (A-i). It is more preferable to have a partial structure of (A-a), (A-b) or (A-c) from the viewpoint of easily expressing higher-order smectic liquid crystallinity. In addition, in following (A-a)-(A-i), * represents a bond (single bond).

[chemical 17]

As a polymeric liquid crystal compound (Z), specifically, the compound represented by a formula (A-1) - a formula (A-25) is mentioned, for example. When the polymerizable liquid crystal compound (Z) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans form.

[chemical 18]

[chemical 19]

[chemical 20]

[chem 21]

[chem 22]

Among these, at least one selected from the group consisting of compounds represented by formula (A-2), formula (A-3), formula (A-4), formula (A-5), formula (A-6), formula (A-7), formula (A-8), formula (A-13), formula (A-14), formula (A-15), formula (A-16) and formula (A-17) is 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) can be produced, for example, by a known method described in Lub et al., Recl. Trav. Chim. 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 300-400 nm, and the polymerizable liquid crystal compound forming the vertically aligned liquid crystal cured film is preferably a polymerizable liquid crystal compound having a maximum absorption wavelength between 300-400 nm. When the photopolymerization initiator is contained in the polymerizable liquid crystal composition, the polymerization reaction and gelation of the polymerizable liquid crystal compound may progress during long-term storage. However, if the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm, even if it is exposed to ultraviolet light during storage, it can effectively inhibit the generation of reactive species from the photopolymerization initiator and the progress of polymerization and gelation of the polymerizable liquid crystal compound caused by the reactive species. Therefore, it becomes advantageous at the point of the long-term stability of a polymeric liquid crystal composition, and the orientation of the obtained liquid crystal cured film and the uniformity of film thickness can be improved. Furthermore, 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 capable of dissolving a polymerizable liquid crystal compound, and examples thereof include chloroform and the like.

In a laminate formed by laminating a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film using an adhesive layer, energy ray-curable adhesives are considered to be more advantageous than pressure-sensitive adhesives in terms of thinning the laminated body or improving flexibility. However, when the vertically aligned liquid crystal cured film is formed of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a maximum absorption wavelength between 300 and 400 nm, when forming a laminate including the vertically aligned liquid crystal cured film, since the vertically aligned liquid crystal cured film exhibits absorption in the above-mentioned wavelength region, it is difficult to use a UV-curable adhesive that is cured by light (ultraviolet light) in the above-mentioned wavelength region. layers. The present invention is advantageous in thinning the layered body because the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film can be formed continuously without an adhesive layer. Not only that, it is also advantageous in that a thin layered layer with high optical characteristics can be obtained because a so-called polymeric liquid crystal compound exhibiting a large absorption in the wavelength region of 300 to 400 nm, which has a large absorption in the wavelength region of 300 to 400 nm, can be used for the composition of the layered body.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition forming a vertically aligned liquid crystal cured film is, for example, 70-99.5 parts by mass, preferably 80-99 parts by mass, more preferably 85-98 parts by mass, and still more preferably 90-95 parts by mass, relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. It is favorable from the viewpoint of the orientation of the obtained liquid crystal cured film that content of a polymeric liquid crystal compound exists in the said range. In addition, in this invention, the solid content of a polymeric liquid crystal composition means all components after removing the volatile components, such as an organic solvent, from a polymeric liquid crystal composition.

The polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film may further contain additives such as solvents, polymerization initiators, leveling agents, antioxidants, and photosensitizers, in addition to vertical alignment promoters and polymerizable liquid crystal compounds. These components may use only 1 type, respectively, and may use it in combination of 2 or more types.

Since the polymerizable liquid crystal composition for vertical alignment liquid crystal cured film formation is applied to a base material etc. normally in the state dissolved in the solvent, it is preferable to contain a solvent. The solvent is preferably a solvent that can dissolve the polymerizable liquid crystal compound, and is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound. Examples of solvents include alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; 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, and 2-heptanone Ketone solvents such as ketone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; Isoamide-based solvents, etc. 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-based solvents, and aromatic hydrocarbon solvents are preferable.

The content of the solvent in the polymerizable liquid crystal composition is preferably from 50 to 98 parts by mass, more preferably from 70 to 95 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal composition. Therefore, it is preferable that the solid content in 100 mass parts of polymerizable liquid crystal compositions is 2-50 mass parts. When the solid content is 50 parts by mass or less, the viscosity of the polymerizable liquid crystal composition becomes low, so the thickness of the film tends to become substantially uniform and unevenness is less likely to occur. The above-mentioned 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 that can generate a reactive species with the help of heat or light, and start the polymerization reaction of a polymerizable liquid crystal compound or the like. Examples of the reactive species include active species such as radicals and cations or anions. Among them, a photopolymerization initiator that generates radicals by light irradiation is preferable from the viewpoint of easy reaction control.

Examples of photopolymerization initiators include benzoin compounds, benzophenone compounds, benzoyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, oxime compounds, trioxane compounds, iodonium salts, and phosphonium 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 (above manufactured by BASF Japan Co., Ltd.), SEIKUOL BZ, SEIKUOL Z, SEIKUOL BEE (manufactured by Seiko Chemical Co., Ltd. above), Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Corporation), Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer Optomer N-1919, Adeka Arkls NCI-831, Adeka Arkls NCI-930 (manufactured by ADEKA Co., Ltd. above), TAZ-A, TAZ-PP (manufactured by Nihon Siber Hegner Co., Ltd. above), and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).

The photopolymerization initiator can fully utilize the energy emitted from the light source and is excellent in productivity. The maximum absorption wavelength is preferably 300 nm to 400 nm, and more preferably 300 nm to 380 nm. Among them, α-acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferred.

Examples of the α-acetophenone compound include 2-methyl-2-metholinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4-metholinylphenyl)-2-benzylbutane-1-one, and 2-dimethylamino-1-(4-metholinylphenyl)-2-(4-methylphenylmethyl)butane-1-one, and more preferably 2-methyl-2 - 𠰌linyl-1-(4-methylthiophenyl)propan-1-one and 2-dimethylamino-1-(4-𠰌linylphenyl)-2-benzylbutan-1-one. Examples of commercially available α-acetophenone compounds include Irgacure 369, 379EG, and 907 (the above, manufactured by BASF Japan Co., Ltd.), SEIKUOL BEE (manufactured by Seiko Chemical Co., Ltd.), and the like.

The oxime-based photopolymerization initiator can generate radicals such as phenyl radicals and methyl radicals by irradiating light. Polymerization of the polymerizable liquid crystal compound proceeds favorably by the radicals, and among them, an oxime-based photopolymerization initiator that generates methyl radicals is preferable in that the initiation efficiency of the polymerization reaction is high. Moreover, it is preferable to use the photoinitiator which can utilize the ultraviolet-ray of wavelength 350 nm or more effectively from a viewpoint of advancing a polymerization reaction more efficiently. As a photopolymerization initiator capable of effectively utilizing ultraviolet light with a wavelength of 350 nm or more, a trioxane 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-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethanone-1-(O-acetyl oxime), and the like. Examples of commercially available oxime ester-based photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, and Irgacure OXE-03 (the above, manufactured by BASF Japan Co., Ltd.), Adeka Optomer N-1919, and Adeka Arkls NCI-831 (the above, manufactured by ADEKA Co., Ltd.).

Content of a photoinitiator is 0.1-30 mass parts normally with respect to 100 mass parts of polymerizable liquid crystal compounds, Preferably it is 1-20 mass parts, More preferably, it is 1-15 mass parts. When it is in the said range, the reaction of a polymeric group will fully progress, and it will become difficult to disturb the alignment of a polymeric liquid crystal compound.

The so-called leveling agent is an additive that has the function of adjusting the fluidity of the polymerizable liquid crystal composition to make the coating film obtained by the coating composition more flat. Examples include silicone-based, polyacrylate-based and perfluoroalkyl-based leveling agents. Commercially available products can also be used as the leveling agent. Specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of the above are manufactured by Toray Dow Corning Co., Ltd.); KP321, KP323, KP324, KP326, KP340, KP 341, X22-161A, KF6001 (all of the above are manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (all of the above are manufactured by Momentive Performance Materials Japan Co., Ltd.); Fluorin ert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (the above, all manufactured by Sumitomo 3M Co., Ltd.); MEGAFAC (registered trademark) R-08, MEGAFAC R-30, MEGAFAC R-90, MEGAFAC F-410, MEGAFAC F-411, MEGAFAC F-443, MEGAF AC F-445, MEGAFAC F-470, MEGAFAC F-477, MEGAFAC F-479, MEGAFAC F-482, MEGAFAC F-483, MEGAFAC F-556 (the above are all manufactured by DIC); Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (the above are all Mi manufactured by subishi Materials Electronic Chemicals Co., Ltd.); Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40, SA-100 (all of the above are manufactured by AGC SEIMI CHEMICAL Co., Ltd.); trade names E1830, trade name E5844 (manufactured by Daikin Institute of Fine Chemicals Co., Ltd.); BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (all trade names: manufactured by BM Chemie), etc. A leveling agent may be used individually or in combination of 2 or more types.

The content of the leveling agent is preferably from 0.01 to 5 parts by mass, more preferably from 0.05 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, the polymerizable liquid crystal compound tends to be easily aligned, and the obtained liquid crystal cured film tends to be smoother, which is preferable.

By formulating antioxidants, the polymerization reaction of polymerizable liquid crystal compounds can be controlled. The antioxidant may be a primary antioxidant selected from phenol-based antioxidants, amine-based antioxidants, quinone-based antioxidants, and nitroso-based antioxidants, or a secondary antioxidant selected from phosphorus-based antioxidants and sulfur-based antioxidants. In order not to cause the polymerizable liquid crystal compound to be polymerized without disturbing the alignment of the polymerizable liquid crystal compound, the content of the antioxidant is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. Antioxidants can be used individually or in combination of 2 or more types.

Moreover, by using a photosensitizer, a photoinitiator can be made highly sensitive. Examples of photosensitizers include: ketone, 9-oxosulfur Such as ketones; anthracenes with substituents such as anthracene and alkyl ethers; 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 0.1-3 mass parts.

The polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film can be obtained by stirring a vertical alignment promoter, a polymerizable liquid crystal compound, a solvent or a photopolymerization initiator, and other components other than the vertical alignment promoter and the polymerizable liquid crystal compound at a specific temperature.

In the present invention, the vertical alignment liquid crystal cured film preferably satisfies the following formula (2). RthC(450)/RthC(550)≦1 (2) [In the 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 retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm]. By satisfying the above-mentioned formula (2), the decrease in ellipticity can be suppressed on the short-wavelength side in the laminate including the vertically aligned liquid crystal cured film, and the oblique reflection hue at the time of black display when the vertically aligned liquid crystal cured film is applied to a display device can be improved. The value of RthC(450)/RthC(550) in the vertical alignment liquid crystal cured film is more preferably 0.95 or less, more preferably 0.92 or less, especially preferably 0.9 or less, and is preferably 0.7 or more, more preferably 0.75 or more, and still more preferably 0.8 or more.

The retardation value RthC(λ) of the vertically aligned liquid crystal cured film in the film thickness direction can be adjusted by the thickness dC of the vertically aligned liquid crystal cured film. The in-plane phase difference value is given by the following formula: RthC(λ)=((nxC(λ)+nyC(λ))/2－nzC(λ))×dC (In the formula, nxC(λ) represents the in-plane principal refractive index of the vertically aligned liquid crystal cured film at a wavelength of λnm, nyC(λ) represents the refractive index in the direction perpendicular to nxC(λ) in the plane at a wavelength of λnm, and 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) can be set as the refractive index in any direction in the film , dC represents the film thickness of vertically aligned liquid crystal cured film) Therefore, in order to obtain the desired retardation value RthC(λ) in the film thickness direction, it is only necessary to adjust the three-dimensional refractive index and the film thickness dC. Furthermore, the three-dimensional refractive index depends on the molecular structure and alignment state of the polymerizable liquid crystal compound.

Also, in the present invention, the vertically aligned cured liquid crystal film is preferably aligned with a high degree of order in the vertical direction of the cured liquid crystal film. In the vertically aligned liquid crystal cured film, by aligning the polymerizable liquid crystal compound with a high degree of order, when a laminate including the vertically aligned liquid crystal cured film is incorporated into an organic EL display device, there is a tendency that the effect of suppressing the hue change of oblique reflection during black display is excellent. As an index indicating the higher alignment state of the polymerizable liquid crystal compound in the vertically aligned liquid crystal cured film and indicating the degree of oblique optical compensation effect during black display, the vertically aligned liquid crystal cured film preferably satisfies the following formula (5). -120nm≦RthC(550)≦-30nm (5) In formula (5), RthC(550) has the same meaning as above. From the viewpoint of further improving the oblique reflection hue during 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 -80 nm or more, and more preferably -40 nm or less, and more preferably -50 nm or less.

[Horizontal Alignment Liquid Crystal Curing Film] The horizontal alignment liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymerizable liquid crystal composition formed by curing a polymerizable liquid crystal compound in a state aligned horizontally with respect to the plane of the liquid crystal cured film, preferably a liquid crystal cured film formed by curing a polymerizable liquid crystal compound having at least one radical polymerizable group in a state 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 for forming a horizontally aligned liquid crystal cured film means a liquid crystal compound having a polymerizable group, preferably a liquid crystal compound having at least one radically polymerizable group. When the horizontal alignment cured liquid crystal film is laminated on the vertical alignment cured liquid crystal film via the horizontal photo-alignment film formed from a polymer having (meth)acryl group, if both the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film are cured products of a polymerizable liquid crystal compound having at least one radical polymerizable group, the adhesion between the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film continuously formed through the horizontal alignment film can be easily improved. In particular, since the adhesion between the horizontal alignment cured liquid crystal film and the vertical alignment liquid crystal cured film tends to be more improved, it is preferable that the polymerizable liquid crystal compound constituting the horizontal alignment liquid crystal cured film and the polymerizable liquid crystal compound constituting the vertical alignment liquid crystal cured film have polymerizable groups similar to or identical to those of the polymer forming the horizontal alignment film.

The polymerizable liquid crystal compound constituting the horizontally aligned liquid crystal cured film is not particularly limited, and for example, previously known polymerizable liquid crystal compounds in the field of retardation films can be used. Specifically, a compound represented by formula (X), (Y) or (Z) can be used as an example of a polymerizable liquid crystal compound that can be used in the formation of a vertically aligned liquid crystal cured film. Among them, a polymerizable liquid crystal compound that exhibits so-called reverse wavelength dispersion is preferable, for example, a compound represented by the above-mentioned formula (X) can be suitably used. In the polymeric liquid crystal composition for vertical alignment liquid crystal cured film formation, a polymeric liquid crystal compound can be used individually or in combination of 2 or more types.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 parts by mass, and still more preferably 90 to 95 parts by mass, relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. It is favorable from the viewpoint of the orientation of the obtained liquid crystal cured film that content of a polymeric liquid crystal compound exists in the said range.

The polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film may further contain additives such as solvents, polymerization initiators, leveling agents, antioxidants, and photosensitizers in addition to polymerizable liquid crystal compounds. As these components, the same thing as what was exemplified previously as the component which can be used for a vertical alignment liquid crystal cured film is mentioned, Each may use only 1 type, and may use it in combination of 2 or more types.

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

Also, in the present invention, for the same reason that it is advantageous that the vertically aligned liquid crystal cured film has at least one maximum absorption between wavelengths of 300 to 400 nm, it is preferable that the horizontally aligned liquid crystal cured film has at least one maximum absorption between wavelengths of 300 to 400 nm. In a preferred aspect 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 at a wavelength of 300-400 nm.

In the present invention, the horizontal alignment 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 a wavelength of λnm, ReA(λ)=(nxA(λ)-nyA(λ))×dA (wherein, nxA(λ) represents the main refractive index at the wavelength λnm in the plane of the horizontally aligned liquid crystal cured film, nyA(λ) represents the refractive index at the wavelength λnm in the direction perpendicular to the direction of nxA in the same plane as nxA, and dA represents the level Alignment liquid crystal cured film thickness)]

When the horizontally aligned liquid crystal cured film satisfies the formula (1), the horizontally aligned liquid crystal cured film exhibits so-called inverse wavelength dispersion in which the in-plane retardation value at short wavelengths becomes smaller than that at long wavelengths. By combining such a horizontally aligned liquid crystal cured film with the above-mentioned vertically aligned liquid crystal cured film, a laminate excellent in the effect of improving the front and oblique reflection hues during black display when incorporated into an organic EL display device can be obtained. In order to improve the reverse wavelength dispersibility, and further increase the effect of improving the reflection hue in the front direction of the horizontally aligned liquid crystal cured film, ReA(450)/ReA(550) is preferably at least 0.70, more preferably at least 0.78, and is preferably at most 0.95, more preferably at most 0.92.

The above-mentioned in-plane retardation value can be adjusted by the thickness dA of the horizontal alignment liquid crystal cured film. The in-plane retardation value is determined by the above formula ReA(λ)=(nxA(λ)-nyA(λ))×dA, so in order to obtain the required in-plane retardation value (ReA(λ): the in-plane retardation value of the horizontally aligned liquid crystal cured film at the wavelength λ(nm)), it is only necessary to adjust the three-dimensional refractive index and film thickness dA.

Moreover, it is preferable that a horizontal alignment liquid crystal cured film satisfies the following formula (6). 120 nm≦ReA(550)≦170 nm (6) [In the formula (6), ReA(λ) has the same meaning as above] If the in-plane retardation ReA(550) of the horizontally aligned liquid crystal cured film is within the range of formula (6), the effect of improving the front reflection hue during black display becomes remarkable when the laminate (ellipsoidal polarizer) including the horizontally aligned liquid crystal cured film is applied to an organic EL display device. A further preferable range of in-plane phase difference 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 of a polymer having a (meth)acryl group. The horizontal alignment film is one that has a horizontal alignment restriction force that aligns the polymerizable liquid crystal compound in a horizontal direction with respect to the plane of the coating film. The alignment restriction force can be arbitrarily adjusted by the type of alignment film, surface state, rubbing conditions, etc. If it is a photo-alignment film formed of a photo-alignment polymer, it can be arbitrarily adjusted by polarized light irradiation conditions, etc. In the present invention, a vertically aligned liquid crystal cured film is formed on a substrate, a horizontally aligned liquid crystal film is formed thereon, and a horizontally aligned liquid crystal cured film is formed thereon, but in this case, the orientation of the horizontally aligned liquid crystal cured film tends to deteriorate. The reason has not been determined, but it is speculated that the surface energy decreases due to additives such as leveling agents contained in the vertically aligned liquid crystal cured film, and the alignment of the liquid crystal compound is easily damaged when the horizontally aligned liquid crystal cured film is formed on the upper layer. Especially in the case of forming a vertically aligned liquid crystal cured film without a vertically aligned film, since an alignment promoter is further included, its influence becomes more remarkable. Therefore, the liquid crystal alignment at the time of forming the vertically aligned liquid crystal cured film is easily affected by the type and thickness of the horizontally aligned film.

When the horizontal alignment film has a polymeric group similar to or identical to the polymerizable liquid crystal compound constituting the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film, the adhesion between the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film tends to be improved through the horizontal alignment film. Therefore, it is preferable that the horizontal alignment film is formed of a polymer having a (meth)acryl group. Formed from a liquid crystal composition.

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

The photoreactive group refers to a group that produces alignment ability by light irradiation. Specifically, groups that participate in photoreactions that are the origin of liquid crystal alignment ability, such as induction of molecular alignment by light irradiation, isomerization reaction, dimerization reaction, photocrosslinking reaction, or photodecomposition reaction, can be mentioned. Among them, a group that participates in a dimerization reaction or a photocrosslinking reaction is preferable in terms of being excellent in alignment. As the photoreactive group, it is preferably a group having an unsaturated bond, especially a double bond, and is especially preferably a group having at least one selected from the group consisting of a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N bond), and a carbon-oxygen double bond (C=O bond).

Examples of the photoreactive group having a C=C bond include a vinyl group, a polyalkenyl group, a stilbene group, a stilazolyl group, a stilazolium group, a chalcone group, and a cinnamoyl group. As a photoreactive group which has a C=N bond, the group which has structures, such as an aromatic Schiff base and an aromatic hydrazone, is mentioned, for example. As the photoreactive group having an N=N bond, for example, an azophenyl group, an azonaphthyl group, an aromatic heterocyclic azo group, a disazo group, a formazan group, and a group having an oxyazobenzene structure are exemplified. Examples of photoreactive groups having a C=O bond include benzophenone groups, coumarin groups, anthraquinone groups, and maleimide groups. These groups may have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and halogenated alkyl.

Among them, photoreactive groups that participate in photodimerization reactions are preferred, and azo groups, cinnamonyl groups, and chalcone groups are preferred in terms of the relatively small amount of polarized light irradiation required for photoalignment and the ease of obtaining a photoalignment film with excellent thermal stability or stability over time. As a polymer having a photoreactive group, a polymer having an azo group or a cinnamic acid group is preferable, and a polymer having a cinnamic acid group in which the end of the side chain of the polymer becomes a cinnamic acid structure is particularly preferable from the viewpoint of improving the adhesion between the horizontal alignment film, the vertical alignment liquid crystal cured film, and the horizontal alignment liquid crystal cured film.

Examples of solvents that can be contained in the composition for forming a photoalignment film include the same solvents as those exemplified above as solvents that can be used in the polymerizable liquid crystal composition, and can be appropriately selected depending on the solubility of the polymer or monomer having a photoreactive group.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment film can be appropriately adjusted according to the type of polymer or monomer or the thickness of the target photoalignment film. It is preferably at least 0.2% by mass, more preferably in the range of 0.3 to 10% by mass, relative to the mass of the composition for forming a photoalignment film. The composition for forming a photoalignment film may also contain a polymer material such as polyvinyl alcohol or polyimide, or a photosensitizer within a range that does not significantly impair the properties of the photoalignment film.

The thickness of the horizontal alignment film (photo-alignment film) is usually 10-5000 nm, preferably 100-1000 nm, more preferably 100-500 nm, further preferably 100-300 nm, especially 100-250 nm. When the thickness of the alignment film is within the above-mentioned range, the horizontal alignment restraint force is sufficiently provided, and the alignment film in the laminate is less prone to coagulation failure.

[substrate] As a base material which comprises the laminated body of this invention, a glass base material, a film base material, etc. are mentioned, for example, A resin film base material is preferable from a processability viewpoint. As the resin constituting the film substrate, for example, polyolefins such as polyethylene, polypropylene, and northylene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate; polyacrylate; cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; Plastics such as ether. Such a resin can be formed into a film by a known method such as a solvent casting method and a melt extrusion method, and can be used as a base material. Surface treatments such as polysiloxane treatment, corona treatment, and plasma treatment can also be performed on the surface of the substrate.

A commercially available product can also be used as a base material. Examples of commercially available cellulose ester substrates include cellulose ester substrates manufactured by Fuji Film Co., Ltd. such as FUJITAC FILM; cellulose ester substrates manufactured by Konica Minolta Co., Ltd. such as “KC8UX2M”, “KC8UY” and “KC4UY”. Examples of commercially available cyclic olefin-based resins include: Cyclic olefin-based resins manufactured by Ticona (Germany) such as "Topas (registered trademark)"; Cyclic olefin-based resins manufactured by JSR Co., Ltd. such as "ARTON (registered trademark)"; Cyclic olefin-based resins manufactured by Japan Zeon Co., Ltd. such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)"; Cyclic olefin resin. Commercially available cyclic olefin-based resin substrates can also be used. Examples of commercially available cyclic olefin resin substrates include Sekisui Chemical Co., Ltd. cyclic olefin resin substrates such as "S-SINA (registered trademark)" and "SCA40 (registered trademark)", cyclic olefin resin substrates manufactured by Optronics Co., Ltd. such as "ZEONOR FILM (registered trademark)", and cyclic olefin resin substrates manufactured by JSR Co., Ltd. such as "ARTON FILM (registered trademark)".

In the present invention, the substrate is preferably one that can finally be peeled off from the laminate of the present invention. For example, an elliptically polarizing plate can be obtained by laminating the vertically aligned liquid crystal cured film of the laminate after peeling off the substrate to a polarizing film via an adhesive layer.

The thickness of the substrate is usually 5 to 300 μm, preferably 10 to 150 μm, from the viewpoints of thinning the laminate, ease of peeling of the substrate, and rationality of the substrate.

The laminate of the present invention may also include layers other than the base material, vertical alignment liquid crystal cured film, horizontal alignment film, and horizontal alignment liquid crystal cured film within the range that does not affect the effect of the present invention. Examples of such another layer include a cured resin layer, a hard coat layer, and a primer layer for the purpose of improving the solvent resistance of the substrate, improving the mechanical strength of the liquid crystal cured film, or reinforcing. For example, the base material and vertically aligned liquid crystal cured film can be laminated through a layer that does not have vertical alignment restrictive force, and the vertically aligned liquid crystal cured film and horizontal alignment film can also be laminated through a layer that does not have vertical alignment restrictive force (except the adhesive layer).

The cured resin layer can be formed of, for example, acrylic resin, methacrylic resin, epoxy resin, oxetane resin, urethane resin, melamine resin, or the like. By providing the cured resin layer, the solvent resistance of the substrate can be 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 can also be used as a protective layer or a reinforcing layer to fully compensate for the strength of the vertically aligned liquid crystal cured film.

When the laminate of the present invention includes other layers such as the above-mentioned cured resin layer, the thickness of the other layer may be appropriately determined according to the purpose or type of the layer provided, and is preferably 0.1 to 10.0 μm, more preferably 0.3 to 5.0 μm.

[Manufacturing method of laminated body] The laminate of the present invention can be produced, for example, by the following production method, which sequentially includes: Forming a coating film of a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film containing a polymerizable liquid crystal compound, and forming a vertical alignment liquid crystal cured film from the coating film (hereinafter also referred to as "vertical alignment liquid crystal cured film forming step"), A step of forming a coating film of the composition for forming a horizontal alignment film and forming a horizontal alignment film from the coating film (hereinafter also referred to as "horizontal alignment film forming step"), and 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 also referred to as "horizontally aligned liquid crystal cured film forming step"). In the case where the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film are adjacent to each other in the laminate of the present invention, it is preferable to perform the vertical alignment liquid crystal cured film forming step, the horizontal alignment film forming step, and the vertical alignment liquid crystal cured film forming step sequentially.

In the step of forming the vertically aligned liquid crystal cured film, the vertically aligned liquid crystal cured film can be manufactured by, for example, the following method, which includes: A step of coating a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film on a substrate to obtain a coating film; a step of drying the above-mentioned coating film to form a dry coating film; and A step of forming a vertically aligned liquid crystal cured film by irradiating active energy rays to the dried coating film.

Formation of the coating film of the polymerizable liquid crystal composition can be carried out by, for example, coating the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film on the substrate or on other layers such as a cured resin layer that has no vertical alignment restricting force provided on the substrate.

Examples of methods for applying the polymerizable liquid crystal composition to substrates include known methods such as spin coating methods, extrusion methods, gravure coating methods, die coating methods, bar coating methods, coating methods such as applicator methods, and printing methods such as flexographic methods.

Next, the solvent is removed by drying or the like to form a dry coating film. As a drying method, a natural drying method, a ventilating drying method, a heat drying method, and a reduced-pressure drying method etc. are mentioned. At this time, by heating the coating film obtained from the polymerizable liquid crystal composition, the solvent can be dried and removed from the coating film, and the polymerizable liquid crystal compound can be aligned in a direction perpendicular to the plane of the coating film. The heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound used and the material of the substrate forming the coating film, etc. In order to phase transition the polymerizable liquid crystal compound to the liquid crystal phase state, it is usually necessary to be at a temperature above the liquid crystal phase transition temperature. In order to remove the solvent contained in the polymerizable liquid crystal composition and bring the polymerizable liquid crystal compound into a homeotropic alignment state, for example, it may be heated to a temperature equal to or higher than the liquid crystal phase transition temperature (smectic phase transition temperature or nematic phase transition temperature) of the polymerizable liquid crystal compound contained in the above polymerizable liquid crystal composition. Furthermore, 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. Also, when two or more polymerizable liquid crystal compounds are used in combination, the above-mentioned phase transition temperature means the temperature measured using a mixture of polymerizable liquid crystal compounds obtained by mixing all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition in the same ratio as the composition of the polymerizable liquid crystal composition in the same manner as the case of using one kind of polymerizable liquid crystal compound. Furthermore, it is generally known that the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the above polymerizable liquid crystal composition is sometimes lower than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound alone.

The heating time can be appropriately determined depending on the heating temperature, the type of polymerizable liquid crystal compound used, the type of solvent or its boiling point and its amount, 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 the polymerizable liquid crystal compound to a liquid crystal phase transition temperature or higher, or may be performed separately, but it is preferably performed simultaneously from the viewpoint of productivity improvement. Before heating the polymerizable liquid crystal compound to the liquid crystal phase transition temperature or higher, a pre-drying step may be provided for appropriately removing the solvent in the coating film under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition is not polymerized. As the drying method in the pre-drying step, natural drying method, ventilating drying method, heating drying and reduced-pressure drying method, etc. can be mentioned. The drying temperature (heating temperature) in the drying step can be appropriately determined depending on the type of polymerizable liquid crystal compound used, the type of solvent or its boiling point and its amount.

Next, in the obtained dry coating film, the polymerizable liquid crystal compound is polymerized while maintaining the homeotropic alignment state of the polymerizable liquid crystal compound, thereby forming a homeotropically aligned liquid crystal cured film. As a polymerization method, a thermal polymerization method or a photopolymerization method is mentioned, and a photopolymerization method is preferable from a viewpoint of easy control of a polymerization reaction. In photopolymerization, the light irradiated to the dry coating film is appropriately selected depending on the type of polymerization initiator contained in the dry coating film, the type of polymerizable liquid crystal compound (especially the type of polymerizable group contained in the polymerizable liquid crystal compound) and its amount. Specific examples thereof include one or more kinds of light or active electron beams selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays. Among them, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction, or it can be used by a wide range of users in this field as a photopolymerization device, and it is preferable to select in advance the type of polymerizable liquid crystal compound or polymerization initiator contained in the polymerizable liquid crystal composition so that photopolymerization can be carried out by ultraviolet light. In addition, during polymerization, the coating film can be cooled and dried by an appropriate cooling method and then irradiated with light, thereby controlling the polymerization temperature. By adopting such a cooling method, if the polymerization of the polymerizable liquid crystal compound is performed at a lower temperature, even if a base material with relatively low heat resistance is used, a cured film of a vertically aligned liquid crystal can be appropriately formed. Also, the polymerization reaction can be accelerated by increasing the polymerization temperature within a range in which abnormalities caused by heat during light irradiation (heat-induced deformation of the substrate, etc.) do not occur. During photopolymerization, a patterned cured film can also be obtained by performing masking or development.

Examples of light sources for the active energy rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten filament lamps, gallium lamps, excimer lasers, LED light sources emitting light in the wavelength range of 380-440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, and metal halide lamps.

The ultraviolet irradiation intensity is usually 10 to 3,000 mW/cm ² . The intensity of ultraviolet irradiation is preferably an intensity in a wavelength region effective for activation of 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 still more preferably 0.1 second to 1 minute. If the ultraviolet irradiation intensity is irradiated once or multiple times, the cumulative light intensity is 10-3,000 mJ/cm ² , preferably 50-2,000 mJ/cm ² , more preferably 100-1,000 mJ/cm ² .

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

In the step of forming the horizontal alignment film, the photo alignment film can be obtained by, for example, coating the photo alignment film forming composition on the vertical alignment liquid crystal cured film, removing the solvent, and then irradiating polarized light (preferably polarized UV).

As a method of coating the composition for forming a photoalignment film on the cured film of vertical alignment liquid crystal, the same method as the method of coating the polymerizable liquid crystal composition for forming a cured film of vertical alignment liquid crystal on the base material and the like may be mentioned. As a method of removing a solvent from the applied composition for forming a photoalignment film, a natural drying method, an air drying method, a heat drying method, a reduced pressure drying method, etc. are mentioned, for example.

When irradiating polarized light, it may be a form of directly irradiating polarized light UV to a coating film obtained by removing the solvent from the composition for forming a photoalignment film, or may be a form of irradiating polarized light from the vertically aligned liquid crystal cured film side (substrate side) to transmit the polarized light. In addition, the polarized light is preferably substantially parallel light. Regarding the wavelength of the irradiated polarized light, it may be a polymer having a photoreactive group or a wavelength region where the photoreactive group of a monomer can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength of 250 to 400 nm is particularly preferable. The light source used for the polarized light irradiation includes xenon lamp, high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, ultraviolet laser such as KrF, ArF, etc., more preferably high-pressure mercury lamp, ultra-high pressure mercury lamp and metal halide lamp. Among them, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferable because the luminous intensity of ultraviolet rays with a wavelength of 313 nm is relatively large. Polarized light UV can be irradiated by passing light from the above-mentioned light source through an appropriate polarizing element and irradiating it. As the polarizing element, a polarizer, a polarizer such as Glenn-Thompson, Glenn-Taylor, or a wire-grid type polarizing element can be used. In addition, when irradiating polarized light, if shielding is performed, a plurality of regions (patterns) in which liquid crystal alignment directions are different can also be formed.

In the step of forming the horizontally aligned liquid crystal cured film, the horizontally aligned liquid crystal cured film can be produced, for example, by the following method, which includes: A step of applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on a horizontally aligned film to obtain a coating film, A step of drying the above-mentioned coating film to form a dry coating film, and A step of forming a horizontally aligned liquid crystal cured film by irradiating active energy rays to the dried coating film.

Formation of the coating film of a polymeric liquid crystal composition can be performed by coating the polymeric liquid crystal composition for forming a cured film of a horizontal alignment liquid crystal on a horizontal alignment film, for example. As a coating method of a polymeric liquid crystal composition, the method similar to the method applicable to the manufacturing method of a vertical alignment liquid crystal cured film is mentioned.

Next, the solvent is removed by drying or the like to form a dry coating film. As a drying method, a natural drying method, a ventilating drying method, a heat drying method, and a reduced-pressure drying method etc. are mentioned. In terms of productivity, heat drying is preferred, and in this case, the heating temperature is preferably at least the phase transition temperature of the polymerizable liquid crystal compound at which the solvent can be removed. About the procedure and conditions in this process, the thing similar to the procedure or condition applicable to the manufacturing method of the vertical alignment liquid crystal cured film is mentioned.

The obtained dry coating film is irradiated with active energy rays (more specifically, ultraviolet rays, etc.) to polymerize the polymerizable liquid crystal compound while maintaining the state of aligning the polymerizable liquid crystal compound in the horizontal direction with respect to the plane of the coating film, thereby forming a horizontally aligned liquid crystal cured film. As a polymerization method, the method similar to the method applicable to the manufacturing method of the vertical alignment liquid crystal cured film is mentioned.

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

In the present invention, the vertical alignment liquid crystal cured film is formed of a polymerizable liquid crystal composition containing a vertical alignment promoter, thereby obtaining a vertical alignment liquid crystal cured film with no or few alignment defects even without using a vertical alignment film. The laminate of the present invention comprising such a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film in combination tends to have excellent optical properties, especially when applied to an organic EL display device, it is excellent in the effect of suppressing changes in frontal and oblique reflection hues during black display. In addition, since the step of forming a vertical alignment film is unnecessary, it is also advantageous in terms of production efficiency and production cost.

[Elliptical polarizer] 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 adsorbed with an anisotropic absorption pigment or a film coated with an anisotropic absorption pigment as a polarizing element. Examples of dyes having absorption anisotropy include dichroic dyes.

A film including a stretched film adsorbed with a dye having absorption anisotropy as a polarizing element is generally produced by uniaxially stretching the polyvinyl alcohol-based resin film, dyeing the polyvinyl alcohol-based resin film with a dichroic dye to absorb the dichroic dye, treating the polyvinyl alcohol-based resin film adsorbed with the dichroic dye with a boric acid aqueous solution, and washing the polyvinyl alcohol-based resin film with the dichroic dye after the treatment with a boric acid aqueous solution. Clamp.

Polyvinyl alcohol-based resins are obtained by saponifying polyvinyl acetate-based resins. As the polyvinyl acetate resin, for example, in addition to polyvinyl acetate which is a homopolymer of vinyl acetate, a copolymer of vinyl acetate and other monomers that can be copolymerized therewith can also be used. Examples of other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having ammonium groups.

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

Those made of such polyvinyl alcohol-based resins are used as base films for polarizing films. The method of forming a polyvinyl alcohol-based resin into a film is not particularly limited, and a known method can be used to form a film. The film thickness of a polyvinyl-alcohol-type base film can be made into about 10-150 micrometers, for example.

The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before dyeing with a dichroic dye, simultaneously with dyeing, or after dyeing. When performing uniaxial stretching after dyeing, the uniaxial stretching may be performed before or during boric acid treatment. In addition, uniaxial stretching can also be performed in these plural stages. In the case of uniaxial stretching, it may be uniaxially stretched between rolls having different circumferential speeds, or may be uniaxially stretched using a heated roll. In addition, the uniaxial stretching may be a dry stretching in which stretching is performed in the air, or a wet stretching in which a polyvinyl alcohol-based resin film is stretched in a state in which a polyvinyl alcohol-based resin film is swollen. The elongation ratio is usually about 3 to 8 times.

The dyeing of a polyvinyl-alcohol-type resin film with a dichroic dye is performed by the method of immersing a polyvinyl-alcohol-type resin film in the aqueous solution containing a dichroic dye, for example.

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

When iodine is used as a dichroic dye, the method of immersing and dyeing a polyvinyl alcohol-type resin film in the aqueous solution containing iodine and potassium iodide is employ|adopted normally. Content of the iodine in this aqueous solution is about 0.01-1 mass part normally with respect to 100 mass parts of water. Moreover, content of potassium iodide is about 0.5-20 mass parts normally with respect to 100 mass parts of water. The temperature of the aqueous solution used for dyeing is usually about 20-40°C. In addition, the immersion time (dyeing time) in the aqueous solution is usually about 20 to 1,800 seconds.

On the other hand, when using a dichroic organic dye as a dichroic dye, a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye for dyeing is generally employed. The content of the dichroic organic dye in the aqueous solution is usually about 1×10 ^-4 to 10 parts by mass, preferably 1×10 ^-3 to 1 part by mass, more preferably 1×10 ^-3 to 1×10 ^-2 parts by mass relative to 100 parts by mass of water. The aqueous solution may also contain inorganic salts such as sodium sulfate as dyeing aids. The temperature of the dichroic dye aqueous solution used for dyeing is about 20-80 degreeC normally. In addition, the immersion time (dyeing time) in the aqueous solution is usually about 10 to 1,800 seconds.

The boric acid treatment after dyeing with a dichroic dye can be generally performed by a method of immersing a dyed polyvinyl alcohol-based resin film in a boric acid aqueous solution. Content of the boric acid in this boric-acid aqueous solution is about 2-15 mass parts normally with respect to 100 mass parts of water, Preferably it is 5-12 mass parts. When using iodine as a dichroic dye, the boric acid aqueous solution preferably contains potassium iodide, and the content of potassium iodide in this case is usually about 0.1 to 15 parts by mass, preferably 5 to 12 parts by mass, relative to 100 parts by mass of water. The immersion time in the boric acid aqueous solution is about 60 to 1,200 seconds normally, Preferably it is 150 to 600 seconds, More preferably, it is 200 to 400 seconds. The temperature of the boric acid treatment is usually above 50°C, preferably 50-85°C, more preferably 60-80°C.

The polyvinyl alcohol-based 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-based resin film in water. The temperature of water in the washing process is usually about 5 to 40°C. Moreover, immersion time is about 1 to 120 seconds normally.

After washing with water, drying treatment was performed to obtain a polarizing element. The drying treatment can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying treatment is usually about 30-100°C, preferably 50-80°C. The drying time is usually about 60-600 seconds, preferably 120-600 seconds. By drying, the moisture content of the polarizer is reduced to a practical level. The water content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. If the moisture content is less than 5% by mass, the flexibility of the polarizing element may be lost, and the polarizing element may be damaged or broken after drying. Moreover, when the moisture content exceeds 20 mass %, there exists a possibility that the thermal stability of a polarizing element may deteriorate.

The thickness of the polarizing element obtained by uniaxially stretching the polyvinyl alcohol-based resin film in this way, dyeing with a dichroic dye, treating with boric acid, washing with water, and drying is preferably 5 to 40 μm.

Examples of the film coated with a dye having absorption anisotropy include a film obtained by coating a composition containing a liquid crystalline dichroic dye, or a composition containing a dichroic dye and a polymerizable liquid crystal. The film preferably has a protective film on one or both sides thereof. As this protective film, the thing similar to the resin film mentioned above 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 anisotropic absorption is preferably thin, and if it is too thin, the strength tends to decrease and the processability tends to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, more preferably 0.5-3 μm.

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

A transparent protective film may be laminated on at least one side of the thus obtained polarizing element, for example, via an adhesive layer. As the transparent protective film, the same transparent film as the resin film exemplified above as the base material usable for the production of the vertically aligned liquid crystal cured film can be used.

The elliptically polarizing plate of the present invention includes 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 elliptically polarizing plate of the present invention can be obtained by laminating the laminate of the present invention and the polarizing film through an adhesive layer or the like. Moreover, the elliptically polarizing plate of this invention can be obtained by bonding the laminate obtained by removing a base material from the laminate of this invention, and a polarizing film.

In one embodiment of the present invention, when the laminate of the present invention is laminated with a polarizing film, it is preferable to laminate in such a way that the angle formed by the retardation axis (optical axis) of the horizontal alignment liquid crystal cured film constituting the laminate and the absorption axis of the polarizing film becomes 45±5°.

The elliptically polarizing plate of the present invention may also have the configurations of conventional elliptically polarizing plates, polarizing films, and retardation films. Such a configuration includes, for example, an adhesive layer (sheet) for bonding an elliptical polarizing plate to a display element such as an organic EL, and a protective film used for protecting the surface of a polarizing film or a cured liquid crystal film from damage or contamination.

The laminate and elliptically polarizing plate of the present invention can be used in various display devices. The so-called display device refers to a device having a display element, including 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 (such as a field emission display device (FED), a surface field emission display device (SED)), an electronic paper (a display device using electronic ink or an electrophoretic element, a plasma display device, a projection display device (such as a grid light valve (GLV) display device, a display device with a digital micromirror device (DMD)), and a piezoelectric ceramic display. The device includes any one 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 type liquid crystal display device. These display devices can be display devices that display two-dimensional images, and can also be stereoscopic display devices that display three-dimensional images. Especially the elliptical polarizer of the present invention can be suitably used for organic electroluminescence (EL) display devices in terms of easily and significantly exerting its effect, and the laminate of the present invention can be suitably used for liquid crystal display devices and touch panel display devices. By using the laminate of the present invention Or an elliptically polarizing plate can easily realize thinning of the display device, and can obtain a display device with excellent optical characteristics and good image display characteristics. [Example]

Hereinafter, the present invention will be described more specifically with reference to examples. In addition, "%" and "part" in an example mean % by mass and parts by mass, respectively, unless otherwise specified.

1. Example 1 (1) Preparation of a composition for forming a horizontal alignment film A composition for forming a horizontal alignment film was obtained by mixing 5 parts by mass of a photo-alignment material (weight average molecular weight: 30,000) having the following structure and 95 parts by mass of cyclopentanone (solvent) as components, and stirring the obtained mixture at 80° C. for 1 hour. [chem 23]

(2) Preparation of polymerizable liquid crystal compounds A polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (X2) having the following molecular structures were prepared respectively. The polymerizable liquid crystal compound (X1) was produced according to the method described in JP-A-2010-31223. Moreover, the polymerizable liquid crystal compound (X2) was manufactured according to the method described in Unexamined-Japanese-Patent No. 2009-173893.

Polymeric Liquid Crystal Compound (X1) [Chem. 24]

Polymeric Liquid Crystal Compound (X2) [Chem. 25]

A solution was obtained by dissolving 1 mg of the polymerizable liquid crystal compound (X1) in 50 mL of tetrahydrofuran. The solution obtained as a measurement sample was put into a measurement cell with an optical path length of 1 cm, and the measurement sample was set in an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, "UV-2450") to measure the absorption spectrum, and the wavelength of maximum absorption was read from the obtained absorption spectrum. As a result, the maximum absorption wavelength λ _max in the wavelength range of 300 to 400 nm was 350 nm.

(3) Preparation of a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film To the polymerizable liquid crystal compound LC242 represented by the following formula (LC242): Paliocolor LC242 (registered trademark of BASF Corporation), 0.1 parts by mass of a leveling agent ("F-556" manufactured by DIC Corporation) and 3 parts by mass of a polymerization initiator Irg 369 were added. Furthermore, cyclopentanone was added so that solid content density|concentration might become 13 %, and these were mixed, and the polymerizable liquid crystal composition for horizontal alignment liquid crystal cured film formation was obtained.

LC242: PaliocolorLC242 (BASF Corporation, registered trademark) [Chem. 26]

(4) Preparation of a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film With respect to 100 parts by mass of liquid crystal compound (X2), 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC Corporation), 2.0 parts by mass of ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, 0.5 parts by mass of silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 2-dimethylamino- 6 parts by mass of 2-benzyl-1-(4-𠰌linylphenyl)butan-1-one (“Irgacure (registered trademark) 369 (Irg369)” manufactured by BASF Japan Co., Ltd.). Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration might become 13%. This mixture was stirred at 80 degreeC for 1 hour, and the polymerizable liquid crystal composition for vertical alignment liquid crystal cured film formation was obtained.

Ionic Compound A: [Chem. 27]

(5) Preparation of base material: 50 parts by mass of dipentaerythritol hexaacrylate (ARONIX M-403 multifunctional acrylate manufactured by Toa Gosei Co., Ltd.), 50 parts by mass of acrylate resin (Ebecryl 4858 manufactured by Daicel-UCB Co., Ltd.), 2-methyl-1[4-(methylthio)phenyl]-2-𠰌linylpropan-1-one (Irgacure 907; Ciba Specialty Chemical s company) 3 parts by mass were dissolved in 250 parts by mass of isopropyl alcohol to prepare a solution to obtain a composition for forming a cured resin layer containing an acrylate compound. Next, the composition for cured resin layer formation was apply|coated with the bar coater on the TAC film (KC4UY) by Konica Minolta Co., Ltd., and it dried at 50 degreeC for 1 minute. Thereafter, a cured resin layer was formed by irradiating ultraviolet rays (accumulated light intensity at a wavelength of 365 nm in a nitrogen atmosphere: 400 mJ/cm ² ) using a high-pressure mercury lamp ("UNICURE VB-15201BY-A", manufactured by Ushio Electric Co., Ltd.). The film thickness of the obtained cured resin layer was measured with a contact film thickness gauge, and it was 2.0 μm. At this time, using "KOBRA-WPR" manufactured by Oji Scientific Instruments Co., Ltd., the retardation value Re550 of the laminate of the TAC film and the cured resin layer was measured, and the retardation value Re550 derived from the TAC film was subtracted. As a result, it was confirmed that the retardation value was 3 nm or less and was optically isotropic.

(6) Production of vertical alignment liquid crystal cured film Using a bar coater, coat the polymerizable liquid crystal composition for vertical alignment liquid crystal cured film formation on the cured resin layer on the base material prepared as above, and heat at 120° C. for 60 seconds. Then, using a high-pressure mercury lamp (UNICURE VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.), heated to 120°C, irradiated ultraviolet radiation (under a nitrogen atmosphere, cumulative light intensity at a wavelength of 365 nm: 500 mJ/cm ² ) from the surface coated with a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film, thereby forming a vertically aligned liquid crystal cured film, and obtaining a substrate, a cured resin layer, and a vertically aligned liquid crystal cured film. The laminated body obtained by successive lamination. The film thickness of the obtained vertically aligned liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Corporation), and it was 0.6 μm.

<Measurement of Retardation Value of Vertically Aligned Liquid Crystal Cured Film> Corona treatment was performed on the vertical alignment liquid crystal cured film surface of the laminate including the base material, cured resin layer, and vertical aligned liquid crystal cured film produced by the above procedure, and the TAC film and cured resin layer were peeled off after the 25 μm pressure-sensitive adhesive manufactured by LINTEC was attached to the glass. Using KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd. for the obtained laminate including peeling, adhesive, and vertically aligned liquid crystal cured film, the incident angle of light to the sample for measuring optical characteristics was changed, and the front retardation value and the retardation value when it was inclined 40° from the center of the phase advance axis were measured. The average refractive index at each wavelength was measured using an ellipsometer M-220 manufactured by JASCO Corporation. In addition, the film thickness was measured using Optical NanoGauge film thickness meter C12562-01 manufactured by Hamamatsu Photonics Co., Ltd. According to the above front phase difference value, the phase difference value when it is inclined to the center of the phase axis at 40°, the average refractive index, and the value of film thickness, the three-dimensional refractive index is calculated with reference to the technical data of Oji Instruments (http://www.oji-keisoku.co.jp/products/kobra/reference.html). According to 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), and αth=Rth(450)/Rth(550) are calculated. The results are shown in Table 1. RthC(λ)=((nxC(λ)+nyC(λ))/2－nzC(λ))×dC Furthermore, RthC(λ) represents the retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of λnm. Also, nxC(λ) represents the in-plane principal refractive index of the vertically aligned liquid crystal cured film at a wavelength of λnm, nyC(λ) represents the refractive index in the direction perpendicular to nxC(λ) in the plane at a wavelength of λnm, and nzC(λ) represents the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of λnm. C represents the film thickness of the vertically aligned liquid crystal cured film.

(7) Production of horizontal alignment liquid crystal cured film Corona treatment was performed on the surface of the vertical alignment liquid crystal cured film of the laminate comprising the base material (TAC film), cured resin layer, and vertical alignment liquid crystal cured film produced by the above method, and the horizontal alignment film forming composition was coated using a bar coater, and dried at 80° C. for 1 minute. Next, using a polarized UV irradiation device (SPOT CURE SP-9; manufactured by Ushio Electric Co., Ltd.), polarized UV exposure was performed at a wavelength of 313 nm at an integrated light intensity of 100 mJ/cm ² to obtain a horizontal alignment film. The film thickness of the obtained horizontal alignment film was measured with an ellipsometer, and the result was 200 nm.繼而，於水平配向膜上塗佈水平配向液晶硬化膜形成用聚合性液晶組合物，於120℃下加熱60秒鐘後，使用高壓水銀燈(UNICURE VB-15201BY-A，牛尾電機股份有限公司製造)，自塗佈有水平配向液晶硬化膜形成用聚合性液晶組合物之面照射紫外線(氮氣氛圍下，波長365 nm下之累計光量：500 mJ/cm ² )，藉此形成水平配向液晶硬化膜，獲得將基材、硬化樹脂層、垂直配向液晶硬化膜、水平配向膜、水平配向液晶硬化膜依此順序鄰接地積層而成之積層體。 The film thickness of the obtained horizontally aligned liquid crystal cured film was measured with an ellipsometer, and it was 1.1 μm. In this laminate, the total film thickness T1 from the substrate-side surface of the vertical alignment cured liquid crystal film to the surface of the horizontal alignment cured liquid crystal film opposite to the horizontal alignment film was 1.9 μm. The laminated system obtained in Example 1 has a laminate composed of substrate (TAC film)/cured resin layer/vertical alignment liquid crystal cured film/horizontal alignment film/horizontal aligned liquid crystal cured film.

<Measurement of Retardation Value of Horizontally Aligned Liquid Crystal Cured Film> Corona treatment was performed on the surface of the horizontal alignment liquid crystal cured film of the above-mentioned laminate including the substrate, cured resin layer, vertical alignment liquid crystal cured film, horizontal alignment film, and horizontal aligned liquid crystal cured film, and the TAC film and cured resin layer were peeled off after the 25 μm pressure-sensitive adhesive manufactured by LINTEC was bonded to the glass. For the obtained laminate including peeling, adhesive, vertical alignment liquid crystal cured film, horizontal alignment film, and horizontal alignment liquid crystal cured film, use KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd. to measure, and subtract the Re (450) and Re (550) of the vertical alignment liquid crystal cured film measured in advance from the measured values of Re (450) and Re (550) to calculate the ReA (450) and ReA of the horizontal alignment liquid crystal cured film. (550), and further calculate αA=ReA(450)/ReA(550). The results are shown in Table 1.

(8) Evaluation of laminated body ＜Orientation evaluation of laminates＞ The obtained laminate was bonded to a glass of 5×5 cm×0.7 mm in thickness with a pressure-sensitive adhesive (25 μm) manufactured by LINTEC, and only the substrate was peeled off. The obtained sample was observed at a magnification of 200 times using a polarizing microscope (“BX-51” manufactured by Olympus Co., Ltd.), and the number of alignment defects in a field of view of 480 μm×320 μm was counted. Here, as the number of alignment defects, only the alignment defects caused by the sample for measurement were counted, and the number of defects caused by environmental foreign matter other than the sample was not counted, except for the number of defects. Based on the results of observation with a polarizing microscope, the alignment of the laminate was evaluated based on the following evaluation criteria. If it is 0, it is judged that the alignment property is excellent, and if it is △, it is judged that it is the degree of alignment which does not affect the 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. × (poor): The number of alignment defects is 21 or more, or there is no alignment at all.

＜Adhesive test of laminated body＞ With reference to the adhesion test (cross-cut method) of JIS K5600-5-6, the adhesion test of the laminate was carried out in the following manner. First, the horizontal alignment liquid crystal cured film side of the laminate was bonded to glass of 5 x 5 cm x thickness 0.7 mm through a pressure-sensitive adhesive (25 μm) manufactured by LINTEC, and only the substrate was peeled off from the laminate. Incisions of 1 mm□ for 100 pieces were made with a cutter on the laminated body side of the obtained sample. Sellotape (registered trademark) (manufactured by Michbon Corporation) was attached to the cuts of the obtained 100 pieces, and after the Sellotape was peeled off, the number of pieces peeled between the layers in the laminate was confirmed, and the adhesion was judged according to the following criteria. The results are shown in Table 1. Evaluation criteria: 〇: After the Sellotape was peeled off, the number of pieces peeled between the layers in the laminate was less than 30 pieces. △: After Sellotape peeling, the number of peeled pieces between the layers in the laminate is 30 to 59 pieces. ×: After the Sellotape was peeled off, the number of pieces peeled between the layers in the laminate was 60 or more.

2. Embodiment 2 The preparation of the polymerizable liquid crystal composition for forming the horizontally aligned liquid crystal cured film and the formation of the horizontally aligned liquid crystal cured film were changed as follows. In the same manner as in Example 1, a laminate in which the base material, the cured resin layer, the vertically aligned liquid crystal cured film, the horizontally aligned film, and the horizontally aligned liquid crystal cured film were sequentially laminated was prepared, and the adhesion and alignment of the laminate were evaluated. The results are shown in Table 1.

(1) Preparation of a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 0.1 part by mass of a leveling agent "BYK-361N" (manufactured by BM Chemie) and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-?olinylphenyl)butan-1-one (manufactured by BASF Japan Co., Ltd. "Irgacure (registered trademark) 369 (Irg 369)") as a photopolymerization initiator were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration might become 13%. By stirring this mixture at 80 degreeC for 1 hour, the polymeric liquid crystal composition for horizontal alignment liquid crystal cured film formation was obtained.

(2) Formation of horizontal alignment liquid crystal cured film Corona treatment was performed on the surface of the vertical alignment liquid crystal cured film of the laminate of the base material (TAC film), cured resin layer, and vertical alignment liquid crystal cured film produced by the same procedure as in Example 1, and the composition for forming a horizontal alignment film was coated with a bar coater, and dried at 80° C. for 1 minute. Next, using a polarized UV irradiation device (SPOT CURE SP-9; manufactured by Ushio Electric Co., Ltd.), polarized UV exposure was performed at a wavelength of 313 nm at an integrated light intensity of 100 mJ/cm ² to obtain a horizontal alignment film. The film thickness of the obtained horizontal alignment film was measured with an ellipsometer, and the result was 200 nm.繼而，於水平配向膜上塗佈水平配向液晶硬化膜形成用聚合性液晶組合物，於120℃下加熱60秒鐘後，使用高壓水銀燈(UNICURE VB-15201BY-A，牛尾電機股份有限公司製造)，自塗佈有水平配向液晶硬化膜形成用聚合性液晶組合物之面照射紫外線(氮氣氛圍下，波長365 nm下之累計光量：500 mJ/cm ² )，藉此形成水平配向液晶硬化膜，獲得將基材、硬化樹脂層、垂直配向液晶硬化膜、水平配向膜、水平配向液晶硬化膜依序鄰接積層而成之積層體。 The film thickness of the obtained horizontally aligned liquid crystal cured film was measured with an ellipsometer and found to be 2.2 μm.

3. Embodiment 3 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. In the same manner as in Example 2, a laminate in which a base material, a cured resin layer, a vertically aligned liquid crystal cured film, a horizontally aligned film, and a horizontally aligned liquid crystal cured film were sequentially laminated was produced, and the adhesion and alignment of the laminate were evaluated. The results are shown in Table 1.

(1) Preparation of a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC Corporation), 2.0 parts by mass of ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, 0.5 parts by mass of silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 2-dimethylamino-2-benzyl as a photopolymerization initiator were added. 6 parts by mass of 1-(4-?olinylphenyl)butan-1-one ("Irgacure (registered trademark) 369 (Irg 369)" manufactured by BASF Japan Co., Ltd.). Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration might become 13%. By stirring this mixture at 80 degreeC for 1 hour, the polymeric liquid crystal composition for vertical alignment liquid crystal cured film formation was obtained.

(2) Production of Vertical Alignment Liquid Crystal Cured Film On the cured resin layer on the base material prepared by the same procedure as in Example 1, a bar coater was used to coat the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film, and after heating at 120° C. for 60 seconds, a high-pressure mercury lamp (UNICURE VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) was used to irradiate ultraviolet rays (under a nitrogen atmosphere, wavelength 36 Cumulative light intensity at 5 nm: 500 mJ/cm ² ), thereby forming a vertically aligned liquid crystal cured film. The film thickness of the obtained vertically aligned liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Corporation), and it was 1.2 μm.

4. Embodiment 4 The formation of the horizontal alignment liquid crystal cured film was changed as follows, except that, in the same manner as in Example 3, a laminate in which the base material, the cured resin layer, the vertical alignment liquid crystal cured film, the cured resin layer, the horizontal alignment film, and the horizontal alignment liquid crystal cured film were sequentially laminated was produced, and the adhesiveness and alignment of the laminate were evaluated. The results are shown in Table 1.

(1) Formation of the horizontally aligned liquid crystal cured film: 50 parts by mass of dipentaerythritol hexaacrylate (ARONIX M-403 multifunctional acrylate manufactured by Toa Gosei Co., Ltd.), 50 parts by mass of acrylate resin (Ebecryl 4858 manufactured by Daicel-UCB Co., Ltd.), 2-methyl-1[4-(methylthio)phenyl]-2-𠰌linylpropan-1-one (Irgacure 907; Ciba Spec Alty Chemicals) 3 parts by mass were dissolved in 250 parts by mass of isopropyl alcohol to prepare a solution to obtain a composition for forming a cured resin layer containing an acrylate compound. Next, corona treatment was performed on the surface of the vertical alignment liquid crystal cured film of the laminate including the substrate (TAC film), the cured resin layer, and the vertical alignment liquid crystal cured film, and the composition for forming the cured resin layer was coated with a bar coater, and dried at 50° C. for 1 minute. Thereafter, a cured resin layer was formed by irradiating ultraviolet rays (accumulated light intensity at a wavelength of 365 nm in a nitrogen atmosphere: 400 mJ/cm ² ) using a high-pressure mercury lamp ("UNICURE VB-15201BY-A", manufactured by Ushio Electric Co., Ltd.). The film thickness of the obtained cured resin layer was measured with a contact film thickness gauge, and it was 2.0 μm. Next, corona treatment was performed on the cured resin layer which is the outermost layer of the laminate comprising the substrate (TAC film), cured resin layer, vertically aligned liquid crystal cured film, and cured resin layer produced by the above method, and the composition for forming a horizontal alignment film was coated using a bar coater, and dried at 80° C. for 1 minute. Next, using a polarized UV irradiation device (SPOT CURE SP-9; manufactured by Ushio Electric Co., Ltd.), polarized UV exposure was performed at a wavelength of 313 nm at an integrated light intensity of 100 mJ/cm ² to obtain a horizontal alignment film. The film thickness of the obtained horizontal alignment film was measured with an ellipsometer, and the result was 200 nm.繼而，於水平配向膜上塗佈水平配向液晶硬化膜形成用聚合性液晶組合物，於120℃下加熱60秒鐘後，使用高壓水銀燈(UNICURE VB-15201BY-A，牛尾電機股份有限公司製造)，自塗佈有水平配向液晶硬化膜形成用聚合性液晶組合物之面照射紫外線(氮氣氛圍下，波長365 nm下之累計光量：500 mJ/cm ² )，藉此形成水平配向液晶硬化膜，獲得將基材、垂直配向液晶硬化膜、水平配向膜、水平配向液晶硬化膜依序鄰接積層而成之積層體。 The film thickness of the obtained horizontally aligned liquid crystal cured film was measured with an ellipsometer and found to be 2.2 μm.

5. Embodiment 5 The production method of the vertically aligned liquid crystal cured film was changed as follows, except that, in the same manner as in Example 3, a laminate in which the base material, the vertically aligned liquid crystal cured film, the horizontally aligned liquid crystal film, and the horizontally aligned liquid crystal cured film were sequentially adjacently laminated was produced, and the adhesiveness and alignment of the laminated body were evaluated. The results are shown in Table 1.

(1) Production of vertically aligned liquid crystal cured film: After corona treatment was performed on the COP film (ZF14-23) manufactured by Japan ZEON Co., Ltd., a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was coated with a bar coater, and heated at 120° C. for 60 seconds. Next, while heating to 120°C, using a high-pressure mercury lamp (UNICURE VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.), irradiate ultraviolet rays (accumulated light intensity at a wavelength of 365 nm in a nitrogen atmosphere: 500 mJ/cm ² ) from the surface coated with the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film to form a vertically aligned liquid crystal cured film. laminated body. The film thickness of the obtained vertically aligned liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Corporation), and it was 1.2 μm.

6. Embodiment 6 The preparation of the base material was changed as follows, except that, in the same manner as in Example 3, a laminate in which 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 were successively laminated was produced, and the adhesiveness and alignment of the laminate were evaluated. The results are shown in Table 1.

(1) Preparation of base material 50 parts by mass of dipentaerythritol hexaacrylate (ARONIX M-403 multifunctional acrylate manufactured by Toa Gosei Co., Ltd.), 50 parts by mass of acrylate resin (Ebecryl 4858 manufactured by Daicel-UCB Co., Ltd.), 2-methyl-1[4-(methylthio)phenyl]-2-𠰌linylpropan-1-one (Irgacure 907; Ciba Specialty Chemical s company) 3 parts by mass were dissolved in 250 parts by mass of isopropyl alcohol to prepare a solution to obtain a composition for forming a cured resin layer containing an acrylate compound. Next, on a PET film (DIAFOIL T140E25) manufactured by Mitsubishi Plastics Co., Ltd., the composition for forming a cured resin layer was coated with a bar coater, dried at 50°C for 1 minute, and then irradiated with ultraviolet light (accumulated light intensity at a wavelength of 365 nm in a nitrogen atmosphere: 400 mJ/cm ² ) using a high-pressure mercury lamp ("UNICURE VB-15201BY-A", manufactured by Ushio Electric Co., Ltd.) to form a cured resin. layers. The film thickness of the obtained cured resin layer was measured with a contact film thickness gauge, and it was 2.0 μm.

7. Embodiment 7 The film thickness of the horizontal alignment film was changed to 30 nm. In the same manner as in Example 5, a laminate was produced in which the base material, the vertically aligned liquid crystal cured film, the horizontal alignment film, and the horizontally aligned liquid crystal cured film were sequentially laminated, and the adhesiveness and alignment of the laminate were evaluated. The results are shown in Table 1.

8. Embodiment 8 The film thickness of the horizontal alignment film was changed to 500 nm. In the same manner as in Example 5, a laminate was produced in which the base material, the vertical alignment liquid crystal cured film, the horizontal alignment film, and the horizontal alignment liquid crystal cured film were adjacently laminated in sequence, and the adhesiveness and alignment of the laminate were evaluated. The results are shown in Table 1.

9. Embodiment 9 The preparation of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, except that, in the same manner as in Example 5, a laminate in which a substrate, a vertically aligned liquid crystal cured film, a horizontally aligned film, and a horizontally aligned liquid crystal cured film were sequentially adjacently laminated was produced, and the adhesiveness and alignment of the laminated body were evaluated. The results are shown in Table 1.

(1) Preparation of a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 0.25 parts by mass of leveling agent "F-556" (manufactured by DIC Corporation), 2.0 parts by mass of ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802, and 2-dimethylamino-2-benzyl-1-(4-? "Irgacure (registered trademark) 369 (Irg 369)" manufactured by Co., Ltd.) 6 parts by mass. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration might become 13%. This mixture was stirred at 80 degreeC for 1 hour, and the polymerizable liquid crystal composition for vertical alignment liquid crystal cured film formation was obtained.

10. Example 10 The preparation of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, except that, in the same manner as in Example 5, a laminate in which a substrate, a vertically aligned liquid crystal cured film, a horizontally aligned film, and a horizontally aligned liquid crystal cured film were sequentially adjacently laminated was produced, and the adhesiveness and alignment of the laminated body were evaluated. The results are shown in Table 1.

(1) Preparation of a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 0.25 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation), 0.5 parts by mass of a silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.), and 2-dimethylamino-2-benzyl-1-(4-? 369 (Irg369)") 6 parts by mass. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration might become 13%. This mixture was stirred at 80 degreeC for 1 hour, and the polymerizable liquid crystal composition for vertical alignment liquid crystal cured film formation was obtained.

11. Comparative example 1 The preparation of the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was changed as follows, except that, in the same manner as in Example 5, a laminate in which a substrate, a vertically aligned liquid crystal cured film, a horizontally aligned film, and a horizontally aligned liquid crystal cured film were sequentially adjacently laminated was produced, and the adhesiveness and alignment of the laminated body were evaluated. The results are shown in Table 1.

(1) Preparation of a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 0.25 parts by mass of a leveling agent "F-556" (manufactured by DIC Corporation) and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-alphalinylphenyl)butan-1-one (manufactured by BASF Japan Co., Ltd. "Irgacure (registered trademark) 369 (Irg 369)") as a photopolymerization initiator were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration might become 13%. This mixture was stirred at 80 degreeC for 1 hour, and the polymerizable liquid crystal composition for vertical alignment liquid crystal cured film formation was obtained.

12. Comparative example 2 The manufacturing steps of the horizontally aligned liquid crystal cured film were changed as follows, except that, in the same manner as in Example 5, a laminate in which the base material, the vertically aligned liquid crystal cured film, the horizontally aligned film, and the horizontally aligned liquid crystal cured film were sequentially adjacently laminated was produced, and the adhesiveness and alignment of the laminated body were evaluated. The results are shown in Table 1.

(1) Preparation of a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. With respect to 100 parts by mass of the obtained mixture, 0.1 part by mass of a leveling agent "BYK-361N" (manufactured by BM Chemie Co., Ltd.) and 6 parts by mass of 2-dimethylamino-2-benzyl-1-(4-?olinylphenyl)butan-1-one (manufactured by BASF Japan Co., Ltd. "Irgacure (registered trademark) 369 (Irg 369)") as a photopolymerization initiator were added. Furthermore, cyclopentanone was added so that the solid content concentration might become 13%. The mixture was stirred at 80° C. for 1 hour, whereby a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film was obtained.

(2) Formation of Horizontally Aligned Liquid Crystal Cured Film Corona treatment was performed on the vertically aligned liquid crystal cured film of the laminate comprising the base material and the vertically aligned liquid crystal cured film produced by the above method. Next, a 4% by mass aqueous solution of polyvinyl alcohol (polyvinyl alcohol 1000 complete saponification type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied and dried to form a film with a thickness of 0.2 μm. Then, rubbing treatment was performed on the surface of the obtained film to obtain a horizontal alignment film. The rubbing treatment was carried out using a semi-automatic rubbing device (trade name: LQ-008, manufactured by Changyang Engineering Co., Ltd.) with a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Chemical Co., Ltd.) under the conditions of 0.15 mm indentation, 500 rpm, and 16.7 mm/s.繼而，於水平配向膜上塗佈水平配向液晶硬化膜形成用聚合性液晶組合物，於120℃下加熱60秒鐘後，使用高壓水銀燈(UNICURE VB-15201BY-A，牛尾電機股份有限公司製造)，自塗佈有水平配向液晶硬化膜形成用聚合性液晶組合物之面照射紫外線(氮氣氛圍下，波長365 nm下之累計光量：500 mJ/cm ² )，藉此形成水平配向液晶硬化膜，獲得將基材、垂直配向液晶硬化膜、水平配向膜、水平配向液晶硬化膜依序鄰接積層而成之積層體。 The film thickness of the obtained horizontally aligned liquid crystal cured film was measured with an ellipsometer and found to be 2.2 μm.

[Table 1]

According to the present invention, it was possible to produce a vertically aligned liquid crystal cured film without forming a vertically aligned film, and it was confirmed that both liquid crystal alignment and adhesiveness could be improved (Examples 1 to 10). On the other hand, in the case of using a polymerizable liquid crystal composition that does not contain a vertical alignment promoter, a vertically aligned liquid crystal cured film cannot be obtained without forming a vertical alignment film, so the retardation value of the horizontally aligned liquid crystal cured film cannot be calculated (Comparative Example 1). Furthermore, in Comparative Example 2 in which the horizontal alignment film was not a photo-alignment film, the adhesiveness between the vertical alignment cured liquid crystal film and the horizontal alignment liquid crystal cured film was poor.

1‧‧‧Substrate 2‧‧‧Vertically aligned liquid crystal cured film 3‧‧‧Horizontal alignment film 4‧‧‧Horizontal alignment liquid crystal cured film 5‧‧‧hardened resin layer 11‧‧‧Laminated body

Fig. 1 is a schematic cross-sectional view showing an example of the layer configuration of the laminate of the present invention. Fig. 2 is a schematic cross-sectional view showing an example of the layer configuration of the laminate of the present invention. Fig. 3 is a schematic cross-sectional view showing an example of the layer configuration of the laminate of the present invention.

Claims (21)

A laminate comprising a substrate, a vertically aligned liquid crystal cured film, a horizontally aligned film, and a horizontally aligned liquid crystal cured film in the following order. The vertically aligned liquid crystal cured film is a cured product of a polymeric liquid crystal composition formed by hardening a polymerizable liquid crystal compound in a state aligned vertically relative to the plane of the liquid crystal cured film. The horizontally aligned liquid crystal cured film is a cured product of a polymeric liquid crystal composition formed by curing a polymerizable liquid crystal compound in a state aligned horizontally relative to the plane of the liquid crystal cured film, and satisfies the following formula (1): ReA(450)/ReA(550)≦1 (1)[In the formula (1), ReA(450) represents the in-plane retardation value at a wavelength of 450nm in the in-plane direction of the horizontally aligned liquid crystal cured film, and ReA(550) represents the in-plane retardation value at a wavelength of 550nm in the in-plane direction of the horizontally aligned liquid crystal cured film], the above-mentioned vertically aligned liquid crystal cured film contains a vertical alignment promoter, and the above-mentioned horizontal alignment film is made of (meth)acryl A photo-alignment film made of a polymer, and the total film thickness from the surface of the vertical alignment cured liquid crystal film on the substrate side to the surface of the horizontal alignment cured liquid crystal film opposite to the horizontal alignment film is 10 μm or less. A laminate comprising a base material, a vertically aligned liquid crystal cured film, a horizontally aligned film, and a horizontally aligned liquid crystal cured film in the following order, wherein the vertically aligned liquid crystal cured film is a cured product of a polymeric liquid crystal composition that is cured in a state where a polymerizable liquid crystal compound is aligned vertically relative to the plane of the liquid crystal cured film, and satisfies the following formula (2): RthC(450)/RthC(550)≦1 (2)[In the formula (2), RthC(450) represents the retardation value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 450nm, and RthC(550) represents the retardation value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550nm], the above-mentioned horizontally aligned liquid crystal cured film is a polymerized liquid crystal compound that is cured in a state aligned horizontally with respect to the plane of the liquid crystal cured film. A cured product of a non-volatile liquid crystal composition, wherein the above-mentioned vertical alignment liquid crystal cured film contains a vertical alignment promoter, the above-mentioned horizontal alignment film is a photo-alignment film formed of a polymer having a (meth)acryl group, and the total film thickness from the surface of the above-mentioned vertical alignment liquid crystal cured film on the substrate side to the surface of the horizontal alignment liquid crystal cured film opposite to the horizontal alignment film is 10 μm or less. The laminate according to claim 1 or 2, wherein the substrate is a peelable substrate. The laminate according to claim 1 or 2, wherein the base material, the vertically aligned liquid crystal cured film, the horizontally aligned liquid crystal cured film, and the horizontally aligned liquid crystal cured film exist adjacently in this order. The laminate of claim 1 or 2, wherein the film thickness of the horizontal alignment film is 10-5000 nm. The laminate according to claim 1 or 2, wherein the horizontal alignment film is a photo-alignment film formed of a polymer having an azo group or a cinnamonyl group. The laminate according to claim 1 or 2, wherein the horizontally aligned liquid crystal cured film has at least one maximum absorption between 300 and 400 nm in wavelength. The laminate according to claim 1 or 2, wherein the vertical alignment liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter. The laminate according to claim 1 or 2, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter, and the nonionic silane compound is a silane coupling agent. The laminate according to claim 1 or 2, wherein the vertical alignment liquid crystal cured film contains an ionic compound containing non-metal atoms as a vertical alignment promoter. The laminate according to claim 1 or 2, wherein the vertical alignment liquid crystal cured film contains an ionic compound containing non-metal atoms as a vertical alignment promoter, and the molecular weight of the ionic compound is 100 to 10,000. The laminate according to claim 1 or 2, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound and an ionic compound containing nonmetal atoms as a vertical alignment promoter. The laminate according to claim 1 or 2, wherein the horizontal alignment cured liquid crystal film is a cured liquid crystal film formed by curing a polymerizable liquid crystal compound having at least one radically polymerizable group in a state aligned horizontally with respect to the in-plane direction of the cured liquid crystal film, and the vertically aligned liquid crystal cured film is a cured liquid crystal film cured by curing a polymerizable liquid crystal compound having at least one radically polymerizable group in a state aligned vertically with respect to the in-plane direction of the cured liquid crystal film. The laminate according to claim 1 or 2, wherein the vertically aligned liquid crystal cured film has at least one maximum absorption at a wavelength of 300-400 nm. The laminated body of claim item 1, wherein the vertically aligned liquid crystal cured film satisfies the following formula (2): RthC(450)/RthC(550)≦1 (2) [In the formula (2), RthC(450) represents the retardation value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 450nm, and RthC(550) represents the retardation value of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550nm]. An elliptically polarizing plate comprising the laminate according to any one of Claims 1 to 15 and a polarizing film. An elliptically polarizing plate comprising a laminate obtained by removing a substrate from the laminate according to any one of claims 1 to 15, and a polarizing film. The elliptically polarizing plate according to claim 16 or 17, wherein the angle formed by the retardation axis of the horizontally aligned liquid crystal cured film constituting the laminate and the absorption axis of the polarizing film is 45±5°. An organic EL display device comprising the elliptically polarizing plate according to any one of claims 16-18. A method for manufacturing a laminate according to any one of Claims 1 to 15, which comprises the following steps: The method comprises the following steps: forming a coating film of a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film containing a polymerizable liquid crystal compound, forming a vertical alignment liquid crystal cured film from the coating film; forming a coating film of a composition for forming a horizontal alignment film, forming a horizontal alignment film from the coating film; According to the manufacturing method of Claim 20, the step of forming a vertically aligned liquid crystal cured film, the step of forming a horizontally aligned liquid crystal film, and the step of forming a horizontally aligned liquid crystal cured film are continuously performed in the following order.