TWI791764B - Laminated body and manufacturing method thereof - Google Patents

Abstract

The lamination system of the present invention includes the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film in sequence, The cured product of the polymerizable liquid crystal composition obtained by curing the polymerizable liquid crystal compound of the horizontally aligned liquid crystal cured film in a state aligned horizontally with respect to the plane of the liquid crystal cured film, and the polymerizable liquid crystal compound of the vertically aligned liquid crystal cured film a cured product of a polymerizable liquid crystal composition cured in a state of being aligned perpendicular to the plane of the liquid crystal cured film, and The above-mentioned vertical alignment liquid crystal cured film contains a vertical alignment promoter, from the surface of the above-mentioned horizontal alignment liquid crystal cured film on the opposite side to the above-mentioned vertical alignment liquid crystal cured film to the above-mentioned vertical alignment liquid crystal cured film on the opposite side to the above-mentioned horizontal alignment liquid crystal cured film The total film thickness on the surface is 5 μm or less.

Description

Laminated body and manufacturing method thereof

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

An elliptical polarizer is an optical member formed by laminating a polarizer and a phase difference plate. For example, in a device that displays an image in a flat state such as an organic EL image display device, it is used to prevent light reflection on the electrodes that constitute 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, it is suitable for a retardation plate constituting an elliptically polarizing plate to exhibit inverse wavelength dispersion. As such a retardation plate, there is known a retardation plate comprising a polymerizable liquid crystal compound exhibiting inverse wavelength dispersion that is polymerized and hardened while being aligned in the horizontal direction with respect to the plane of the retardation plate. Alignment liquid crystal hardening film. In addition, it is known that by incorporating a vertically aligned liquid crystal cured film into an elliptically polarized plate having a horizontally aligned liquid crystal cured film, it is known that when the elliptically polarized plate is used in an organic EL display device, the oblique hue at the time of black display can be suppressed. As a variation, 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, as described in the above-mentioned patent documents, the laminated body including the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film was previously prepared in many cases by independently manufacturing the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film, and then using Adhesives and the like bond the two together and manufacture them. Also, conventionally, the vertical alignment film for aligning the polymerizable liquid crystal compound in the vertical direction is required in the manufacture of the vertical alignment cured liquid crystal film, and the vertical alignment film must be formed before forming the vertical alignment liquid crystal cured film. Therefore, the production 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 there is a problem that productivity tends to decrease.

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

Furthermore, the inventors of the present invention have found that when forming a vertically aligned cured liquid crystal film instead of forming a vertically aligned liquid crystal cured film on the horizontally aligned liquid crystal cured film, the liquid crystal alignment is likely to decrease. Therefore, the object of the present invention is also to improve liquid crystal alignment in a laminate including a vertically aligned liquid crystal cured film formed on a horizontally aligned liquid crystal cured film without a vertically aligned liquid crystal 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 following aspects are included in this invention. [1] A laminate comprising a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film in this order, and The cured product of the polymerizable liquid crystal composition obtained by curing the polymerizable liquid crystal compound of the horizontally aligned liquid crystal cured film in a state aligned horizontally with respect to the plane of the liquid crystal cured film, and the polymerizable liquid crystal compound of the vertically aligned liquid crystal cured film a cured product of a polymerizable liquid crystal composition cured in a state of being aligned perpendicular to the plane of the liquid crystal cured film, and The above-mentioned vertical alignment liquid crystal cured film contains a vertical alignment promoter, from the surface of the above-mentioned horizontal alignment liquid crystal cured film on the opposite side to the above-mentioned vertical alignment liquid crystal cured film to the above-mentioned vertical alignment liquid crystal cured film on the opposite side to the above-mentioned horizontal alignment liquid crystal cured film The total film thickness on the surface is 5 μm or less. [2] The laminate according to the above [1], wherein the horizontally aligned liquid crystal cured film is adjacent to the vertically aligned liquid crystal cured film. [3] The laminate described in [1] or [2] above, wherein the horizontally aligned liquid crystal cured film is a polymerizable liquid crystal compound having at least one radical polymerizable group in the plane of the liquid crystal cured film. A liquid crystal cured film cured in a state where the direction is horizontally aligned, and a vertically aligned liquid crystal cured film is a polymerizable liquid crystal compound having at least one radically polymerizable group that is vertically aligned relative to the in-plane direction of the liquid crystal cured film The liquid crystal cured film hardened in the state. [4] The laminate according to any one of [1] to [3] above, wherein the horizontally aligned liquid crystal cured film has at least one absorption maximum at a wavelength of 300 to 400 nm. [5] The laminate described in any one of [1] to [4] above, wherein the horizontally aligned liquid crystal cured film satisfies the following formula (1): ReA(450)/ReA(550)≦1 (1) [In formula (1), ReA(450) represents the in-plane retardation value of the in-plane direction of the horizontally aligned liquid crystal cured film at a wavelength of 450 nm, and ReA(550) represents the in-plane direction of the horizontally aligned liquid crystal cured film at a wavelength of 550 nm In-plane retardation value under nm]. [6] The laminate according to any one of [1] to [5] above, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter. [7] The laminate as described in any one of [1] to [6] above, wherein the vertical alignment liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter, and the nonionic silane compound is a silane diisocyanate. mixture. [8] The laminate according to any one of the above [1] to [7], wherein the vertical alignment liquid crystal cured film contains an ionic compound containing a non-metal atom as a vertical alignment promoter. [9] The laminate as described in any one of [1] to [8] above, wherein the vertical alignment liquid crystal cured film contains an ionic compound containing a non-metal atom as a vertical alignment promoter, and the molecular weight of the ionic compound is 100 to 10,000. [10] The laminate according to any one of [1] to [9] 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 promoter. [11] The laminate according to any one of [1] to [10] above, wherein the vertically aligned liquid crystal cured film has at least one maximum absorption at a wavelength of 300 to 400 nm. [12] The laminate described in any one of [1] to [11] above, wherein the vertical alignment 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 phase difference of the vertically aligned liquid crystal cured film in the thickness direction at a wavelength of 550 nm difference]. [13] The laminate according to any one of [1] to [12] above, which includes a horizontal alignment film, and the horizontal alignment film, the horizontal alignment cured liquid crystal film, and the vertical alignment liquid crystal cured film exist adjacently in this order . [14] The laminate described in [13] above, wherein the horizontal alignment film is a photo-alignment film formed of a polymer having a (meth)acryl group. [15] The laminate described in [13] or [14] above, wherein the film thickness of the horizontal alignment film is 100 to 5000 nm. [16] The laminate according to any one of [13] to [15] above, wherein the horizontal alignment film is a photo-alignment film formed of a polymer having an azo group or a cinnamoyl group. [17] An elliptically polarizing plate comprising the laminate described in any one of [1] to [16] above and a polarizing film. [18] The elliptically polarizing plate as described in [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 the above [17] or [18]. [20] A method for manufacturing the laminate described in any one of the above [1] to [16], which includes the following steps in the following order: 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; and A coating film of a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film containing a polymerizable liquid crystal compound is formed, and a vertical 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 cured liquid crystal film for horizontal alignment and the step of forming a cured liquid crystal film for vertical alignment are performed continuously in the following order. [22] The production method described in [20] or [21] above, which includes forming a coating film of a composition for forming a horizontal alignment film before the step of forming a horizontally aligned liquid crystal cured film, and forming a horizontal alignment layer from the coating film. membrane steps. [Effect of Invention]

According to the present invention, there can be provided a laminate capable of continuously forming a vertically aligned cured liquid crystal film without forming a vertically aligned liquid crystal cured film on a horizontally aligned liquid crystal cured film, especially the above laminate having excellent liquid crystal alignment, and a method for producing the same.

The laminate of the present invention sequentially includes a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film. 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 laminated body 11 shown in FIG. 1 is formed by sequentially laminating a horizontally aligned liquid crystal cured film 1 and a vertically aligned liquid crystal cured film 2 . In the laminated body 11 shown in FIG. 1 , the vertically aligned liquid crystal cured film 2 is directly formed on the horizontally aligned liquid crystal cured film 1 without interposing a layer having a vertical alignment restricting force (hereinafter also referred to as "vertical alignment film"). Above, the horizontal alignment liquid crystal cured film 1 and the vertical alignment liquid crystal cured film 2 exist adjacently. The laminate of the present invention may further include other layers in addition to the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film. Examples of other layers include substrates, horizontal alignment films, cured resin layers such as protective layers and hard coat layers, further vertical or horizontal alignment liquid crystal cured films, and adhesives for bonding the laminate of the present invention to polarizing films. Adhesive layer, etc.

As a laminate including other layers, for example, in the laminate 11 shown in FIG. 2 as another aspect of the present invention, the horizontal alignment liquid crystal cured film 1 is formed on the horizontal alignment film 3, and the horizontal alignment liquid crystal cured film 1 is formed by laminating a vertically aligned liquid crystal cured film 2 . Furthermore, in the laminated body 11 shown in FIG. 3 which is another aspect of the present invention, the horizontal alignment film 3 is formed on the substrate 5 on which the cured resin layer 4 is formed, and layers are sequentially stacked on the horizontal alignment film 3 The horizontal liquid crystal cured film 1 and the vertical alignment liquid crystal cured film 2 are formed. An elliptically polarizing plate can be obtained by bonding the laminate 11 and a polarizing film via an adhesive layer. At this time, either side of the horizontally aligned liquid crystal cured film 1 and the vertically aligned liquid crystal cured film 2 of the laminate 11 can be attached to the polarizing film, for example, the vertically aligned liquid crystal cured film 2 of the laminate 11 in FIG. The films are attached through the adhesive layer, and after the substrate 5 of the laminate 11 in FIG. 3 is peeled off, the cured resin layer 4 and the polarizing film may be attached through the adhesive layer. Furthermore, hereinafter, in this specification, among the layer configurations of the laminate of the present invention, the smallest layer configuration including the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film in order is also referred to as "basic layer configuration (I) ". That is, in the case where the laminate of the present invention includes a plurality of sheets of horizontally or vertically aligned liquid crystal cured films, and when there are other layers between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film, they are arranged closest to each other. The horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film form the basic layer composition (I). For example, when the lamination system of the present invention is formed by successively laminating the substrate, the horizontal alignment film, the first horizontal alignment liquid crystal cured film, the second horizontal alignment liquid crystal cured film, and the vertical alignment liquid crystal cured film, from the second The horizontal alignment liquid crystal cured film to the vertical alignment liquid crystal cured film become the basic layer composition (I) of the laminated body of the present invention.

In the laminated body of the present invention, the total film thickness (hereinafter , also referred to as "total film thickness T1", refers to the thickness between a-b in Figures 1 to 3) is 5 μm or less. Since the laminated body of the present invention can directly form a vertically aligned liquid crystal cured film on a horizontally aligned liquid crystal cured film, it is different from making a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film and bonding them together with an adhesive or an adhesive. The total film thickness T1 can be made thinner than the conventional laminate obtained. 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 4.5 μm or less, more preferably 4 μm or less. The lower limit of the above-mentioned total film thickness T1 is not particularly limited, and it is usually not less than 1 μm, for example, not less than 1.5 μm. Furthermore, in the basic layer configuration (I) of the laminate of the present invention, the side opposite to the vertically aligned liquid crystal cured film of the horizontally aligned liquid crystal cured film, or the opposite side of the vertically aligned liquid crystal cured film to the horizontally aligned liquid crystal cured film Furthermore, in the case of having a vertically aligned liquid crystal cured film and/or a horizontally aligned liquid crystal cured film, the above-mentioned total film thickness T1 means that the horizontally aligned liquid crystal cured film constituting (I) from the basic layer is on the opposite side to the vertically aligned liquid crystal cured film. The total film thickness from the surface of the vertically aligned liquid crystal cured film to the surface opposite to the horizontally aligned liquid crystal cured film.

In the laminate of the present invention, the vertically aligned liquid crystal cured film is formed on the horizontally aligned liquid crystal cured film or the layer without vertical alignment restrictive force provided on the horizontally aligned liquid crystal cured film without intervening the vertically aligned liquid crystal film. In the laminate of the present invention, the vertical alignment liquid crystal cured film can be formed without the vertical alignment film, so the number of manufacturing steps of the laminate is reduced, and the laminate can be manufactured with good productivity. In a more suitable aspect, the multilayer system of the present invention is formed by adjacently existing the cured film of the horizontal alignment liquid crystal and the cured film of the vertical alignment liquid crystal. A laminate having such a layer structure can continuously form a vertically aligned liquid crystal cured film on a horizontally aligned liquid crystal cured film without a vertically aligned liquid crystal cured film, and thus 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 accelerator. That is, in the present invention, the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film contains a vertical alignment promoter. In the present invention, the term "vertical alignment promoter" refers to a material that promotes the liquid crystal alignment of the polymerizable liquid crystal compound in the vertical direction with respect 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 the present invention, it is not necessary to form a vertical alignment film, the manufacturing steps of the laminated body are simplified, and the laminated body can be manufactured with good productivity. Furthermore, in the case of forming a vertically aligned liquid crystal cured film on a horizontally aligned liquid crystal cured film, the liquid crystal alignment of the polymerizable liquid crystal compound constituting the vertically aligned liquid crystal cured film is easily affected by the liquid crystal alignment of the horizontally aligned liquid crystal cured film, and it is difficult to align the liquid crystals with respect to the cured liquid crystal. The polymerizable liquid crystal compound is aligned with high precision in the vertical direction of the film plane. On the other hand, by containing the vertical alignment accelerator, the alignment of the polymerizable liquid crystal compound in the vertical direction is promoted, and the accuracy of liquid crystal alignment can be improved, so it is easy to improve the liquid crystal alignment of a laminate including the vertically aligned liquid crystal cured film.

Examples of the vertical alignment accelerator that promotes the alignment of the polymerizable liquid crystal compound in the vertical direction include ionic compounds containing non-metal atoms, nonionic silane compounds, and the like. 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 formed by the polymerizable liquid crystal composition In the film, non-ionic silane compounds tend to be segregated at the interface between the dry coating film and the air, which improves the vertical alignment restriction force of the polymerizable liquid crystal compound. In the dry coating film, the polymerizable liquid crystal compound is relative to the film plane. The tendency to align vertically. Thereby, the polymerizable liquid crystal compound can be kept in a state of vertical alignment to form a cured liquid crystal film.

The nonionic silane compound is a nonionic compound containing Si element. Examples of nonionic silane compounds include silicone polymers such as polysilanes, polysiloxane resins such as polysiloxane oils and polysiloxane resins, polysiloxane oligomers, and silsesquioxanes. and organic-inorganic silane compounds such as alkoxysilanes (more specifically, silane coupling agents, etc.).

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-mercaptopropyl Trimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer Copolymers containing mercaptopropyl group; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane 3-Methacryloxypropyltrimethylsilane Oxysilane-Tetramethoxysilane Copolymer, 3-Methacryloxypropyltrimethoxysilane-Tetraethoxysilane Copolymer, 3-Methacryloxypropyltriethoxysilane -Tetramethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane -Tetramethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxy methacryloxypropyl group-containing silane-tetramethoxysilane copolymer, and 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer Copolymer; 3-acryloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxysilane propyltriethoxysilane-tetramethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyl di Methoxysilane-tetramethoxysilane copolymer, 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldiethoxy Copolymers containing acryloxypropyl groups such as silane-tetramethoxysilane copolymer and 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer; ethylene Trimethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane Silane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethoxysilane Diethoxysilane-tetramethoxysilane copolymer, and vinyl-containing copolymers such as vinylmethyldiethoxysilane-tetraethoxysilane copolymer; 3-aminopropyl trimethyl Oxysilane-Tetramethoxysilane Copolymer, 3-Aminopropyltrimethoxysilane-Tetraethoxysilane Copolymer, 3-Aminopropyltriethoxysilane-Tetramethoxysilane Copolymer , 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropyl methyl Dimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer, and 3-aminopropylmethyldiethoxysilane Amine-containing copolymers such as silane-tetraethoxysilane copolymers, 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 adjacent layers such as a horizontal alignment liquid crystal cured film.

The silane coupling agent has a terminal group selected from vinyl, epoxy, styrene, methacryl, acryl, amine, isocyanurate, ureido, mercapto, isocyanate, carboxyl, A compound containing Si element, such as at least one functional group of the group consisting of hydroxyl group and at least one alkoxysilyl group or silanol group. By properly selecting these functional groups, it is possible to impart special effects such as the improvement of the mechanical strength of the vertically aligned liquid crystal cured film, the surface modification of the vertically aligned liquid crystal cured film, and the improvement of the adhesion to the layer adjacent to the vertically aligned liquid crystal cured film. . From the viewpoint of adhesiveness, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and another different reactive group (such as the above-mentioned functional group). The silane coupling agent is further 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 likely to be further improved, and the effect of promoting vertical alignment can be obviously obtained. As a polar group, an epoxy group, an amine group, an isocyanurate group, a mercapto group, a carboxyl group, and a hydroxyl group are mentioned, for example. In addition, the polar group may have a substituent or a protecting group as appropriate in order to control the reactivity of the silane coupling agent.

As the silane coupling agent, specifically, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-amino Ethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-Mercaptopropyltrimethoxysilane, 3-Glycidoxypropyltrimethoxysilane, 3-Glycidoxypropyltriethoxy Silane, 3-glycidoxypropyldimethoxymethylsilane, and 3-glycidoxypropylethoxydimethylsilane.

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

When the polymerizable liquid crystal composition forming a vertically aligned liquid crystal cured film contains a nonionic silane compound, its content is usually 0.01 to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition. 5 parts by mass, more preferably 0.05 to 4 parts by mass, still more preferably 0.1 to 3 parts by mass. If the content of the nonionic silane compound 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.

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 polymerizability will be exhibited by electrostatic interaction. The vertical alignment restriction force of the liquid crystal compound has a tendency to align the polymerizable liquid crystal compound in the vertical direction relative to the film plane in the dried coating film. Thereby, the polymerizable liquid crystal compound can be kept in a state of vertical alignment to form a cured liquid crystal film.

As an ionic compound containing a nonmetal atom, for example, an onium salt (more specifically, a quaternary ammonium salt having a positive charge on a nitrogen atom, a tertiary permeic acid salt, and a quaternary phosphonium salt having a positive charge on a phosphorus atom, etc.) . Among these onium salts, quaternary onium salts are preferred from the viewpoint of further improving the vertical alignment of the polymerizable liquid crystal compound, and quaternary phosphonium salts are more preferred from the viewpoint of improving availability and mass production. salt or quaternary ammonium salt. 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 composition. The molecular weight of the ionic compound is more preferably 5,000 or less, further preferably 3,000 or less.

Examples of the cationic component of the ionic compound containing a nonmetal atom include inorganic cations and organic cations. Among them, organic cations are preferable in terms of the alignment defect of the polymerizable liquid crystal compound being less likely to occur. 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 correspond one-to-one.

As an anion component, specifically, the following are mentioned, for example. Chloride anion [Cl ^- ], bromide anion [Br ^- ], iodide anion [I ^- ], tetrachloroaluminate anion [AlCl ₄ ^- ], heptachlorodialuminate anion [Al ₂ Cl ₇ ^- ], tetra Fluoborate anion [BF ₄ ^- ], hexafluorophosphate anion [PF ₆ ^- ], perchlorate anion [ClO ₄ ^- ], nitrate anion [NO ₃ ^- ], acetate anion [CH ₃ COO ^- ], Trifluoroacetate anion [CF ₃ COO ^- ], fluorosulfonate anion [FSO ₃ ^- ], mesylate anion [CH ₃ SO ₃ ^- ], trifluoromethanesulfonate anion [CF ₃ SO ₃ ^- ], p-toluene Sulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ^- ], bis(fluorosulfonyl)imide anion [(FSO ₂ ) ₂ N ^- ], bis(trifluoromethanesulfonyl)imide anion [(CF ₃ SO ₂ ) ₂ N ^- ], tris(trifluoromethanesulfonyl)methane anion [(CF ₃ SO ₂ ) ₃ C ^- ], hexafluoroarsenate anion [AsF ₆ ^- ], hexafluoroantimonate anion [SbF ₆ ^- ], hexafluoroniobate anion [NbF ₆ ^- ], hexafluorotantalate anion [TaF ₆ ^- ], dimethylphosphinate anion [(CH ₃ ) ₂ POO ^- ], (poly)hydrofluorofluoride anion [F(HF) _n ^- ] (for example, n represents an integer of 1 to 3), dicyanoimide anion [(CN) ₂ N ^- ], thiocyanide anion [SCN ^- ], perfluorobutanesulfonate anion [ C ₄ F ₉ SO ₃ ^- ], bis(pentafluoroethanesulfonyl)imide anion [(C ₂ F ₅ SO ₂ ) ₂ N ^- ], perfluorobutyrate anion [C ₃ F ₇ COO ^- ], and (Trifluoromethanesulfonyl)(trifluoromethanecarbonyl)imide anion [(CF ₃ SO ₂ )(CF ₃ CO)N ⁻ ].

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

(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 or in combination of two or more. Among them, ionic compounds containing phosphonium salts or ammonium salts are preferred.

The ionic compound 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. When the ionic compound has Si element and/or F element in the molecular structure of the cation site, it becomes easy to segregate the ionic compound to the surface of the vertically aligned liquid crystal cured film. Among these, the ionic compounds whose constituent elements are all non-metallic elements are preferably the following ionic compounds (i) to (iii) and the like.

(離子性化合物(ii)) [化2]

(離子性化合物(iii)) [化3]

(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 length 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" (Maruzen Co., Ltd.), etc.), to further improve the vertical alignment of polymerizable liquid crystal compounds. 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 the substituents directly bonded to the atom 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 a 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 the substituent having two or more positively charged atoms, it will be regarded as having the basic point. The number of covalent bonds from the atom with a positive charge to the nearest atom with a positive charge 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. . 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 the substituent bonded to the ring structure is totaled The one with the larger number of valence bonds is the "number of covalent bonds from the positively charged atom to the end of the molecular chain" described in the definition of M above.

When the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film contains an ionic compound containing a non-metal atom, its content is usually relative to 100 parts by mass of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition, preferably It is 0.01-5 mass parts, More preferably, it is 0.05-4 mass parts, More preferably, it is 0.1-3 mass parts. When the content of the ionic compound 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.

Formed from a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film 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 the dried coating film, the vertical alignment of the polymerizable liquid crystal compound becomes easier to further promote due to the electrostatic interaction from the ionic compound and the surface tension lowering 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 hardened product of a polymerizable liquid crystal composition containing the above-mentioned alignment accelerator and at least one polymerizable liquid crystal compound, preferably a polymerizable liquid crystal compound having at least one free radical polymerizable group relative to the A liquid crystal cured film cured in a state where the in-plane direction of the liquid crystal cured film is aligned vertically. 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 term "polymerizable group" refers to a group that can participate in a polymerization reaction by active radicals or acids generated from a polymerization initiator. Examples of polymerizable groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxiranyl , Oxetanyl, etc. 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 vertically aligned liquid crystal cured film is adjacent to the horizontally aligned liquid crystal cured film, both the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film are cured products of polymerizable liquid crystal compounds having at least one radically polymerizable group In this case, it is easy to improve the adhesiveness between the continuously formed horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film.

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 enabling dense film thickness control. Also, as the phase order structure in the thermotropic liquid crystal, it may be a nematic liquid crystal or a smectic liquid crystal. The polymerizable liquid crystal compound can be used alone or in combination of two or more.

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, and either polymerizable liquid crystal compound may be used alone, or both polymerizable liquid crystal compounds may be mixed. Liquid crystal compounds are used. It is preferable to contain a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion from the viewpoint that the effect of suppressing oblique reflection hue at the time of black display 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) has π electrons in a direction [crossing direction (b)] intersecting with the major axis direction (a). (D) Polymerization defined by the following formula (i) where the total of π electrons present in the major axis direction (a) is N(πa), and the total molecular weight present in the major axis direction is N(Aa) The π-electron density of the long axis direction (a) of the liquid crystal compound: D(πa)=N(πa)/N(Aa) (i) Polymerization defined by the following formula (ii) where the total of π electrons present in the crossing direction (b) is N(πb) and the total molecular weight present in the crossing direction (b) is N(Ab) The π-electron density of the cross direction (b) of the liquid crystal compound: D(πb)=N(πb)/N(Ab) (ii) satisfy 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. ・In the case of a compound having, for example, a rod-like structure, the long-axis direction (a) is the long-axis direction of the rod. ・Number of π electrons N(πa) present in the major axis direction (a) does not include π electrons that disappear due to polymerization. ・The number of π electrons N(πa) present in the major axis direction (a) is the total number of π electrons on the major axis and their conjugated π electrons, for example, including those present in the major axis direction (a) and satisfying Hückel The number of π-electrons present on the ring of the rule (Huckel rule). ・Number of π electrons N(πb) present in the crossing direction (b) does not include π electrons that disappear due to polymerization reaction. The polymerizable liquid crystal compound satisfying the above has a mesogen structure in the long axis direction. This mesogen structure expresses a liquid crystal phase (nematic phase, smectic phase).

A nematic phase or a smectic phase can be formed by coating a polymerizable liquid crystal compound satisfying the above (A) to (D) on the film (layer) forming a cured liquid crystal film, and heating to a temperature above the phase transition temperature. In the nematic phase or smectic phase formed by aligning the polymerizable liquid crystal compound, the long axis directions of the polymerizable liquid crystal compound are usually aligned so that they become parallel to each other, and the long axis direction becomes the alignment direction of the nematic phase . If such a polymerizable liquid crystal compound is made into a film and polymerized in a state of a nematic phase or a smectic phase, a polymer including a polymer polymerized in a state aligned along the major axis direction (a) can be formed. physical film. 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 crossing direction (b) be λbmax. λbmax is usually 300 nm to 400 nm. The density of π electrons satisfies the above formula (iii), and the π electron density in the cross direction (b) is greater than the π electron density in the long axis direction (a), so it becomes a linearly polarized ultraviolet light (wavelength of λbmax) is larger than the polymer film that absorbs linearly polarized ultraviolet light (wavelength λbmax) having a vibrating surface in the long axis direction (a). The ratio (absorbance in the cross direction (b) of linearly polarized ultraviolet rays/absorbance in the major axis direction (a)) exceeds 1.0, preferably 1.2 or more, and is usually 30 or less, for example, 10 or less.

Generally, many polymerizable liquid crystal compounds having the above-mentioned characteristics show reverse wavelength dispersion. 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 so-called aromatic group here means that the number of π electrons possessed by the ring structure is [4n+2] according to Hückel's rule, for example, it can also have more than 2 through a divalent linking group as follows (Ar-1)～ Ar group exemplified by (Ar-23). Here, n represents an integer. In the case of forming a ring structure containing heteroatoms such as -N= or -S-, it also includes the case of non-covalent bond electron pairs on these heteroatoms that satisfy Huckel's rule and have aromaticity. Preferably, at least one of nitrogen atom, oxygen atom, and sulfur atom is contained in the aromatic group. The aromatic group contained 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 there are two or more aromatic groups contained in the divalent group Ar, the two or more aromatic groups can also be bonded to each other by a single bond, -CO-O-, -O-, etc. . 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 be substituted by a halogen atom, an alkyl group having 1 to 4 carbons, a fluoroalkyl group having 1 to 4 carbons, a carbon number 1 to 4 alkoxy groups, cyano groups or nitro groups, carbon atoms constituting the divalent aromatic groups or divalent alicyclic hydrocarbon groups may be substituted with oxygen atoms, sulfur atoms or nitrogen atoms. L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group. k and l independently represent integers from 0 to 3, and satisfy the relationship of 1≦k+l. Here, in the case of 2≦k+l, B ¹ and B ² , and G ¹ and G ² may be the same as or different from each other. E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbons, and here, more preferably an alkanediyl group having 4 to 12 carbons. Also, the hydrogen atom contained in the alkanediyl group may be substituted by a halogen atom, and the -CH ₂ - contained in the alkanediyl group may be substituted by -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 preferably independently 1,4-phenylenediyl groups which may be substituted by at least one substituent selected from the group consisting of halogen atoms and alkyl groups with 1 to 4 carbons. 1,4-cyclohexanediyl substituted by at least one substituent in the group consisting of a free halogen atom and an alkyl group with 1 to 4 carbons, more preferably 1,4-phenylenediyl substituted by methyl, 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 plurality of G ¹ and G ² is a divalent alicyclic hydrocarbon group, and it is more preferable that at least one of G ¹ and G ² bonded to L ¹ or L ² is Divalent alicyclic hydrocarbon group.

L ¹ and L ² are preferably each independently 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. More preferably, L ¹ and L ² are each independently 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 further preferably each independently a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or -OCO-.

B ¹ and B ² are preferably each independently 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. More preferably, B ¹ and B ² are each independently 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 further preferably each independently 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, methyl group, etc. Acryloxy group, oxirane group, and oxetanyl group, etc. 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 furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyridine ring, pyrimidine ring, triazole ring, and triazole ring. , pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, and morpholine ring, etc. 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, it is preferable that the nitrogen atom 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, especially preferably 16 or more . Moreover, it is preferably 30 or less, more preferably 26 or less, and still more preferably 24 or less.

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

[chemical 5]

In formulas (Ar-1) to (Ar-23), the mark * denotes a linking part, and Z ⁰ , Z ¹ and Z ² independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 12 carbons, a cyano group, Nitro, alkylsulfinyl with 1 to 12 carbons, alkylsulfonyl with 1 to 12 carbons, carboxyl, fluoroalkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, Alkylthio with 1 to 12 carbons, N-alkylamino with 1 to 12 carbons, N,N-dialkylamino with 2 to 12 carbons, N-alkylamine with 1 to 12 carbons Sulfonyl or N,N-dialkylsulfamoyl with 2 to 12 carbons. In addition, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

Q ¹ and Q ² independently represent -CR ^2' R ^3' -, -S-, -NH-, -NR ^2' -, -CO- or -O-, R ^2' and R ^3' independently represent hydrogen Atoms or alkyl groups with 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 independently represent a hydrogen atom, a cyano group, a methyl group or a halogen atom, and m represents an integer of 0-6.

As the aromatic hydrocarbon groups in Y ¹ , Y ² and Y ³ , there may be mentioned: phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl and other aromatic hydrocarbon groups with 6 to 20 carbon atoms, preferably phenyl, Naphthyl, more preferably phenyl. Examples of the aromatic heterocyclic group include furan, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl, etc., having at least one heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom, having 4 to 20 carbon atoms. The aromatic heterocyclic group is preferably furan, thienyl, pyridyl, thiazolyl, and benzothiazolyl.

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

Z ⁰ , Z ¹ and Z ² are preferably each independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 12 carbons, a cyano group, a nitro group, or an alkoxy group with 1 to 12 carbons, and Z ⁰ is even more preferably is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyano group, and ^Z1 and ^Z2 are more 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 preferred.

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 also form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . Examples of the aromatic heterocyclic group include those described above as the aromatic heterocyclic ring that Ar may have, for example, a pyrrole ring, an imidazole ring, a pyrroline ring, a pyridine ring, a pyridine ring, a pyrimidine ring, and an indole ring. , quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring, etc. This aromatic heterocyclic group may have a substituent. In addition, Y ¹ may form 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.

Also, 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) "). 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) [In the formula (Y), P11 represents a polymerizable group; A11 represents a 2-valent alicyclic hydrocarbon group or a 2-valent aromatic hydrocarbon group; the 2-valent alicyclic hydrocarbon group And the hydrogen atom contained in the divalent aromatic hydrocarbon group can be replaced by a halogen atom, an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, a cyano group or a nitro group. The hydrogen atoms contained in the alkyl group and the alkoxy group with a carbon number of 1 to 6 can be replaced by a fluorine atom; B11 represents -O-, -S-, -CO-O-, -O-CO-, -O- CO-O-, -CO-NR ¹⁶ -, -NR ¹⁶ -CO-, -CO-, -CS- or a single bond; R ¹⁶ represents a hydrogen atom or an alkyl group with 1 to 6 carbons; B12 and B13 are independent Indicates -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- or a single bond; E11 represents an alkanediyl group with 1 to 12 carbons, the hydrogen atom contained in the alkanediyl group can be replaced by an alkoxy group with 1 to 5 carbons, and the alkoxy group contained in the alkoxy group A hydrogen atom may be substituted by a halogen atom; and -CH ₂ - constituting the alkanediyl group may be substituted by -O- or -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-. Specifically, methylene, ethylidene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6 -diyl, heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl, undecane-1, 11-diyl and dodecane-1,12-diyl and other linear alkanediyl groups with 1 to 12 carbon atoms; -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - wait. As B11, -O-, -S-, -CO-O-, -O-CO- are preferable, and -CO-O- is more preferable among them. As B12 and B13, it is preferred to be independently -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O )-O-, wherein, more preferably is -O- or -OC(=O)-O-.

[式(P-11)～(P-15)中， R¹⁷ ～R²¹ 分別獨立表示碳數1～6之烷基或氫原子]The polymerizable group represented by P11 is preferably a radically polymerizable group or a cationically polymerizable group in terms of high polymerization reactivity, especially photopolymerization reactivity, in terms of ease of handling and production of liquid crystal compounds. In terms of ease, the polymerizable group is preferably a group represented by the following formula (P-11) to formula (P-15). [chemical 6]

[In the formulas (P-11) to (P-15), R ¹⁷ to R ²¹ independently represent an alkyl group with 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. The group represented by P11-B11- is further preferably an acryloxy group or a methacryloxy group.

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) (In the formula, A12～A14 have the same meaning as A11 independently, B14～B16 have the same meaning as B12 independently, B17 and B11 have the same meaning, E12 has the same meaning as E11; F11 represents a hydrogen atom, an alkane with 1 to 13 carbons group, alkoxy group with 1 to 13 carbons, cyano group, nitro group, trifluoromethyl group, dimethylamino group, hydroxyl group, hydroxymethyl group, formyl group, sulfo group (-SO ₃ H), carboxyl group, carbon An alkoxycarbonyl group or a halogen atom with the number 1 to 10, the -CH ₂ - constituting the alkyl and alkoxy groups may be substituted with -O-)

Specific examples of the polymerizable liquid crystal compound (Y) include: "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 nematic liquid crystal material" is a compound with a polymerizable group; Japanese Patent Laid-Open No. 2010-31223, Japanese Patent Laid-Open No. 2010-270108, Polymerizable liquid crystals described in JP-A-2011-6360 and JP-A-2011-207765.

Specific examples of the polymerizable liquid crystal compound (Y) include the following formulas (I-1) to (I-4), formulas (II-1) to (II-4), and formulas (III-1 )～Formula (III-26), Formula (IV-1)～Formula (IV-26), Formula (V-1)～Formula (V-2) and Formula (VI-1)～Formula (VI-6) The indicated compound. 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 present invention, when a polymerizable liquid crystal compound exhibiting smectic liquid crystallinity is used as a polymerizable liquid crystal compound forming a vertical alignment liquid crystal cured film, from the viewpoint of realizing a higher degree of alignment order, the polymerizable liquid crystal The compound is more preferably a higher smectic phase (higher smectic liquid crystal state). 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 phase, smectic K phase, and smectic L phase, and among these, smectic B phase, smectic F phase, and smectic I phase are more preferable. Liquid crystallinity may be a thermotropic liquid crystal or a lyotropic liquid crystal, and a thermotropic liquid crystal is preferable from the point which can realize dense film thickness control. In addition, the polymerizable liquid crystal compound exhibiting smectic liquid crystallinity may be a monomer, or an oligomer or polymer obtained by polymerizing a polymerizable group.

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 vertical alignment liquid crystal cured film . Examples of polymerizable groups include (meth)acryloxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, oxiranyl, and oxygen heterocycles. Butyl, etc., among them, it is preferable to include (a base) 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) [In formula (Z), X ^1z and X ^2z independently represent divalent An aromatic group or a divalent alicyclic hydrocarbon group, where the hydrogen atoms contained in the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted by a halogen atom, an alkyl group having 1 to 4 carbon atoms, a carbon A fluoroalkyl group with a number of 1 to 4, an alkoxy group with a carbon number of 1 to 4, a cyano group or a nitro group, the carbon atoms constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be replaced by oxygen atoms or sulfur Atom or nitrogen atom; However, at least one of X ^1z and X ^2z is a 1,4-phenylene group that may have a substituent or a cyclohexane-1,4-diyl group that may have a substituent; Y ^1z is a single A bond or a divalent linking group; nz is 1 to 3, and when nz is 2 or more, the plural X ^1z may be the same or different from each other; X ^2z may be the same as any one or all of the plural X ^1z , It can also be different; and, when nz is 2 or more, the plurality of Y ^1z can be the same or different from each other; in terms of liquid crystallinity, nz is preferably 2 or more; U ^1z represents a hydrogen atom or (methyl ) acryloxy; 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 alkane with a carbon number of 1 to 20 that may have a substituent The -CH ₂ - constituting the alkanediyl group can be substituted by -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 , at least one of X ^1z and X ^2z is a 1,4-phenylene group that may have a substituent, or a cyclohexane-1,4-diyl group that may have a substituent, preferably trans-cyclohexane Alkane-1,4-diyl. Examples of substituents that may be optionally substituted with 1,4-phenylene or optionally substituted cyclohexane-1,4-diyl include carbon such as methyl, ethyl, and butyl. Alkyl groups of 1 to 4, cyano groups, chlorine atoms, fluorine atoms and other halogen atoms. Preferably it is unsubstituted.

Also, the polymerizable liquid crystal compound (Z) is in formula (Z), formula (Z1): -(X ^1z -Y ^1z -) _nz -X ^2z - (Z1) [wherein, X ^1z , Y ^1z , X ^2z and nz each represent the same meaning as above] [hereinafter referred to as a partial structure (Z1)] is preferably an asymmetric structure 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. Also, a compound in which nz is 2 and two Y ^1z have the same structure as each other, and two X ^1z have the same structure as each other, and one X ^2z has a structure different from the two X ^1z is also exemplified. Liquid crystal compound (Z); among the two X ^1z , the X ^1z bonded to the W ^1z has a different structure from the other X ^1z and X ^2z , and the other X ^1z and X ^2z have the same structure as each other. Liquid crystal compound (Z). Furthermore, it can be enumerated: nz is 3, a compound in which three Y ^1z have the same structure as each other, and any one of 3 X ^1z and 1 X ^2z is a polymerizable liquid crystal compound having a structure different from the other three ( Z).

Y ^1z is preferably -CH ₂ CH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ O-, -COO-, -OCOO-, 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 , the Y ^1z bonded to X ^2z is more preferably -CH ₂ CH ₂ - or CH ₂ O -. When both X ^1z and X ^2z have the same structure, it is preferable that two or more Y ^1z having different bonding modes exist. When there are a plurality of Y ^1z having different bonding methods, it becomes an asymmetric structure, and therefore tends to easily exhibit smectic liquid crystallinity.

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

As the alkanediyl group represented by V ^1z and V ^2z , there may be mentioned: 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 Diyl, tetradecane-1,14-diyl, and eicosane-1,20-diyl, 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.

Examples of the substituent that the alkanediyl group optionally has include a cyano group and a halogen atom, and the alkanediyl group is preferably unsubstituted, more preferably an unsubstituted straight-chain alkanediyl group.

W ^1z and W ^2z are preferably a single bond, -O-, -S-, -COO- or OCOO- independently of each other, 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 exhibiting high-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 them, preferably selected from 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) represented by the group of compounds At least 1 of them. 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 300-400 nm in wavelength, and the polymerizable liquid crystal compound forming the vertically aligned liquid crystal cured film preferably has at least one absorption maximum between 300-400 nm in wavelength. Polymeric liquid crystal compound with maximum absorption wavelength. When the photopolymerization initiator is contained in the polymerizable liquid crystal composition, there is a possibility that the polymerization reaction and gelation of the polymerizable liquid crystal compound may proceed during long-term storage. However, if the maximum absorption wavelength of the polymerizable liquid crystal compound is 300 to 400 nm, even if it is exposed to ultraviolet light during storage, it can effectively suppress the generation of reactive species from the photopolymerization initiator and the generation of reactive species by the reactive species. The polymerization reaction and gelation of the polymerizable liquid crystal compound can be carried out. Therefore, it becomes advantageous at the point of long-term stability of a polymerizable liquid crystal composition, and the uniformity of the orientation of the obtained liquid crystal cured film, and 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 that can dissolve the polymerizable liquid crystal compound, and examples thereof include chloroform and the like.

In the laminate formed by laminating the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film with an adhesive layer, it is considered that it is suitable for pressure-sensitive adhesion in terms of thinning the laminated body or improving the flexibility. Compared with other adhesives, energy ray hardening adhesives are advantageous. However, in the case where 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, in a laminate including the vertically aligned liquid crystal cured film During formation, since the vertically aligned liquid crystal cured film exhibits absorption in the above-mentioned wavelength range, it is difficult to use an ultraviolet curable adhesive that is cured by light (ultraviolet light) in the above-mentioned wavelength range to combine the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film. And other layers are laminated with higher adhesion. Since the present invention can continuously form a vertically aligned liquid crystal cured film on a horizontally aligned liquid crystal cured film without an adhesive layer, it is advantageous in reducing the thickness of the laminate. In addition, it can avoid the above-mentioned problems related to adhesion. In many cases, a polymeric liquid crystal compound that exhibits so-called inverse wavelength dispersion, which has a maximum absorption in the wavelength region of 300 to 400 nm, is used in the composition of the laminate, so it is possible to obtain a thin laminate with high optical characteristics. Also beneficial.

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 to 99.5 parts by mass, preferably 80 to 99 parts by mass relative to 100 parts by mass of the solid content of the polymerizable liquid crystal composition parts, more preferably 85 to 98 parts by mass, still more preferably 90 to 95 parts by mass. 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 used to form 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 forming a vertical alignment liquid crystal cured film is usually applied on a horizontal liquid crystal cured film or the like in a state dissolved in a 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 water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxy Alcohol solvents such as ethyl alcohol 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, Ketone solvents such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; fatty acids such as ethyl cyclohexane Cyclic hydrocarbon solvents; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorinated solvents such as chloroform and chlorobenzene; dimethylacetamide, dimethyl Amide-based solvents such as methylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used alone or in combination of two or more. Among these, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide-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 weight, based on 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 be 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 Salt. 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 For BASF Japan Co., Ltd. Company), 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 N-1919, Adeka arc Luz NCI-831, Adeka arc Luz NCI-930 (manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP ( The above are manufactured by Nihon Siber Hegner Co., Ltd.) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).

As far as the photopolymerization initiator can make full use of the energy emitted from the light source and is excellent in productivity, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and α-benzene is preferred. Acetone-based polymerization initiators, oxime-based photopolymerization initiators.

Examples of α-acetophenone compounds include: 2-methyl-2-metholinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1- (4-𠰌linylphenyl)-2-benzylbutan-1-one and 2-dimethylamino-1-(4-𠰌linylphenyl)-2-(4-methylphenyl Methyl) butane-1-one, etc., more preferably 2-methyl-2-?olinyl-1-(4-methylthiophenyl)propane-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 (manufactured by BASF Japan Co., Ltd.), SEIKUOL BEE (manufactured by Seiko Chemical Co., Ltd.), and the like.

The oxime-based photopolymerization initiator generates radicals such as phenyl radicals and methyl radicals when irradiated with light. The polymerization of the polymerizable liquid crystal compound proceeds suitably by the radical, and among them, an oxime-based photopolymerization initiator that generates a methyl radical is preferable in terms of high polymerization reaction initiation efficiency. Moreover, from a viewpoint of advancing a polymerization reaction more efficiently, it is preferable that it is a photoinitiator which can utilize the ultraviolet-ray of wavelength 350 nm or more efficiently. As a photopolymerization initiator capable of efficiently utilizing ultraviolet light having a wavelength of 350 nm or more, a trioximide 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. azole compounds. Examples of carbazole compounds containing an oxime structure include: 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethyl ketone, 1-[ 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like. Examples of commercially available oxime ester-based photopolymerization initiators include: Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (the above are manufactured by BASF Japan Co., Ltd.), Adeka Optomer N-1919, Adeka arc Luz NCI-831 (the above are manufactured by ADEKA Co., Ltd.), etc.

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 refers to an additive that has the function of adjusting the fluidity of the polymerizable liquid crystal composition and making the coating film obtained by coating the composition flatter. For example, silicone-based, polyacrylate-based and Perfluoroalkyl leveling agent. As the leveling agent, commercially available products can be used, specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (the above are manufactured by Toray Dow Corning Co., Ltd.) ); KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (the above are manufactured by Shin-Etsu Chemical Co., Ltd.); TSF4460 (the above are all manufactured by Momentive High-tech Materials Japan Co., Ltd.); Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (all above are manufactured by Sumitomo 3M (stock)); Megafac (registered trademark) R-08, Megafac R-30, Megafac R-90, Megafac F-410, Megafac F-411, Megafac F-443, Megafac 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 Co., Ltd.); Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (all of the above are Mitsubishi 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 name E1830, trade name E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.); BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (both trade names: manufactured by BM Chemie Co., Ltd.) and the like. A leveling agent can 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 is easily aligned, and the obtained liquid crystal cured film tends to become smoother, which is preferable.

By formulating antioxidants, the polymerization reaction of polymerizable liquid crystal compounds can be controlled. As an antioxidant, it can be a primary antioxidant selected from phenolic antioxidants, amine antioxidants, quinone antioxidants, and nitroso antioxidants, or it can be selected from phosphorus antioxidants and sulfur antioxidants. The second antioxidant. In order to polymerize the polymerizable liquid crystal compound without disturbing the alignment of the polymerizable liquid crystal compound, the content of the antioxidant is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound parts, more preferably 0.1 to 3 parts by mass. Antioxidants can be used individually or in combination of 2 or more types.

等𠮿酮類；蒽及烷基醚等具有取代基之蒽類；啡噻𠯤；紅螢烯。光增感劑可單獨使用或組合2種以上使用。光增感劑之含量相對於聚合性液晶化合物100質量份，通常為0.01～10質量份，較佳為0.05～5質量份，進而較佳為0.1～3質量份。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 prepared by mixing a vertical alignment accelerator and a polymerizable liquid crystal compound with components other than the vertical alignment accelerator and a polymerizable liquid crystal compound such as a solvent or a photopolymerization initiator at a specific temperature. obtained by stirring or the like.

In the present invention, the vertical alignment liquid crystal cured film preferably satisfies the following formula (2). RthC(450)/RthC(550)≦1 (2) [In formula (2), RthC(450) represents the retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm; RthC(550) represents the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm phase difference] By satisfying the above-mentioned formula (2), it is possible to suppress the decrease in ellipticity on the short-wavelength side in the laminate including the vertically aligned liquid crystal cured film, and to improve the oblique reflection hue at the time of black display. The value of RthC(450)/RthC(550) of the vertical alignment liquid crystal cured film is more preferably 0.95 or less, further preferably 0.92 or less, especially preferably 0.9 or less, and preferably 0.7 or more, more preferably 0.75 or more, and further Preferably it is 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 is given by the following formula: RthC(λ)=((nxC(λ)+nyC(λ))/2－nzC(λ))×dC (Here, nxC(λ) in the formula represents the in-plane principal refractive index of the vertically aligned liquid crystal cured film at a wavelength of λ nm, and nyC(λ) represents the in-plane orthogonal to nxC(λ) at a wavelength of λ nm The refractive index in the direction, nzC(λ) represents the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of λ nm. In the case of nxC(λ)=nyC(λ), nxC(λ) can be set as the film Refractive index in any direction in the plane, 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, black display occurs It tends to be excellent in the suppression effect of oblique reflection hue change. 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 perspective 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, and more preferably -90 nm or more, More preferably, it is not less than -80 nm, more preferably not more than -40 nm, further preferably not more than -50 nm.

[Horizontal Alignment Liquid Crystal Curing Film] The cured product of the polymerizable liquid crystal composition formed by curing the horizontally aligned liquid crystal cured film-based polymeric liquid crystal compound that constitutes the laminate of the present invention in a state aligned horizontally with respect to the plane of the liquid crystal cured film preferably has at least A liquid crystal cured film formed by curing a polymerizable liquid crystal compound of 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 horizontal alignment 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. In the case where the horizontal alignment liquid crystal cured film is adjacent to the vertical alignment liquid crystal cured film, if both the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film are cured products of polymerizable liquid crystal compounds having at least one free radical polymerizable group , it is easy to improve the adhesion between the continuously formed horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film. In particular, there is a tendency for the adhesiveness between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film to be further improved, and it is preferable that the polymerizable liquid crystal compound constituting the horizontally aligned liquid crystal cured film and the polymerizable liquid crystal compound constituting the vertically aligned liquid crystal cured film have the same Similar or identical polymerizable groups, more preferably both the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film are composed of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a (meth)acryl group.

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) exemplified as a polymerizable liquid crystal compound that can be used to form a vertically aligned liquid crystal cured film can be used, and among them, it is preferable to exhibit a so-called reverse wavelength dispersion As a polymerizable liquid crystal compound, 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 horizontal alignment liquid crystal cured film is, for example, 70 to 99.5 parts by mass, preferably 80 to 100 parts by mass of the solid content of the polymerizable liquid crystal composition. 99 mass parts, More preferably, it is 85-98 mass parts, More preferably, it is 90-95 mass parts. 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, what was illustrated above as the component which can be used for a vertical alignment liquid crystal cured film is mentioned, and only 1 type may be used, respectively, and 2 or more types may be used in combination.

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

Also, in the present invention, for the same reason as the case where the vertically aligned liquid crystal cured film has at least one maximum absorption at a wavelength of 300 to 400 nm is advantageous, it is preferable that the horizontally aligned liquid crystal cured film has a wavelength of 300 to 400 nm. There is at least one maximum absorption between 400 nm. In a preferred aspect of the present invention, the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film adjacent to the above-mentioned vertically aligned liquid crystal cured film or placed at a position where light is irradiated when the above-mentioned vertically aligned liquid crystal cured film is laminated All have at least one maximum absorption between 300 and 400 nm in wavelength.

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 λ nm, ReA(λ)=(nxA(λ)-nyA(λ))×dA(where , nxA(λ) represents the main refractive index at the wavelength λ nm in the plane of the horizontally aligned liquid crystal cured film, and nyA(λ) represents the main refractive index at the wavelength λ nm in the direction perpendicular to the direction of nxA in the same plane as nxA Refractive index, dA represents the film thickness of the horizontally aligned liquid crystal cured film)]

When the horizontally aligned liquid crystal cured film satisfies the formula (1), the horizontally aligned liquid crystal cured film exhibits the so-called inverse wavelength dispersion in which the in-plane retardation value at short wavelengths is smaller than that at long wavelengths. By combining such a horizontally aligned liquid crystal cured film and the aforementioned 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 terms of improving the reverse wavelength dispersion and further improving 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 0.70 or more, more preferably 0.78 or more, And it is preferably 0.95 or less, more preferably 0.92 or less.

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): wavelength λ(nm ) under the in-plane retardation value of the horizontally aligned liquid crystal cured film), as long as the three-dimensional refractive index and film thickness dA are adjusted.

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), the meaning of ReA(λ) is the same 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 application of the laminate (elliptic polarizer) including the horizontally aligned liquid crystal cured film to an organic EL display device will be improved. The effect of the time black displaying the front reflection hue of the time becomes remarkable. A more preferable range of the in-plane retardation value is 130 nm≦ReA(550)≦150 nm.

[Manufacturing method of laminated body] The laminate of the present invention can be produced, for example, by a method comprising the following steps in the following order: Forming a coating film of a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film containing a polymerizable liquid crystal compound, and forming a horizontal alignment liquid crystal cured film from the coating film (hereinafter also referred to as "horizontal alignment liquid crystal cured film forming step") );and Step of 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") ). When the vertically aligned liquid crystal cured film and the horizontally aligned liquid crystal cured film are adjacent to each other in the laminate of the present invention, it is preferable to sequentially and continuously perform the forming step of the horizontally aligned liquid crystal cured film and the forming step of the vertically aligned liquid crystal cured film. Furthermore, it is preferable to include a step of forming a coating film of a composition for forming a horizontal alignment film and forming a horizontal alignment film from the coating film (hereinafter, also referred to as a "horizontal alignment film forming step") before forming a horizontal alignment liquid crystal cured film. ), and preferably sequentially and continuously perform the step of forming the horizontal alignment film, the step of forming the horizontal alignment cured film and the step of forming the vertical alignment cured film. By the manufacturing method including the step of forming the horizontal alignment film, a laminate including the horizontal alignment film, the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film can be obtained.

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 a method including the following steps: Coating the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on a substrate or an alignment film to obtain a coating film; drying the above-mentioned coating film to form a dry coating film; and The dry coating film is irradiated with active energy rays to form a horizontally aligned liquid crystal cured film.

The coating film of the polymerizable liquid crystal composition can be formed by, for example, coating the polymerizable liquid crystal composition for forming a cured film of a horizontal alignment liquid crystal on a substrate or an alignment film described later. As a base material, 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 base material, for example, polyolefins such as polyethylene, polypropylene, and northylene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; Polymethacrylates; Polyacrylates; Cellulose esters such as triacetylcellulose, diacetylcellulose, and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Polyethylene; Polyether ketone; polyether ketone; plastics such as polyphenylene sulfide and polyphenylene 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. On the surface of the substrate, there can be a protective layer formed of acrylic resin, methacrylic resin, epoxy resin, oxetane resin, urethane resin, melamine resin, etc., and polysilicon resin can also be implemented. Oxygen treatment such as release treatment, corona treatment, plasma treatment and other surface treatments.

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 Fujifilm Co., Ltd. such as FUJITAC film; Konica Minolta Opto such as "KC8UX2M", "KC8UY", and "KC4UY" Cellulose ester base material manufactured by Co., Ltd. Examples of commercially available cyclic olefin-based resins include: Cyclic olefin-based resins manufactured by Ticona Corporation (Germany) such as "Topas (registered trademark)"; JSR Co., Ltd. such as "ARTON (registered trademark)" Cyclic olefin-based resins manufactured by the company; Cyclic olefin-based resins manufactured by Zeon Corporation Co., Ltd. such as "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)"; "Apel" (registered trademark) and the like Cyclic olefin-based resin manufactured by Mitsui Chemicals Co., Ltd. Commercially available cyclic olefin-based resin substrates can also be used. Examples of commercially available cyclic olefin-based resin substrates include Cyclic olefin-based resin substrates manufactured by Sekisui Chemical Industry Co., Ltd. such as "S-SINA (registered trademark)" and "SCA40 (registered trademark)". Cyclic olefin-based resin substrates manufactured by Optes Co., Ltd. such as "Zeonor Film (registered trademark)"; Cyclic olefin-based resin substrates manufactured by JSR Co., Ltd. such as "ARTON Film (registered trademark)".

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 handleability of the substrate.

As a method of applying the polymerizable liquid crystal composition to a base material, etc., there may be mentioned: spin coating method, extrusion method, gravure coating method, die coating method, rod coating method, applicator method, etc. Known methods such as printing methods such as the cloth method and the flexo method.

Next, a dry coating film is formed by removing a solvent by drying etc. 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 horizontally with respect 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 make the polymerizable liquid crystal compound phase transition to the liquid crystal phase state, the liquid crystal phase transition temperature must usually be above temperature. In order to remove the solvent contained in the polymerizable liquid crystal composition and make the polymerizable liquid crystal compound into a horizontal alignment state, for example, it may be heated to the liquid crystal phase transition temperature (smectic temperature) of the polymerizable liquid crystal compound contained in the above polymerizable liquid crystal composition. The temperature above the phase transition temperature or nematic phase transition temperature). 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 that all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition have the same composition as that in the polymerizable liquid crystal composition. The temperature of a mixture of polymerizable liquid crystal compounds mixed in a ratio, measured in the same manner as in the case of using one kind of polymerizable liquid crystal compound. Furthermore, generally speaking, it is known that the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the above polymerizable liquid crystal composition is also lower than that of the single component of the polymerizable liquid crystal compound.

The heating time can be appropriately determined according to 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 to the liquid crystal phase transition temperature or higher of the polymerizable liquid crystal compound, or may be performed separately, but it is preferably performed simultaneously from the viewpoint of improving productivity. It is also possible to set to moderately remove the coating film under the condition that the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize before heating to the liquid crystal phase transition temperature or higher of the polymerizable liquid crystal compound The pre-drying step of the solvent in it. 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 determined according to the polymerizable liquid crystal compound used. The type, the type of solvent, its boiling point, and its amount are appropriately determined.

Next, in the obtained dried coating film, the polymerizable liquid crystal compound is polymerized while maintaining the horizontal alignment state of the polymerizable liquid crystal compound, thereby forming a horizontally 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, as the light irradiated to the dry coating film, it can be determined according to the type of the polymerization initiator contained in the dry coating film, the type of the polymerizable liquid crystal compound (especially, the polymerizability of the polymerizable liquid crystal compound), The type of base) and its amount are properly selected. 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 use a method that can perform photopolymerization by ultraviolet light. The kind of the polymerizable liquid crystal compound or the polymerization initiator contained in the polymerizable liquid crystal composition is selected in advance. In addition, during polymerization, the polymerization temperature can also be controlled by irradiating light while cooling the dried coating film with an appropriate cooling mechanism. By employing such a cooling mechanism, 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 horizontally aligned liquid crystal cured film can be appropriately formed. Furthermore, the polymerization reaction can also be accelerated by increasing the polymerization temperature within a range that does not cause problems due to heat during light irradiation (heat-induced deformation of the substrate, etc.). A patterned cured film can also be obtained by performing masking or development during photopolymerization.

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, and emission wavelengths. LED light sources with a range of 380-440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, etc.

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. When irradiated once or multiple times at such an intensity of ultraviolet radiation, 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 horizontal alignment liquid crystal cured film can be appropriately selected according to the display device to be used, preferably 0.2-5 μm, more preferably 0.2-4 μm, and still more preferably 0.2-3 μm.

In order to improve the alignment order of the horizontally aligned liquid crystal cured film, in the present invention, the coating film of the polymerizable liquid crystal composition for forming the horizontally aligned liquid crystal cured film is preferably formed in a horizontal direction relative to the plane of the obtained liquid crystal cured film On the horizontal alignment film with alignment restriction force. Therefore, the laminate of the present invention preferably includes a horizontal alignment film, and sequentially includes a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a vertical alignment liquid crystal cured film, and is more preferably a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a vertical alignment film. The liquid crystal cured films exist adjacent to each other sequentially. Furthermore, the alignment restriction force of the alignment film can be adjusted arbitrarily by the type of the alignment film, the surface state, or the rubbing conditions. Adjust arbitrarily.

As the horizontal alignment film, it is preferable to have solvent resistance that does not dissolve due to coating of the polymerizable liquid crystal composition, etc., and to have heat resistance for solvent removal or heat treatment for alignment of the polymerizable liquid crystal compound described below . Alignment films include alignment films containing alignment polymers, photo-alignment films, trench alignment films with concave-convex patterns or multiple grooves on the surface, and stretched films extending along the alignment direction. From a viewpoint, it is preferably a photo-alignment film.

As the alignment polymer, for example, polyamide or gelatin having an amide bond in the molecule, polyimide having an amide bond in the molecule, and polyamic acid which is a hydrolyzate thereof, polyamide Vinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyoxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylates. Among them, polyvinyl alcohol is preferred. The alignment polymer can be used alone or in combination of two or more.

Alignment films containing alignment polymers are usually coated on substrates with a composition of alignment polymers dissolved in solvents (hereinafter, sometimes referred to as "alignment polymer compositions"), and the solvent is removed. Or it can be obtained by coating the alignment polymer composition on the substrate, removing the solvent, and rubbing (rubbing method). As a solvent, what was mentioned above as a solvent which can be used for a polymerizable liquid crystal composition is illustrated.

The concentration of the alignment polymer in the alignment polymer composition should be within the range where the alignment polymer material can be completely dissolved in the solvent. Relative to the solution, the concentration of the alignment polymer is preferably 0.1 to 20% in terms of solid content, and more preferably Preferably about 0.1 to 10%.

As the alignment polymer composition, a commercially available alignment film material can also be directly used. Examples of commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industry Co., Ltd.), Optomer (registered trademark, manufactured by JSR Corporation), and the like.

As the method of applying the alignment polymer composition to the substrate, the same ones as those exemplified above as the method of applying the polymerizable liquid crystal composition to the substrate are exemplified.

Examples of methods for removing the solvent contained in the alignment polymer composition include natural drying, air drying, heat drying, and reduced pressure drying.

In order to impart an alignment-regulating force to the alignment film, a rubbing treatment (rubbing method) may be performed as needed. As a method of imparting an alignment restriction force by a rubbing method, a film of an alignment polymer formed on the surface of a substrate by applying an alignment polymer composition to the substrate and annealing the substrate with a rubbing film wound thereupon may be mentioned. The method of contacting the cloth and rotating friction roller. When performing the rubbing treatment, if masking is performed, a plurality of regions (patterns) having different alignment directions can also be formed on the alignment film.

In a suitable aspect of the present invention, the horizontal alignment film is a photo-alignment film formed of a polymer having (meth)acryl groups. When the horizontal alignment film has a polymerizable group similar to or identical to the polymerizable liquid crystal compound constituting the horizontal alignment cured liquid crystal film, there is a tendency for the adhesion between the horizontal alignment film and the horizontal alignment liquid crystal cured film to be further improved, so it is preferable to use The horizontal alignment film is formed of a polymer having a (meth)acryl group, and the horizontal alignment liquid crystal cured film is formed of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound having a (meth)acryl group. Furthermore, when the horizontal alignment cured film and the vertical alignment cured film are adjacent to each other, the adhesion of the horizontal alignment film, the horizontal alignment cured film, and the vertical alignment cured film is further improved, so it is more preferable that the horizontal alignment film is composed of The polymer with (meth)acryl group is formed, and both the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film are formed from a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound with (meth)acryl group.

A photoalignment film is usually removed by applying a composition comprising a polymer having a photoreactive group or a monomer and a solvent (hereinafter, sometimes referred to as a "photoalignment film forming composition") to a substrate. It is obtained by irradiating polarized light (preferably polarized UV) after solvent. 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 so-called photoreactive group refers to the group that produces liquid crystal 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, especially a group selected from a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond) , a group consisting of at least one nitrogen-nitrogen double bond (N=N bond) and 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 a photoreactive group having an N=N bond, for example, azophenyl group, azonaphthyl group, aromatic heterocyclic azo group, disazo group, formazan group, and those having an oxyazobenzene structure base. As a photoreactive group which has a C=O bond, a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group are mentioned, for example. These groups may have substituents such as alkyl, alkoxy, aryl, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and halogenated alkyl.

Among them, the photoreactive group that participates in the photodimerization reaction is preferred. In terms of the relatively small amount of polarized light irradiation required for photoalignment, and the fact that it is easy to obtain a photoalignment film with excellent thermal stability or stability over time, it is preferred. Preferred are azo group, cinnamoyl group and chalcone group. As a polymer having a photoreactive group, a polymer having an azo group or a cinnamonyl group is preferable, and this polymer is particularly preferable from the viewpoint of improving the adhesion between the horizontal alignment film and the horizontal alignment liquid crystal cured film. The terminal portion of the side chain becomes the cinnamic acid structure with the cinnamoyl group.

A photoalignment inducing layer can be formed on a substrate by coating the composition for forming a photoalignment film on the substrate. As the solvent contained in the composition, there may be mentioned the same solvents as those exemplified above as solvents usable in the polymerizable liquid crystal composition, and may be appropriately selected according to the solubility of the polymer or monomer having a photoreactive group. choose.

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

As a method of applying the composition for photoalignment film formation to a base material, the method similar to the method of applying an alignment polymer composition to a base material is 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 the product obtained by removing the solvent from the composition for forming a photoalignment film coated on the substrate, or it may be irradiated with polarized light from the substrate side to transmit the polarized light. form. Moreover, it is especially preferable if this polarized light is parallel light substantially. The wavelength of the polarized light to be irradiated is preferably in the wavelength range where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength of 250 to 400 nm is particularly preferable. As the light source used for the polarized light irradiation, xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF, ArF, etc. are listed, and high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are more preferable. . 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. By irradiating the light from the above-mentioned light source through an appropriate polarizing element, it is possible to irradiate polarized light UV. As the polarizing element, a polarizing filter, a polarizing filter such as Glan-Thomson, Glan-Taylor, or a wire-grid type polarizing element can be used.

In addition, when performing rubbing or polarized light irradiation, if masking is performed, it is also possible to form a plurality of regions (patterns) in which the directions of liquid crystal alignment are different.

The groove (groove) alignment film is a film with a concave-convex pattern or a plurality of grooves (grooves) on the film surface. When a polymerizable liquid crystal compound is applied to a film having a plurality of linear grooves arranged at equal intervals, liquid crystal molecules are aligned along the grooves.

As a method for obtaining a trench alignment film, it is possible to enumerate: after exposing the surface of the photosensitive polyimide film through an exposure mask having a pattern-shaped slit, developing and rinsing are performed to form a concave-convex pattern; A method of forming a layer of UV curable resin before curing on a plate-shaped master having grooves on the surface, transferring the formed resin layer to a substrate and then curing it; and a film of UV curable resin formed on the substrate before curing A method of pressing a roll-shaped master with a plurality of grooves to form concavities and convexities, and then hardening.

The thickness of the alignment film (or alignment film or photo-alignment film including alignment polymer) is usually 100-5000 nm, preferably 100-1000 nm, more preferably 100-500 nm, and more preferably 100-300 nm, Most preferably, it is 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 cohesive destruction of the alignment film in the laminate is less likely to occur.

In the step of forming the vertically aligned liquid crystal cured film, the vertically aligned liquid crystal cured film can be produced, for example, by a method including the following steps: Coating the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film on the horizontal alignment liquid crystal cured film to obtain a coating film; drying the above-mentioned coating film to form a dry coating film; and The dry coating film is irradiated with active energy rays to form a vertical alignment liquid crystal cured film.

Formation of the coating film of a polymeric liquid crystal composition can be performed by coating the polymeric liquid crystal composition for vertical alignment liquid crystal cured film formation on the horizontal alignment liquid crystal cured 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 the horizontal alignment liquid crystal cured film is mentioned.

As long as the laminated body of the present invention does not affect the effect of the present invention, the horizontal alignment liquid crystal cured film and the vertical alignment liquid crystal cured film can also be laminated via a layer (except the adhesive layer) that does not have a vertical alignment restriction force. As a layer which does not have such vertical alignment restrictive force, the cured resin layer for the purpose of improving or reinforcing the mechanical strength of a liquid crystal cured film, a hard coat layer, etc. are mentioned, for example. When the laminate of the present invention includes other layers as described above between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film, the thickness of the other layer is preferably 0.1 to 4 μm, more preferably 0.5 to 3 μm. μm. In the case where the laminate of the present invention includes other layers as described above between the horizontally aligned liquid crystal cured film and the vertically aligned liquid crystal cured film, it is only necessary to form other layers after forming the horizontally aligned liquid crystal cured film, and then form the other layers on the above-mentioned other layers. What is necessary is just to form the coating film of the polymeric liquid crystal composition for vertical alignment liquid crystal cured film formation.

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, even if the cured liquid crystal film formed adjacent to the cured resin layer is a thin film, the cured resin layer can sufficiently supplement the strength of the cured liquid crystal film as a protective layer or a reinforcing layer.

Next, by drying etc. to remove a solvent, a dry coating film is formed. 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. The order and conditions in this step are the same as those which can be adopted in the manufacturing method of the horizontal alignment liquid crystal cured film.

By irradiating the obtained dry coating film with active energy rays (more specifically, ultraviolet rays, etc.), the polymerizable liquid crystal compound is directly polymerized while maintaining the state of aligning the polymerizable liquid crystal compound in the vertical direction with respect to the plane of the coating film, and A vertical alignment liquid crystal cured film is formed. As a polymerization method, the same method as the method applicable to the manufacturing method of the horizontal alignment liquid crystal cured film is mentioned.

The thickness of the vertically aligned liquid crystal cured film can be appropriately selected according to the display device used, 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 present invention, the vertically aligned liquid crystal cured film is formed of a polymerizable liquid crystal composition containing a vertically aligned promoter, thereby obtaining a vertically aligned liquid crystal cured film with no or few alignment defects even without using an 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 tends to have excellent optical properties, especially when applied to an organic EL display device, the front and oblique reflection hues during black display The effect of suppressing changes is excellent. Moreover, since the step of forming an 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 comprising 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 comprising an extended film adsorbed with an anisotropic absorption pigment as a polarizing element is usually produced by sandwiching at least one side of the polarizing element with a transparent protective film through an adhesive, and the polarizing element is manufactured through the following steps: A step of uniaxially stretching a polyvinyl alcohol-based resin film, a step of adsorbing the dichroic dye by dyeing the polyvinyl alcohol-based resin film with a dichroic dye, and absorbing the dichroic dye with an aqueous solution of boric acid A step of treating the polyvinyl alcohol-based resin film, and a step of washing with water after the treatment with an aqueous solution of boric acid.

Polyvinyl alcohol-based resins are obtained by saponifying polyvinyl acetate-based resins. As the polyvinyl acetate-based resin, 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 previously subjected to a water immersion treatment 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 part by mass relative to 100 parts by mass of water 10 ^-3 to 1×10 ^-2 parts by mass. 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. parts by mass. 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 composition containing a liquid crystalline dichroic dye, a film obtained by coating a composition containing a dichroic dye and a polymerizable liquid crystal, and the like. 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 the horizontal alignment liquid crystal cured film is mentioned.

The thinner the film coated with the pigment having absorption anisotropy, the better, but if it is too thin, the strength tends to decrease and the processability tends to deteriorate. 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 above-mentioned dye having anisotropic absorption include films described in JP-A-2012-33249 and the like.

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

The elliptically polarizing plate of the present invention includes 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.

In one embodiment of the present invention, when the laminated body of the present invention is laminated with a polarizing film, it is preferable that the slow axis (optical axis) of the horizontal alignment liquid crystal cured film constituting the laminated body and the polarizing film Layers are stacked so that the angle formed by the absorption axes 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. As such a configuration, for example, an adhesive layer (sheet) for attaching an elliptical polarizing plate to a display element such as an organic EL, or for protecting the surface of a polarizing film or a liquid crystal cured film from damage or contamination protective film, etc.

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) , surface field emission display device (SED)), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device (such as grid light valve (GLV) display device, digital micromirror device (DMD) display device) and piezoelectric ceramic display, etc. Liquid crystal display devices include transmissive liquid crystal display devices, transflective liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices and projection liquid crystal display devices, etc. Either. 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 polarizing plate of the present invention is easy to significantly bring out its effect, It can be suitably used in organic electroluminescent (EL) display devices, and the laminate of the present invention can be suitably used in liquid crystal display devices and touch panel display devices. By using the laminate or elliptical polarizer of the present invention, it is easy to realize The thinning of the display device 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) The composition for forming a horizontal alignment film was prepared by using 5 parts by mass of a photo-alignment material with the following structure (weight average molecular weight: 30000) and 95 parts by mass of cyclopentanone (solvent) as components Mixing was performed, and the obtained mixture was stirred at 80° C. for 1 hour to obtain a composition for forming a horizontal alignment film. [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 In the absorption spectrum, the wavelength of maximum absorption was read from the obtained absorption spectrum, and 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): PaliocolorLC242 (BASF Corporation, registered trademark), 0.1 parts by mass of a leveling agent ("F-556" manufactured by DIC Corporation) and 3 parts by mass of a polymerization initiator Irg369 were added share. 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 Ionic compound A (molecular weight : 645) 1.5 parts by mass, silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass, and 2-dimethylamino-2-benzyl-1 as a photopolymerization initiator -6 parts by mass of (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) Formation of the horizontal alignment liquid crystal cured film After corona treatment was performed on the COP film (ZF14-50) manufactured by Zeon Corporation, the composition for forming the horizontal alignment film was coated with a bar coater and placed at 80°C. After drying for 1 minute, use a polarized UV irradiation device (SPOT CURE SP-9; manufactured by Ushio Electric Co., Ltd.) to perform polarized UV exposure at a wavelength of 313 nm with 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 by an ellipsometer and found to be 200 nm. Then, apply the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on the horizontally aligned film, heat it at 120°C for 60 seconds, and use a high-pressure mercury lamp (UNICURE VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.), The surface on which the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film was applied was irradiated with ultraviolet rays (accumulated light intensity at a wavelength of 365 nm in a nitrogen atmosphere: 500 mJ/cm ² ), thereby forming a horizontally aligned liquid crystal cured film, A laminate is obtained in which the substrate, the horizontal alignment film, and the horizontal alignment liquid crystal cured film are sequentially stacked adjacent to each other. The film thickness of the obtained horizontally aligned liquid crystal cured film was measured by an ellipsometer and found to be 1.1 μm.

<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 laminate comprising the above-mentioned substrate, horizontal alignment film, and horizontal alignment liquid crystal cured film, and bonded to the glass with a 25 μm pressure-sensitive adhesive manufactured by LINTEC. For the obtained laminate including glass, adhesive, horizontal alignment liquid crystal cured film, horizontal alignment film, and substrate, after confirming that there is no retardation of the substrate in advance, the horizontal alignment is measured using KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd. Re(450) and Re(550) of the liquid crystal cured film were calculated as α=Re(450)/Re(550). The results are shown in Table 1.

(6) Manufacture of Vertical Alignment Liquid Crystal Cured Film After performing corona treatment on the horizontal alignment liquid crystal cured film of the laminate comprising the base material, horizontal alignment film, and horizontal alignment liquid crystal cured film produced as described above, bar coating is used to The above-mentioned polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film was coated on a cloth machine, and heated at 120° C. for 60 seconds. Next, in a state heated to 120°C, ultraviolet rays were irradiated from the surface coated with the polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film using a high-pressure mercury lamp (UNICURE VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) (In a nitrogen atmosphere, the cumulative light intensity at a wavelength of 365 nm: 500 mJ/cm ² ), thereby forming a vertical alignment liquid crystal cured film, and obtaining a substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, and a vertical alignment liquid crystal cured film A laminate formed by successively stacking layers. The film thickness of the obtained vertical alignment liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Co., Ltd.), and it was 0.6 μm. The total film thickness T1 of the laminate from the surface of the horizontal alignment cured liquid crystal film opposite to the vertical alignment liquid crystal cured film to the surface of the vertical alignment liquid crystal cured film opposite to the horizontal alignment liquid crystal cured film was 1.7 μm.

<Measurement of Retardation Value of Vertically Aligned Liquid Crystal Cured Film> Corona treatment is performed on the surface of the vertical alignment liquid crystal cured film of the laminate including the substrate, horizontal alignment film, horizontal alignment liquid crystal cured film, and vertical alignment liquid crystal cured film produced by the above procedure, and the 25 μm pressure sensitive film manufactured by LINTEC Co., Ltd. is used. Adhesive to attach to glass. For the obtained laminate, after confirming that there is no phase difference in the base material in advance, use KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd. to change the incident angle of light on the sample for optical characteristic measurement to measure the cured film including vertical alignment liquid crystal and The front retardation value of the laminate of the horizontally aligned liquid crystal cured film, and the retardation value when the center of the phase advance axis is tilted by 40°. In addition, the front retardation value of the laminate including glass, adhesive, horizontal alignment liquid crystal cured film, horizontal alignment film, and substrate, and the retardation value when the center of the phase advance axis is inclined by 40° are measured by the same method . Then, the average refractive index at each wavelength was measured using the ellipsometer M-220 by JASCO Corporation about each of said vertical alignment liquid crystal cured film and horizontal alignment liquid crystal cured film. Moreover, the film thickness was measured using the Optical NanoGauge film thickness meter C12562-01 by Hamamatsu Photonics Co., Ltd. make. From the above-mentioned front phase difference value, the phase difference value when the phase advance axis is tilted by 40°, the average refractive index, and the value of film thickness, the technical data of Oji Instruments (http://www.oji-keisoku.co. jp/products/kobra/reference.html) as a reference to calculate the three-dimensional refractive index. According to the three-dimensional refractive index obtained, according to the following formula, calculate the optical characteristics of the laminate including the vertical alignment liquid crystal cured film and the horizontal alignment liquid crystal cured film, and the horizontal alignment liquid crystal cured film, and calculate the vertical alignment liquid crystal from the difference between the values From the values of Rth(450) and Rth(550) of the cured film, calculate αth=Rth(450)/Rth(550). The results are shown in Table 1. RthC(λ)=((nxC(λ)+nyC(λ))/2－nzC(λ))×dC In the above formula, RthC(λ) represents the retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of λ nm. Also, nxC(λ) represents the in-plane main refractive index of the vertically aligned liquid crystal cured film at a wavelength of λ nm, and nyC(λ) represents the refractive index in the direction perpendicular to nxC(λ) at a wavelength of λ nm , nzC(λ) represents the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of λ nm. In the case of nxC(λ)=nyC(λ), nxC(λ) can be set at any point in the film surface The refractive index of the direction, dC represents the film thickness of the vertically aligned liquid crystal cured film.

(7) Evaluation of laminates ＜Orientation evaluation of laminates＞ The obtained laminate was bonded to a glass of 5×5 cm×0.7 mm in thickness through 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 excluded and not counted. 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 as follows. First, the vertical 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□ were made for 100 pieces on the side of the laminated body of the obtained sample using a cutting machine. Cellotape (registered trademark) (manufactured by Nichiban Corporation) was attached to the obtained 100 cutouts, and after the Cellotape was peeled off, the number of peeled layers in the laminate was confirmed, and the adhesiveness was judged according to the following criteria. The results are shown in Table 1. Evaluation criteria: 〇: After the Cellotape was peeled off, there were less than 30 pieces peeled between the layers in the laminate. △: After Cellotape peeling, there were 30 or more and 59 or more blocks that were peeled between the layers in the laminate. ×: After Cellotape peeling, there were 60 or more blocks that peeled between layers in the laminate.

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, the substrate, horizontally aligned Film, horizontal alignment liquid crystal cured film and vertical alignment liquid crystal cured film are stacked adjacent to each other in order to evaluate the adhesion and alignment of the laminate. 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 2-dimethylamino-2-benzyl- 6 parts by mass of 1-(4-?olinylphenyl)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%. 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 the horizontal alignment liquid crystal cured film After corona treatment was performed on the COP film (ZF14-50) manufactured by Zeon Corporation, the composition for forming the horizontal alignment film was applied using a bar coater, and the temperature was set at 80°C. After drying for 1 minute, polarized UV exposure was performed with a polarized UV irradiation device (SPOT CURE SP-9; manufactured by Ushio Electric Co., Ltd.) at a wavelength of 313 nm: 100 mJ/cm ² to obtain a horizontal alignment film. The film thickness of the obtained horizontal alignment film was measured by an ellipsometer and found to be 200 nm. Next, apply a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on the horizontally aligned film, heat it at 120° C. for 60 seconds, and then use a high-pressure mercury lamp (UNICURE VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) , by irradiating ultraviolet rays from the surface coated with the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film (accumulated light intensity at a wavelength of 365 nm in a nitrogen atmosphere: 500 mJ/cm ² ), thereby forming a horizontally aligned liquid crystal cured film , to obtain 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 are sequentially adjacently laminated. The film thickness of the obtained horizontally aligned liquid crystal cured film was measured by an ellipsometer and found to be 2.2 μm.

3. Embodiment 3 The preparation of the polymerizable liquid crystal composition for forming the vertically aligned liquid crystal cured film and the formation of the vertically aligned liquid crystal cured film were changed as follows, except that, in the same manner as in Example 2, a substrate, horizontally aligned Film, horizontal alignment liquid crystal cured film and vertical alignment liquid crystal cured film are stacked adjacent to each other in order to evaluate the adhesion and alignment of the laminate. 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 the leveling agent "F-556" (manufactured by DIC Corporation) was added, and the ionic compound A (molecular weight: 645) 1.5 parts by mass, silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass, 2-dimethylamino-2-benzyl-1-( 6 parts by mass of 4-?olinylphenyl)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.

(2) Fabrication of Vertical Alignment Liquid Crystal Cured Film Corona treatment was performed on the surface of the horizontal alignment liquid crystal cured film of the laminate comprising the base material, horizontal alignment film, and horizontal alignment liquid crystal cured film produced by the same procedure as in Example 2. Then, the polymerizable liquid crystal composition for vertical alignment liquid crystal cured film formation was apply|coated using the bar coater, and it heated at 120 degreeC for 60 second. Then, using a high-pressure mercury lamp (UNICURE VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.), irradiate ultraviolet light (wavelength 365 nm under nitrogen atmosphere) from the surface coated with the polymerizable liquid crystal composition for vertical alignment liquid crystal cured film formation. Accumulated light intensity: 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 Co., Ltd.), 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, the base material, the cured resin layer, the horizontal alignment film, the horizontal alignment liquid crystal cured film, and the vertical alignment liquid crystal cured film were produced in the same manner as in Example 3. Adhesiveness and orientation evaluation of the laminate is performed on the laminate formed by stacking films adjacent to each other in sequence. The results are shown in Table 1.

(1) Formation and preparation of horizontal alignment liquid crystal cured film 50 parts by mass of dipentaerythritol hexaacrylate (ARONIX M-403, multifunctional acrylate manufactured by Toa Gosei Co., Ltd.), acrylate resin (Ebecryl 4858, Daicel-UCB shares Co., Ltd.) 50 parts by mass, 2-methyl-1[4-(methylthio)phenyl]-2-?olinylpropan-1-one (Irgacure 907; Ciba Specialty Chemicals Co., Ltd.) 3 parts by mass dissolved The obtained solution with 250 mass parts of isopropanols obtained the composition for hardening resin layer formation containing an acrylate compound. Next, after performing corona treatment on the COP film (ZF14-50) manufactured by Zeon Corporation, the above-mentioned composition for forming a cured resin layer was coated with a bar coater, dried at 50°C for 1 minute, and then coated with a high pressure A mercury lamp ("UNICURE VB-15201BY-A", manufactured by Ushio Electric Co., Ltd.) was irradiated with ultraviolet rays (accumulated light intensity at a wavelength of 365 nm in a nitrogen atmosphere: 400 mJ/cm ² ) to form a hardened resin layer. 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 of the laminate including the base material and the cured resin layer produced by the above method, and the polymerizable liquid crystal composition for forming a horizontal alignment film was coated using a bar coater. After drying at 80°C for 1 minute, use a polarized UV irradiation device (SPOT CURE SP-9; manufactured by Ushio Electric Co., Ltd.) to perform polarized UV exposure at a wavelength of 313 nm with a cumulative light intensity of 100 mJ/cm ² to obtain a level Alignment film. The film thickness of the obtained horizontal alignment film was measured by an ellipsometer and found to be 200 nm. Then, apply the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on the horizontally aligned film, heat it at 120°C for 60 seconds, and use a high-pressure mercury lamp (UNICURE VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.), The surface coated with the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film was irradiated with ultraviolet rays (accumulated light intensity at a wavelength of 365 nm in a nitrogen atmosphere: 500 mJ/cm ² ), thereby forming a horizontally aligned liquid crystal cured film. The film thickness of the obtained horizontally aligned liquid crystal cured film was measured by an ellipsometer and found to be 2.2 μm.

5. Embodiment 5 The preparation of the polymerizable liquid crystal composition for forming the vertical alignment liquid crystal cured film was changed as follows, except that, the substrate, the horizontal alignment film, the horizontal alignment liquid crystal cured film, and the vertical alignment film were prepared in the same manner as in Example 3. Aligned liquid crystal cured films are stacked adjacent to each other in order to form a laminate, and the adhesiveness and alignment of the laminate are 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 the leveling agent "F-556" (manufactured by DIC Corporation) was added, and the ionic compound A (molecular weight: 645) 1.5 parts by mass, as a photopolymerization initiator of 2-dimethylamino-2-benzyl-1-(4-alphalinylphenyl) butane-1-one (manufactured by BASF Japan Co., Ltd. "Irgacure (registered trademark) 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.

6. Embodiment 6 The preparation of the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film was changed as follows, except that, in the same manner as in Example 3, a substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, and Vertically aligned liquid crystal cured films are stacked adjacent to each other in sequence, and the adhesiveness and alignment of the laminate are 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 0.5 parts by mass of a silane coupling agent "KBE-9103" (manufactured by Shin-Etsu Chemical Co., Ltd.) were added as 2-Dimethylamino-2-benzyl-1-(4-?olinylphenyl)butan-1-one of the photopolymerization initiator ("Irgacure (registered trademark)" manufactured by BASF Japan Co., Ltd. 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.

7. Comparative example 1 The preparation of the polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film was changed as follows, except that, in the same manner as in Example 3, a substrate, a horizontal alignment film, a horizontal alignment liquid crystal cured film, and Vertically aligned liquid crystal cured films are stacked adjacent to each other in sequence, and the adhesiveness and alignment of the laminate are 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 2-dimethylamino-2-benzyl-1- 6 parts by mass of (4-?olinylphenyl)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.

[Table 1]

According to the present invention, a vertically aligned liquid crystal cured film can be produced without forming a vertically aligned film, and it was confirmed that both liquid crystal alignment and adhesiveness can be improved (Examples 1 to 6). On the other hand, when using the polymerizable liquid crystal composition which does not contain a vertical alignment accelerator, a vertical alignment cured film cannot be obtained without forming a vertical alignment film on a horizontal alignment cured film (comparative example 1).

1‧‧‧Horizontal alignment liquid crystal cured film 2‧‧‧Vertically aligned liquid crystal cured film 3‧‧‧Horizontal alignment film 4‧‧‧hardened resin layer 5‧‧‧Substrate 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 (20)

A laminate comprising a horizontally aligned liquid crystal cured film and a vertically aligned liquid crystal cured film in sequence, wherein the horizontally aligned liquid crystal cured film is cured in a state where a polymerizable liquid crystal compound is aligned horizontally relative to the plane of the liquid crystal cured film The cured product of the polymerizable liquid crystal composition, the cured product of the polymerizable liquid crystal composition obtained by curing the above-mentioned vertically aligned liquid crystal cured film system in a state where the polymerizable liquid crystal compound is aligned in the vertical direction relative to the plane of the liquid crystal cured film, And the vertical alignment liquid crystal cured film contains a vertical alignment accelerator, from the surface of the horizontal alignment liquid crystal cured film opposite to the vertical alignment liquid crystal cured film to the vertical alignment liquid crystal cured film opposite to the horizontal alignment liquid crystal cured film The total film thickness of the side surface is 5 μm or less, and the horizontal alignment liquid crystal cured film satisfies the following formula (1): 0.78≦ReA(450)/ReA(550)≦0.92 (1) [In formula (1), ReA(450 ) represents the in-plane retardation value of the in-plane direction of the horizontally aligned liquid crystal cured film at a wavelength of 450nm, ReA(550) represents the in-plane retardation value of the in-plane direction of the horizontally aligned liquid crystal cured film at a wavelength of 550nm]; vertical alignment The liquid crystal cured film satisfies the following formula (2): 0.8≦RthC(450)/RthC(550)≦0.92 (2) [In the formula (2), RthC(450) represents the thickness of the vertical alignment liquid crystal cured film at a wavelength of 450nm The retardation value in the direction, RthC(550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550nm]. The laminated body according to claim 1, wherein the horizontally aligned liquid crystal cured film is adjacent to the vertically aligned liquid crystal cured film. The laminate according to claim 1 or 2, wherein the horizontally aligned liquid crystal cured film is cured in a state where a polymerizable liquid crystal compound having at least one radically polymerizable group is aligned horizontally with respect to the in-plane direction of the liquid crystal cured film The resulting liquid crystal cured film, and the vertically aligned liquid crystal cured film is a liquid crystal formed by curing a polymerizable liquid crystal compound having at least one free radical polymerizable group in a state of vertical alignment relative to the in-plane direction of the liquid crystal cured film hardened film. The laminate according to claim 1 or 2, wherein the horizontally aligned liquid crystal cured film has at least one maximum absorption at a wavelength of 300 to 400 nm. 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 accelerator. The laminated body according to claim 1 or 2, wherein the vertically aligned liquid crystal cured film contains non-metallic An atomic ionic compound is used as a vertical alignment promoter, and the molecular weight of the ionic compound is not less than 100 and not more than 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 vertically 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, which includes a horizontal alignment film, and the horizontal alignment film, the horizontal alignment liquid crystal cured film, and the vertical alignment liquid crystal cured film exist adjacently in this order. The laminate according to claim 11, wherein the horizontal alignment film is a photo-alignment film formed of a polymer having a (meth)acryl group. The laminated body as claimed in item 11, wherein the film thickness of the horizontal alignment film is 100-5000 nm. The laminate according to claim 11, wherein the horizontal alignment film is a photo-alignment film formed of a polymer having an azo group or a cinnamonyl group. An elliptically polarizing plate comprising the laminate and a polarizing film according to any one of Claims 1 to 14. The elliptically polarizing plate according to claim 15, wherein the horizontal alignment liquid crystal cured film constituting the laminate The angle formed by the retardation axis and the absorption axis of the polarizing film is 45±5°. An organic EL display device comprising the elliptical polarizer according to claim 15 or 16. A method for manufacturing a laminate according to any one of Claims 1 to 14, which comprises the following steps in the following order: forming a coating film of a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film containing a polymerizable liquid crystal compound, by The coating film forms a horizontal alignment liquid crystal cured film; and forms 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 forms a vertical alignment liquid crystal cured film from the coating film. According to the manufacturing method of Claim 18, the step of forming a horizontally aligned liquid crystal cured film and the step of forming a vertically aligned liquid crystal cured film are continuously performed in the following order. The manufacturing method according to claim 18 or 19, which includes the 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 before the step of forming a horizontally aligned liquid crystal cured film.

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