TW202103962A - Layered product, and composition for forming perpendicularly aligned liquid crystal cured film - Google Patents

Abstract

The present invention addresses the problem of providing a layered product which exhibits an optimal substrate peeling force and which is obtained by layering, using an optimal adhesive strength, a substrate and a perpendicularly aligned liquid crystal cured film which is formed without a vertical alignment film. The present invention relates to a layered product that includes a substrate and a perpendicularly aligned liquid crystal cured film that is adjacent to the substrate. The perpendicularly aligned liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing at least one type of vertical alignment promoter and at least one type of polymerizable liquid crystal compound, and is a liquid crystal cured film in which the polymerizable liquid crystal compound is cured in a state that is aligned in a direction perpendicular to a flat surface of the liquid crystal cured film. The layered product satisfies formula (1). Formula (1): 0.02 < P < 1.00 (N/25 mm) [In formula (1), P is the substrate peeling force (N/25 mm) at an interface between the perpendicularly aligned liquid crystal cured film and the substrate that constitute the layered product when the substrate is peeled at a rate of 300 mm/min.].

Description

Laminate and vertical alignment liquid crystal cured film forming composition

The present invention relates to a laminate including a vertically aligned liquid crystal cured film, an ellipsoidal polarizing plate including the laminate, and an organic EL display device. Furthermore, it also relates to a composition for forming a cured film of a vertically aligned liquid crystal that can be used to form the above-mentioned laminate.

The elliptically polarizing plate is an optical member formed by laminating a polarizing plate and a phase difference plate. In devices that display images in a flat state, such as organic EL image display devices, it is used to prevent light reflection at the electrodes constituting the device. As the retardation plate constituting the elliptical polarizing plate, a so-called λ/4 plate is generally used. As such a retardation plate, a retardation plate including a horizontally-aligned liquid crystal cured film is known, which is formed by polymerizing and curing a polymerizable liquid crystal compound in a state where the polymerizable liquid crystal compound is aligned in the horizontal direction with respect to the plane of the retardation plate. In addition, it is known that by further assembling a vertically aligned liquid crystal cured film on an elliptical polarizing plate provided with a horizontally aligned liquid crystal cured film, when the elliptical polarizing plate is used in an organic EL display device, the oblique orientation during black display can be suppressed. Hue changes. Patent Document 1 describes a method of forming a vertical alignment film on a substrate, and coating a composition containing a polymerizable liquid crystal compound on the vertical alignment film, thereby forming a vertical alignment liquid crystal cured film. It also describes a laminate including a vertically aligned liquid crystal cured film formed and a horizontally aligned liquid crystal cured film formed on the horizontally aligned film. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-57646

[The problem to be solved by the invention]

However, in order to manufacture a vertical alignment liquid crystal cured film, a vertical alignment film is generally required, which is used to align the polymerizable liquid crystal compound in the vertical direction. Therefore, there is a problem that the vertical alignment film needs to be formed before the vertical alignment liquid crystal cured film is formed. In order to obtain a coating film from the alignment film forming composition and the liquid crystal cured film forming composition, at least two or more coating film forming steps are required , Productivity is easy to decrease. In this regard, in order to improve productivity, there is a need for a method of forming a vertical alignment liquid crystal cured film without forming a vertical alignment film. The inventors have developed and proposed a laminated body which is included in the case where the vertical alignment film is not formed. In the case of the vertical alignment liquid crystal cured film directly formed on the substrate. During this development, the following new discovery was obtained: In order to directly form a vertical alignment liquid crystal cured film on a substrate without a vertical alignment film, when a compound with vertical alignment regulation power is matched to the vertical alignment liquid crystal cured film, the vertical alignment The adhesion between the aligned liquid crystal cured film and the substrate is likely to decrease, which may cause the substrate to be excessively easily peeled off.

The present invention provides a novel solution to the above-mentioned problems, and aims to provide a vertical alignment liquid crystal cured film formed without a vertical alignment film and a substrate laminated with the best adhesion and exhibiting the best substrate peeling force的层体。 The laminated body. [Technical means to solve the problem]

The inventors of the present invention made diligent studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention includes the following aspects. [1] A laminate comprising a substrate and a vertical alignment liquid crystal cured film adjacent to the substrate, The vertical alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing at least one vertical alignment accelerator and at least one polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is positioned perpendicular to the plane of the liquid crystal cured film. The liquid crystal cured film is cured in the state of alignment in the direction, and The above-mentioned laminate satisfies formula (1). 0.02＜P＜1.00 (N/25 mm) (1) [In formula (1), P is the substrate peeling force when peeling the substrate at a speed of 300 mm/min at the interface between the vertically aligned liquid crystal cured film constituting the laminate and the substrate (N/25 mm)] [2] The layered product as described in [1] above, wherein the thickness of the cured film of the vertical alignment liquid crystal is 0.3 μm or more and 5.0 μm or less. [3] The laminate as described in [1] or [2] above, wherein the vertical alignment liquid crystal cured film satisfies the formula (2). -150 nm≦RthC(550)≦-30 nm (2) [In formula (2), RthC(550) represents the retardation value in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of 550 nm] [4] The laminate as described in any one of [1] to [3] above, wherein the polymerizable liquid crystal compound has a (meth)acryloyl group as a polymerizable group. [5] The laminate as described in any one of [1] to [4] above, wherein the vertical alignment liquid crystal cured film contains an ionic compound containing a non-metal atom as a vertical alignment promoter. [6] The layered product as described in [5] above, which comprises the non-metal atom-containing ionic compound, and the molecular weight of the ionic compound is 100 or more and 10,000 or less. [7] The laminate as described in any one of [1] to [6] above, wherein the polymerizable liquid crystal composition forming the vertical alignment liquid crystal cured film contains at least one vertical alignment promoter, and has (meth)acrylic acid At least one polymerizable liquid crystal compound having an acyl group, and at least one polymerizable non-liquid crystal compound having two or more (meth)acrylic groups. [8] The laminate as described in any one of [1] to [7] above, wherein the vertical alignment liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter. [9] The layered body according to the above [8], which contains the nonionic silane compound, and the nonionic silane compound is a silane coupling agent. [10] The laminate as described in any one of [1] to [4] above, wherein the vertical alignment liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter and an ionic compound containing a nonmetal atom . [11] The laminate as described in any one of [1] to [10] above, wherein the vertically-aligned liquid crystal cured film contains a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acryloyl group in the molecule. Compound. [12] The laminate as described in any one of [1] to [11] above, wherein the vertical alignment liquid crystal cured film satisfies the following relational formula (3). RthC(450)/RthC(550)≦1.0 (3) [In formula (3), RthC (450) represents the phase difference in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the phase difference in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of 550 nm Difference] [13] The laminate as described in any one of [1] to [12] above, which further includes a horizontally-aligned retardation film. [14] The layered product as described in the above [13], wherein the horizontally-aligned retardation film is a horizontally aligned phase difference film obtained by curing at least one polymerizable liquid crystal compound in a state where it is aligned horizontally with respect to the in-plane direction of the retardation film Liquid crystal hardened film. [15] An elliptically polarizing plate comprising the laminate as described in [13] or [14] above, and a polarizing film. [16] The elliptical polarizing plate as described in [15] above, wherein the angle formed by the slow axis of the horizontally aligned retardation film and the absorption axis of the polarizing film is 45±5°. [17] An organic EL display device comprising the elliptically polarizing plate as described in [15] or [16] above. [18] A composition for forming a vertically aligned liquid crystal cured film, comprising: a compound selected from the group consisting of a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acryloyl group in the molecule, and a compound having two or more (methyl) groups. ) At least one of the group consisting of polymerizable non-liquid crystal compounds of acryloyl group, Polymerizable liquid crystal compound, and An ionic compound containing non-metal atoms as a vertical alignment promoter. [19] The composition for forming a vertically aligned liquid crystal cured film as described in [18] above, wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound having a (meth)acryloyl group. [Effects of Invention]

According to the present invention, it is possible to provide a laminate in which a vertical alignment liquid crystal cured film formed without a vertical alignment film and a substrate are laminated with the best adhesion and exhibits the best substrate peeling force.

The laminate of the present invention includes a vertical alignment liquid crystal cured film and a substrate. In the present invention, the vertical alignment liquid crystal cured film is laminated on the substrate without intervening the vertical alignment film, and the substrate and the vertical alignment liquid crystal cured film are adjacent to each other. In the present invention, in the laminate of the present invention, the vertical alignment liquid crystal cured film can be formed without a vertical alignment film. Therefore, the number of manufacturing steps of the laminate is reduced, and the laminate can be manufactured with good productivity.

FIG. 1 shows one form of the laminate of the present invention, and shows the most basic layer structure of the laminate of the present invention, but it is not limited to this. The laminate 11 shown in FIG. 1 is formed by laminating a base material 1 and a vertical alignment liquid crystal cured film 2. In the laminate 11 shown in FIG. 1, the vertical alignment liquid crystal cured film 2 is directly formed on the substrate 1 without interposing a layer with vertical alignment regulation (hereinafter, also referred to as "vertical alignment film"). It is adjacent to the vertical alignment liquid crystal cured film 2. In addition to the base material and the vertical alignment liquid crystal cured film, the laminate of the present invention may further include other layers. Examples of other layers include: a horizontally-aligned retardation film (horizontal-aligned liquid crystal cured film), a horizontally-aligned film, a protective layer, a hard coat layer, and other hardened resin layers, and a layer for bonding the laminate of the present invention to a polarizing film, etc. Adhesive layer, etc.

The laminate of the present invention satisfies the following formula (1). 0.02＜P＜1.00 (N/25 mm) (1) In formula (1), P is the substrate peeling force (N/25 mm) when the substrate is peeled off at a speed of 300 mm/min at the interface between the vertically aligned liquid crystal cured film constituting the laminate and the substrate.

In the present invention, the vertical alignment liquid crystal cured film is directly formed on the substrate without intervening the vertical alignment film. The polymerizable liquid crystal composition used to form the above-mentioned vertical alignment liquid crystal cured film (hereinafter, also referred to as "the composition for forming a vertical alignment liquid crystal cured film") contains a vertical alignment promoter, which is designed to exhibit vertical alignment regulatory power, namely , When coated on the substrate, the polymerizable liquid crystal compound contained in the composition is aligned in a vertical direction with respect to the plane of the coating film. In the present invention, in order to exhibit vertical alignment regulation power, the composition for forming a vertical alignment liquid crystal cured film may contain a component as a vertical alignment promoter (for example, an ionic compound containing a non-metal atom as described below). When the composition is applied to the substrate, the interface on the substrate side (interface a in FIG. 1: hereinafter also referred to as "substrate side interface") generates electrostatic repulsion to the polymerizable liquid crystal compound. However, when the composition for forming a vertically aligned liquid crystal cured film is applied to a substrate, components that generate electrostatic repulsion tend to segregate at the interface on the substrate side. In addition, the component that generates electrostatic repulsion generally does not have a polymerizable group. The component or the component and the polymerizable liquid crystal compound forming the vertical alignment liquid crystal cured film cannot form a network structure, so it is easy to segregate in the vertical alignment. Cohesive failure occurred on the substrate side interface of the liquid crystal cured film. The laminate containing the vertical alignment liquid crystal cured film directly formed on the substrate is prone to cohesive failure near the substrate side interface where the vertical alignment promoter segregates during the cutting process, and the vertical alignment liquid crystal cured film is easily peeled from the substrate Therefore, it is necessary to improve the adhesion between the vertical alignment liquid crystal cured film and the substrate.

If the substrate peeling force P in the laminate of the present invention is 0.02 or less, the adhesion between the substrate and the vertical alignment liquid crystal cured film is insufficient, and it is difficult to sufficiently prevent the vertical alignment liquid crystal cured film from being spontaneous during the cutting process of the laminate. The substrate peels off. On the other hand, if the peeling force of the substrate is 1.00 or more, the adhesion between the substrate and the vertical alignment liquid crystal cured film is too high, a large force is required to peel the substrate from the laminate, and it is difficult to align the substrate with the vertical alignment The liquid crystal cured film is completely peeled off without generating residues on each other. When the laminate of the present invention satisfies the above formula (1), in the laminate, the substrate and the vertically aligned liquid crystal cured film adjacent to it are laminated with moderate adhesion, and cut in the form of a laminate. The vertical alignment liquid crystal cured film is not easy to peel off from the substrate during processing, etc., but when the substrate is peeled from the laminate, the substrate and the vertical alignment liquid crystal cured film can be completely peeled off with less force. In the present invention, the peeling force P of the substrate is preferably 0.03 N/25 mm or more, more preferably 0.035 N/25 mm or more, still more preferably 0.04 N/25 mm or more, and more preferably 0.8 N/25 mm or less, more preferably 0.6 N/25 mm or less, and still more preferably 0.5 N/25 mm or less. In addition, the above-mentioned substrate peeling force P can be measured according to the method described in the following Examples.

The substrate peeling force P in the laminate can be controlled by selecting the composition of the vertical alignment liquid crystal cured film forming composition for forming the vertical alignment liquid crystal cured film and the type of the substrate, especially the surface state of the substrate. Hereinafter, each structure of the laminate of the present invention will be described in detail.

〔Vertical Alignment Liquid Crystal Hardened Film〕 The vertical alignment liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymerizable liquid crystal composition containing at least one vertical alignment accelerator and at least one polymerizable liquid crystal compound. In addition, the vertical alignment liquid crystal cured film is a cured liquid crystal film formed by curing the polymerizable liquid crystal compound in a state where the polymerizable liquid crystal compound is aligned in a vertical direction with respect to the plane of the liquid crystal cured film. In the present invention, the vertical alignment liquid crystal cured film contains a vertical alignment promoter. That is, in the present invention, the composition for forming a vertical alignment liquid crystal cured film (polymerizable liquid crystal composition) for forming a vertical alignment liquid crystal cured film contains a vertical alignment promoter. In the present invention, the vertical alignment promoter means a material that promotes the alignment of the polymerizable liquid crystal compound in the vertical direction of the liquid crystal relative to the film plane. By including the vertical alignment promoter in the vertical alignment liquid crystal cured film, the vertical alignment liquid crystal cured film can be formed without the vertical alignment film. Thereby, in the laminated body of the present invention, it is not necessary to form a vertical alignment liquid crystal cured film, the production steps of the laminated body can be simplified, and the laminated body can be produced with good productivity. Examples of the vertical alignment accelerator include: a component that generates electrostatic repulsion to a polymerizable liquid crystal compound at the interface of the substrate side when the composition is applied to the substrate (for example, the following ionic compound); or coating on the substrate When the composition is fabricated, it can reduce the surface energy at the interface on the opposite side of the substrate of the vertical alignment liquid crystal cured film to exert the vertical alignment regulation force, that is, the polymerizable liquid crystal compound is aligned in the vertical direction with respect to the film plane. Ingredients (for example, the following nonionic silane compound).

In the present invention, as a vertical alignment accelerator that promotes the alignment of the polymerizable liquid crystal compound in the vertical direction, the composition for forming a cured film of a vertical alignment liquid crystal preferably includes the interface on the substrate side when the composition is applied on the substrate. A component that generates electrostatic repulsion to the polymerizable liquid crystal compound. As such a component, an ionic compound can be mentioned, for example. From the viewpoint of suppressing the occurrence of alignment defects in the vertical alignment liquid crystal cured film, the vertical alignment promoter preferably contains an ionic compound containing non-metal atoms. If the composition for forming a vertical alignment liquid crystal cured film contains an ionic compound containing non-metal atoms, the dried coating film formed from the composition exhibits the ability to regulate the vertical alignment of the polymerizable liquid crystal compound by electrostatic interaction , It is possible to align the polymerizable liquid crystal compound in the vertical direction with respect to the film plane in the dried coating film. Thereby, the vertically aligned state of the polymerizable liquid crystal compound can be maintained to form a liquid crystal cured film.

Examples of ionic compounds containing non-metal atoms (hereinafter also referred to as "ionic compounds") include onium salts (more specifically, quaternary ammonium salts with positively charged nitrogen atoms, tertiary sulfonium salts, And quaternary phosphonium salts with positively charged phosphorus atoms, etc.). Among these onium salts, the quaternary onium salt is preferred from the viewpoint of further improving the vertical alignment of the polymerizable liquid crystal compound, and the quaternary onium salt is more preferred from the viewpoint of improving the availability and mass production. Phosphonium 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 polymer.

The molecular weight of the ionic compound is preferably 100 or more and 10,000 or less. If 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 coatability of the composition for forming a vertical alignment liquid crystal cured film. The molecular weight of the ionic compound is more preferably 5,000 or less, and still more preferably 3,000 or less.

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

Ionic compounds generally have counter anions. As an anion component which becomes a counter ion of the said cationic component, an inorganic anion and an organic anion can be mentioned, for example. Among them, an organic anion is preferred in terms of the fact that alignment defects of the polymerizable liquid crystal compound are not easily generated. Furthermore, cations and anions do not necessarily have a one-to-one correspondence.

As an anion component, specifically, the following are mentioned, for example. Chloride anions [Cl ^-], a bromide anion [Br ^-], an iodide anion [I ^-], [tetrachloroaluminate anion AlCl ₄ ^-], heptachlor aluminum anions [Al ₂ Cl ₇ ^-], tetrakis fluoroborate anions [BF ₄ ^-], a hexafluorophosphate anion [PF ₆ ^-], perchloric acid anion [ClO ₄ ^-], nitrate anion [NO ₃ ^-], acetate anion [CH ₃ COO ^-], trifluoroacetic acid anion [CF ₃ COO ^-], fluorosulfonic acid anion [FSO ₃ ^-], methanesulfonate anion [CH ₃ SO ₃ ^-], triflate anion [CF ₃ SO ₃ ^-], p sulfonate anion _{[p-CH 3 C 6 H 4} SO 3 - ], bis (fluoromethyl sulfonylurea) imide anion [(FSO _{2) 2} N ^-], bis (trifluoromethanesulfonyl XI) imide anion [(CF ₃ SO _{2) 2} N ^-], tris (trifluoromethanesulfonyl XI) [methanation anion _{(CF 3 SO 2) 3 C} - ], hexafluoroarsenate anion [AsF ₆ ^-], [hexafluoroantimonate anion SbF ₆ ^-], niobium hexafluorophosphate anion [NbF ₆ ^-], six tantalum fluoride anion [TaF ₆ ^-], dimethylmethylene phosphonate anion [(CH _{3) 2} POO ^-], (poly) hydrogen fluoride anion [F (HF) _n ^-] (for example, n represents an integer of 1 to 3), dicyanamide anion [(CN) ₂ N ^-], [thiocyanate anion SCN ^-], perfluoro butyl sulfonate anion [ C ₄ F ₉ SO ₃ ^-], bis (pentafluoroethane sulfonylurea) imide anion _{[(C 2 F 5 SO 2)} 2 N - ], perfluoro butyrate anion [C ₃ F ₇ COO ^-], and (trifluoromethanesulfonyl acyl) (trifluoromethane-carbonyl) acyl imide anion _{[(CF 3 SO 2) (CF} 3 CO) N - ].

The specific example of an ionic compound can be suitably selected from the combination of the said cationic component and an anion component. As a specific compound of the combination of a cationic component and an anionic component, the following can be mentioned, for example.

(Pyridinium salt) N-hexylpyridinium hexafluorophosphate, N-octylpyridinium hexafluorophosphate, N-methyl-4-hexylpyridinium hexafluorophosphate, N-butyl-4-methylpyridinium hexafluorophosphate, N-octyl-4-methylpyridinium hexafluorophosphate, Bis(fluorosulfonamide) imine N-hexylpyridinium, Bis(fluorosulfonyl)imine N-octylpyridinium, Bis(fluorosulfonyl)imine N-methyl-4-hexylpyridinium, Bis(fluorosulfonamide) imine N-butyl-4-methylpyridinium, Bis (fluorosulfonyl) imine N-octyl-4-methylpyridinium, Bis (trifluoromethanesulfonate) imine N-hexylpyridinium, Bis(trifluoromethanesulfonamide) imine N-octylpyridinium, Bis(trifluoromethanesulfonyl)imine N-methyl-4-hexylpyridinium, Bis(trifluoromethanesulfonyl)imine N-butyl-4-methylpyridinium, Bis (trifluoromethanesulfonate) imine 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)imine 1-ethyl-3-methylimidazolium, Bis(trifluoromethanesulfonyl)imine 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylimidazolium p-toluenesulfonate, 1-butyl-3-methylimidazolium methanesulfonate and the like.

(Pyrolidinium salt) N-butyl-N-methylpyrrolidinium hexafluorophosphate, Bis(fluorosulfonyl)imine N-butyl-N-methylpyrrolidinium, Bis(trifluoromethanesulfonyl)imine N-butyl-N-methylpyrrolidinium, N-butyl-N-methylpyrrolidinium p-toluenesulfonate and the like.

(Ammonium salt) Tetrabutylammonium hexafluorophosphate, Tetrabutylammonium bis(fluorosulfonamide) imide, Tetrahexylammonium bis(fluorosulfonyl)imide, Bis (fluorosulfonamide) trioctyl methyl ammonium, Bis (fluorosulfonamide) imine (2-hydroxyethyl) trimethyl ammonium, Tetrabutylammonium bis(trifluoromethanesulfonate) imide, Tetrahexylammonium bis(trifluoromethanesulfonate)imide, Bis (trifluoromethanesulfonate) imino trioctyl methyl ammonium, Bis (trifluoromethanesulfonate) imine (2-hydroxyethyl) trimethylammonium, Tetrabutylammonium p-toluenesulfonate, Tetrahexylammonium p-toluenesulfonate, Trioctylmethylammonium p-toluenesulfonate, P-toluenesulfonic acid (2-hydroxyethyl) trimethylammonium, Dimethylphosphonite (2-hydroxyethyl) trimethylammonium, Bis(trifluoromethanesulfonyl)imine 1-(3-trimethoxysilylpropyl)-1,1,1-tributylammonium, Bis(trifluoromethanesulfonyl)imine 1-(3-trimethoxysilylpropyl)-1,1,1-trimethylammonium, Bis(trifluoromethanesulfonyl)imine 1-(3-trimethoxysilylbutyl)-1,1,1-tributylammonium, Bis(trifluoromethanesulfonyl)imine 1-(3-trimethoxysilylbutyl)-1,1,1-trimethylammonium, Bis(trifluoromethanesulfonyl)imine N-{(3-triethoxysilylpropyl)aminoformoxyethyl)}-N,N,N-trimethylammonium, and Bis(trifluoromethanesulfonyl)imine N-[2-{3-(3-trimethoxysilylpropylamino)-1-oxopropoxy}ethyl]-N,N,N -Trimethylammonium.

(Phosphonium salt) Bis (trifluoromethanesulfonate) iminotributyl (2-methoxyethyl) phosphonium, Bis (trifluoromethanesulfonate) imide tributyl methyl phosphonium, Bis(trifluoromethanesulfonyl)imine 1,1,1-trimethyl-1-[(trimethoxysilyl)methyl]phosphonium, Bis(trifluoromethanesulfonyl)imine 1,1,1-trimethyl-1-[2-(trimethoxysilyl)ethyl]phosphonium, Bis(trifluoromethanesulfonyl)imine 1,1,1-trimethyl-1-[3-(trimethoxysilyl)propyl]phosphonium, Bis(trifluoromethanesulfonyl)imine 1,1,1-trimethyl-1-[4-(trimethoxysilyl)butyl]phosphonium, Bis(trifluoromethanesulfonyl)imine 1,1,1-tributyl-1-[(trimethoxysilyl)methyl]phosphonium, Bis(trifluoromethanesulfonyl)imine 1,1,1-tributyl-1-[2-(trimethoxysilyl)ethyl]phosphonium, and Bis(trifluoromethanesulfonyl)imine 1,1,1-tributyl-1-[3-(trimethoxysilyl)propyl]phosphonium. These ionic compounds may be used individually, respectively, and may be used in combination of 2 or more types. Among them, ionic compounds containing phosphonium salts, pyridinium salts, and ammonium salts are preferred.

From the viewpoint of further improving the vertical alignment of the polymerizable liquid crystal compound, the ionic compound preferably has Si element and/or F element in the molecular structure of the cation site. If the ionic compound has Si element and/or F element in the molecular structure of the cation site, the ionic compound is easily segregated on the surface of the vertical alignment liquid crystal cured film. Among them, as the ionic compound whose constituent elements are all non-metallic elements, the following ionic compounds (i) to (iii) and the like are preferable.

(離子性化合物(ii)) [化2]

(離子性化合物(iii)) [化3]

(Ionic compound (i)) [化1]

(Ionic compound (ii)) [Chemical 2]

(Ionic compound (iii)) [Chemical Formula 3]

For example, the following methods (for example, refer to Chapter 2 of "Liquid Crystal Handbook", "Orientation and Physical Properties of Liquid Crystals" (issued by Maruzen Co., Ltd.) can be used to further improve the vertical alignment of polymerizable liquid crystal compounds: use a chain length that is somewhat longer The surfactant of the alkyl group treats the surface of the substrate to improve the orientation of the liquid crystal. That is, by treating the surface of the substrate with an ionic compound having an alkyl group with a somewhat longer chain length, the vertical alignment of the polymerizable liquid crystal compound can be effectively improved.

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

Furthermore, when there are more than two positively charged atoms in the molecule of an ionic compound, the substituents with more than two positively charged atoms shall be counted from the positively charged atom as the base point. The number of covalent bonds to the nearest other positively charged atom is set to the "number of covalent bonds from the positively charged atom to the end of the molecular chain" described in the definition of M above. In addition, when the ionic compound is an oligomer or polymer having two or more repeating units, the above-mentioned M is calculated by considering the structural unit as one molecule. When a positively charged atom is incorporated into a ring structure, the number of covalent bonds through the ring structure to the positively charged atom or the number of covalent bonds to the end of the substituent bonded to the ring structure is total The larger number of valence bonds is set as the "number of covalent bonds from the positively charged atom to the end of the molecular chain" described in the definition of M above.

When the composition for forming a vertically aligned liquid crystal cured film contains an ionic compound containing non-metal atoms, its content is usually relative to 100 parts by mass of the polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film. Preferably it is 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.1 parts by mass or more, more preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less . If the content of the non-metal atom-containing ionic compound is within the above range, it is possible to effectively promote the vertical alignment of the polymerizable liquid crystal compound while maintaining good coating properties of the composition for forming a vertical alignment liquid crystal cured film.

The composition for forming a vertical alignment liquid crystal cured film preferably contains a component as a vertical alignment accelerator that can exert a vertical alignment regulating force. The vertical alignment regulating force is reduced by applying the composition on a substrate. The surface energy at the interface on the opposite side of the vertical alignment liquid crystal cured film to the substrate (interface b in Figure 1: hereinafter also referred to as the "non-substrate side interface") makes the polymerizable liquid crystal compound align with the film plane Align in the vertical direction. As such a component, a nonionic silane compound etc. are mentioned, for example. If the composition for forming a vertical alignment liquid crystal cured film contains a nonionic silane compound, the nonionic silane compound will reduce the surface tension of the composition for forming a vertical alignment liquid crystal cured film. In the dry coating film formed from the composition, Often nonionic silane compounds are concentrated in the interface between the dried coating film and the air, which can improve the vertical alignment regulation of the polymerizable liquid crystal compound, and align the polymerizable liquid crystal compound in the vertical direction relative to the film plane in the dried coating film. Thereby, the vertically aligned state of the polymerizable liquid crystal compound can be maintained to form a liquid crystal cured film.

The non-ionic silane compound is a non-ionic compound containing Si element. Examples of nonionic silane compounds include: silicone polymers such as polysiloxane, polysiloxane resins such as polysiloxane oil and polysiloxane resin, and polysiloxane oligomers and silsesquioxane. Organo-inorganic silane compounds such as alkanes and alkoxysilanes (more specifically, silane coupling agents, etc.). These nonionic silane compounds may be used individually by 1 type, or may be used in combination of 2 or more types. Among them, from the viewpoint of further improving the adhesion with the adjacent layer, a silane coupling agent is preferred.

The non-ionic silane compound may be a silicone monomer type or a silicone oligomer (polymer) type. When the polysiloxane oligomer is expressed in the form of (monomer)-(monomer) copolymer, examples include: 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyl Trimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer Mercaptopropyl-containing copolymers; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxy Silane-tetramethoxysilane copolymer and mercaptomethyltriethoxysilane-tetraethoxysilane copolymer, such as mercaptomethyl-containing copolymers; 3-methacryloxypropyltrimethoxy Silane-tetramethoxysilane copolymer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetra Methoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetra Methoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxysilane -Tetramethoxysilane copolymer and 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer, such as methacryloxypropyl-containing copolymers; 3-propylene oxypropyl trimethoxysilane-tetramethoxy silane copolymer, 3-propylene oxy propyl trimethoxy silane-tetraethoxy silane copolymer, 3-propylene oxy propyl Triethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropylmethyldimethoxy Silane-tetramethoxysilane copolymer, 3-propenyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropylmethyldiethoxysilane- Tetramethoxysilane copolymer and 3-propenyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer, such as copolymers containing propyleneoxypropyl; vinyl trimethoxy Silane-tetramethoxysilane copolymer, vinyl trimethoxysilane-tetraethoxysilane copolymer, vinyl triethoxysilane-tetramethoxysilane copolymer, vinyl triethoxysilane-tetra Ethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxy Copolymers containing vinyl groups such as methyl silane-tetramethoxy silane copolymer and vinyl methyl diethoxy silane-tetraethoxy silane copolymer; 3-aminopropyl trimethoxy silane-tetra Methoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-amino Propyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer , 3-Aminopropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-aminopropyl Amino group-containing copolymers such as methyl diethoxysilane-tetraethoxysilane copolymers.

Silane coupling agent is a compound containing Si element, which has a functional group at the end, for example selected from vinyl group, epoxy group, styryl group, methacryl group, acrylic group, amine group, isocyanurate group, urea At least one of the group consisting of a sulfhydryl group, a mercapto group, an isocyanate group, a carboxyl group, and a hydroxyl group, and at least one alkoxysilyl group or silanol group. By appropriately selecting these functional groups, it is possible to provide special effects such as improvement of the mechanical strength of the vertical alignment liquid crystal cured film, surface modification of the vertical alignment liquid crystal cured film, and improvement of the adhesion with the adjacent layer of the vertical alignment liquid crystal cured film. From the viewpoint of adhesion, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and another different reactive group (for example, the above-mentioned functional group). The silane coupling agent is more 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 often easier to improve, and the vertical alignment promoting effect can be significantly obtained. The polar group may, for example, be an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxyl group, and a hydroxyl group. Furthermore, the polar group may have a substituent or a protecting group as appropriate to control the reactivity of the silane coupling agent.

As the silane coupling agent, specifically, for example, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris (2-methoxyethoxy) silane, N-(2-amine) Ethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropane 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane , 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane, 3-glycidoxypropyl dimethoxymethyl silane and 3-glycidoxypropyl ethoxy dimethyl silane.

Moreover, as a commercially available silane coupling agent, for example, the silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., such as KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE -1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602 , KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, and KBE-9007.

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

In the present invention, the vertical alignment liquid crystal cured film preferably contains at least one of an ionic compound containing a non-metal atom and a non-ionic silane compound as a vertical alignment promoter, and more preferably contains an ion containing a non-metal atom The sexual compound is more preferably an ionic compound containing a non-metal atom and a non-ionic silane compound. By making the vertical alignment liquid crystal cured film contain both an ionic compound containing non-metal atoms and a nonionic silane compound, in the dry coating film formed from the composition for forming a vertical alignment liquid crystal cured film, the substrate side interface The electrostatic interaction caused by the ionic compound containing non-metal atoms and the surface energy reduction effect caused by the non-ionic silane compound at the non-substrate side interface, the polymerizable liquid crystal is generated at the two interfaces of the liquid crystal cured film. The compound has the ability to regulate the vertical alignment, so it is easier to promote the vertical alignment of the polymerizable liquid crystal compound. Thereby, it is possible to maintain the state of the polymerizable liquid crystal compound in a more accurate vertical alignment to form a liquid crystal cured film.

The vertical alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing at least one polymerizable liquid crystal compound in addition to the above-mentioned vertical alignment accelerator. In the present invention, the polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film (polymerizable liquid crystal composition) for forming a vertically aligned liquid crystal cured film means a liquid crystal compound having a polymerizable group. The polymerizable liquid crystal compound is not particularly limited, and for example, a polymerizable liquid crystal compound conventionally known in the field of retardation film can be used.

The polymerizable group refers to a group that can participate in the polymerization reaction using living radicals or acids generated by the polymerization initiator. As the polymerizable group, for example, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, (meth)acryloyl group, oxirane group, oxa Cyclobutyl and so on. Among them, it is compatible with compounds having functional groups capable of reacting with hydroxyl or carboxyl groups and (meth)acrylic groups in the molecule and/or polymerizable non-polymerizable compounds having two or more (meth)acrylic groups. In terms of constructing a network structure between the liquid crystal compounds and effectively improving the adhesion to the substrate, a (meth)acryloyl group is preferred. In addition, (meth)acrylic acid group means acrylic acid group or methacrylic acid group, and similarly, (meth)acrylic acid ester means acrylic acid ester or methacrylic acid ester.

The liquid crystallinity exhibited by the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a liquid liquid crystal, but in terms of precise film thickness control, it is preferably a thermotropic liquid crystal. In addition, the phase order structure in the thermotropic liquid crystal may be a nematic liquid crystal or a smectic liquid crystal. The polymerizable liquid crystal compound may be used alone or in combination of two or more kinds.

As the polymerizable liquid crystal compound, generally, a polymerizable liquid crystal compound exhibiting positive wavelength dispersibility and a polymerizable liquid crystal compound exhibiting reverse wavelength dispersibility can be exemplified. Either one of the polymerizable liquid crystal compounds may be used, or the two may be polymerized. Mixed use of liquid crystal compounds. From the viewpoint of enhancing the effect of suppressing the oblique reflection hue during black display in a display device incorporating the obtained laminate, it is preferable to include a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion. As the polymerizable liquid crystal compound, only one type may be used, or two or more types may be used in combination.

The polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is preferably a compound having the following characteristics (A) to (D). (A) Compounds that can form nematic phase or smectic phase. (B) It has π electrons in the long axis direction (a) of the polymerizable liquid crystal compound. (C) There are π electrons in the direction crossing the major axis direction (a) [crossing direction (b)]. (D) When the sum of π electrons existing in the long axis direction (a) is N(πa) and the sum of the molecular weights existing in the long axis direction is N(Aa), it is defined by the following formula (i) Π electron density in the long axis direction (a) of the polymerizable liquid crystal compound: D(πa)=N(πa)/N(Aa) (i) When the sum of the π electrons existing in the cross direction (b) is N(πb) and the sum of the molecular weights existing in the cross direction (b) is N(Ab), the polymerization defined by the following formula (ii) Π electron density in the cross direction (b) of the liquid crystal compound: D(πb)=N(πb)/N(Ab) (ii) For the relationship of formula (iii): 0≦〔D(πa)/D(πb)〕＜1 (iii) [That is, the π electron density in the cross direction (b) is greater than the π electron density in the long axis direction (a)]. In addition, 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.

In the above-mentioned features (A) to (D), the major axis direction (a) and the number of π electrons N are defined as follows. ・As long as it is a compound having a rod-like structure, the long axis direction (a) is the long axis direction of the rod. ・The number of π electrons N(πa) existing in the long axis direction (a) does not include π electrons that disappear due to polymerization. ・The number of π electrons existing in the long axis direction (a) N(πa) is the total count of the π electrons on the long axis and the conjugated π electrons, for example, it includes the ring existing in the long axis direction (a) and satisfies The number of π electrons that exist on the ring of Huckel's law. ・The number of π electrons N(πb) in the cross direction (b) does not include π electrons that disappear due to polymerization. The polymerizable liquid crystal compound satisfying the above characteristics has a mesogen structure in the long axis direction. The liquid crystal phase (nematic phase, smectic phase) is exhibited by the mesogen structure.

A nematic or smectic phase can be formed by coating a polymerizable liquid crystal compound satisfying the above (A) to (D) on the film (layer) forming the liquid crystal cured film and heating it to a phase transition temperature or higher phase. In the nematic phase or smectic phase formed by the alignment of the polymerizable liquid crystal compound, it is usually aligned in such a way that the long axis directions of the polymerizable liquid crystal compound are parallel to each other, and the long axis direction is the alignment direction of the nematic phase. If such a polymerizable liquid crystal compound is made into a film and polymerized in the state of nematic or smectic phase, it can be polymerized in the state of being aligned in the long axis direction (a).物的polymer film. The polymer film absorbs ultraviolet rays by π electrons in the long axis direction (a) and π electrons in the cross direction (b). Here, let the absorption maximum wavelength of ultraviolet rays absorbed by π electrons in the cross direction (b) be λbmax. λbmax is usually 300 nm to 400 nm. Since the π electron density satisfies the above formula (iii), the π electron density in the cross direction (b) is greater than the π electron density in the long axis direction (a), so in the polymer film, a straight line with a vibrating surface in the cross direction (b) The absorption of polarized ultraviolet light (wavelength λbmax) is greater than that of linearly polarized ultraviolet light (wavelength λbmax) with a vibrating surface in the long axis direction (a). The ratio (the ratio of the absorbance in the cross direction (b) of the linearly polarized ultraviolet rays/the absorbance in the long axis direction (a)) is, for example, more than 1.0, preferably 1.2 or more, and usually 30 or less, for example, 10 or less.

Polymerizable liquid crystal compounds having the above-mentioned characteristics generally exhibit reverse wavelength dispersion in most cases. Specifically, for example, a compound represented by the following formula (X) can be exemplified. [化4]

In the formula (X), Ar represents a divalent group having an aromatic group which may have a substituent. The aromatic group mentioned here refers to the number of π electrons in the ring structure is [4n+2] according to Huckel's rule. For example, it can have two or more of the following (Ar -1) Ar group exemplified in (Ar-23). Among them, n represents an integer. When a ring structure is formed by including heteroatoms such as -N= or -S-, it also includes the case where the non-covalent bond electron pair on the heteroatoms satisfies Huckel's law and is aromatic. The aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. 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 that 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 be bonded to each other by a single bond, -CO-O-, -O- and other divalent bonding groups . G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Wherein, the hydrogen atoms contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be halogen atoms, alkyl groups with 1 to 4 carbons, fluoroalkyl groups with 1 to 4 carbons, and 1 to 4 carbons. The alkoxy group, cyano group or nitro group is substituted, and the carbon atoms constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group can be replaced by 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 each independently represent an integer from 0 to 3, and satisfy the relationship of 1≦k+1. Wherein, in the case of 2≦k+1, B ¹ and B ² , 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 carbon atoms, and among them, an alkanediyl group having 4 to 12 carbon atoms is more preferred. In addition, 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 -O-, -S-, -SiH ₂ -, -C(=O) -replace. P ¹ and P ² independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

Preferably, G ¹ and G ² are each independently a 1,4-phenylene diyl group which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, and may be 1,4-cyclohexadiyl substituted with at least one substituent selected from the group consisting of halogen atoms and alkyl groups with 1 to 4 carbon atoms, more preferably 1,4-phenylene substituted with methyl Group, unsubstituted 1,4-phenylene diyl, or unsubstituted 1,4-trans-cyclohexandiyl, especially unsubstituted 1,4-phenylene diyl, or unsubstituted 1,4-phenylene diyl Substituted 1,4-trans cyclohexanediyl. In addition, it is preferable ^{that at least one of the plural 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 Those are divalent alicyclic hydrocarbon groups.

L ¹ and L ^{2 are} preferably each independently a single bond, an alkylene 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-. Wherein, ^Ra1 to ^Ra8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and ^Rd represent an alkyl group having 1 to 4 carbon atoms 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 -. ^{Wherein, R a2-1, R a4-1, R} a6-1 each independently represent a single _{bond, -CH 2 -, - CH 2} CH 2 - in any one. More ^{preferably, L 1} and L ² are each independently a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, or -OCO-.

Preferably, B ¹ and B ² are each independently a single bond, an alkylene 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 -. Among them, ^Ra9 to ^Ra16 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 one of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. More ^{preferably, B 1} and B ² are 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 exhibiting reverse wavelength dispersion, k and l are preferably in the range of 2≦k+1≦6, preferably k+1=4, and more preferably k=2 and l=2. If k=2 and l=2, it becomes a symmetrical structure, so it is preferable.

Examples of the polymerizable group represented by P ¹ or P ² include epoxy, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, propyleneoxy, Methacryloxy group, oxirane group, and oxetanyl group, etc. Among them, propyleneoxy, methacryloxy, vinyl, and ethyleneoxy are preferred, and propyleneoxy 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. As this aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, an anthracene ring etc. are mentioned, for example, A benzene ring and a naphthalene ring are preferable. Examples of the aromatic heterocyclic ring include furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyridine ring, pyrimidine ring, triazole ring, and triazole ring. Ring, pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring, azole ring, benzoazole ring, phenanthroline 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. In addition, when Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

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

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

[化5]

In formulas (Ar-1) to (Ar-23), the * mark represents the connecting portion, and Z ⁰ , Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 12 carbon atoms, and a cyano group , Nitro, C1-C12 alkylsulfinyl group, C1-C12 alkylsulfinyl group, carboxyl group, C1-C12 fluoroalkyl group, C1-C12 alkoxy group , Alkylthio with 1-12 carbons, N-alkylamino with 1-12 carbons, N,N-dialkylamino with 2-12 carbons, N-alkyl with 1-12 carbons Sulfamoyl or N,N-dialkyl sulfamoyl with 2-12 carbons. In addition, Z ⁰ , Z ¹ and Z ² may include a polymerizable group.

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

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

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

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

Examples of the aromatic hydrocarbon groups in Y ¹ , Y ² and Y ³ include: phenyl, naphthyl, anthryl, phenanthryl, biphenyl and other aromatic hydrocarbon groups having 6 to 20 carbon atoms, preferably phenyl , Naphthyl, more preferably phenyl. The aromatic heterocyclic group may, for example, be furyl, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl, etc., containing at least one nitrogen atom, oxygen atom, sulfur atom, and other heteroatoms with 4 to 4 carbon atoms. The aromatic heterocyclic group of 20 is preferably furyl, 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 condensed polycyclic aromatic hydrocarbon group or a group derived from an aromatic ring assembly. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from an aromatic ring assembly.

Z ⁰ , Z ¹ and Z ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbons, a cyano group, a nitro group, an alkoxy group having 1 to 12 carbons, and Z ^{0 is more} preferably A hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group, and Z ¹ and Z ^{2 are more} preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or a cyano group. In addition, Z ⁰ , Z ¹ and Z ² may include a polymerizable group.

Q ¹ and Q ² is preferably -NH -, - S -, - NR 2 '-, - O-, R 2' is preferably a hydrogen atom. Among them, -S-, -O-, and -NH- are particularly preferred.

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

In formulas (Ar-16) to (Ar-23), Y ¹ can 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, such as pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyridine ring, pyrimidine ring, Indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring, etc. The aromatic heterocyclic group may have a substituent. In addition, Y ¹ and the nitrogen atom to which it is bonded and Z ⁰ may be the same as the above-mentioned substituted polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group. For example, a benzofuran ring, a benzothiazole ring, a benzoxazole ring, etc. can be mentioned.

In the present invention, as a polymerizable liquid crystal compound forming a cured film of a vertical alignment liquid crystal, 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) tends to generally exhibit positive wavelength dispersion. The polymerizable liquid crystal compound can be used alone or in combination of two or more kinds.

P11-B11-E11-B12-A11-B13- (Y) [In formula (Y), P11 represents a polymerizable group. A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. B11 means -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹⁶ -, -NR ¹⁶ -CO-, -CO-, -CS -Or single button. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. B12 and B13 independently represent -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-, -H, -C≡N or single bond. E11 represents an alkanediyl group having 1 to 12 carbons. The hydrogen atom contained in the alkanediyl group may be substituted by an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atom contained in the alkoxy group may be substituted by a halogen atom . _{Also, -CH 2} -constituting the alkanediyl group may be substituted by -O- or -CO-]

The carbon number of the aromatic hydrocarbon group and the alicyclic hydrocarbon group of A11 is preferably in the range of 3-18, more preferably in the range of 5-12, and particularly preferably 5 or 6. The hydrogen atoms contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group represented by A11 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 atom contained in the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms may be substituted by a fluorine atom. As A11, cyclohexane-1,4-diyl and 1,4-phenylene are preferred.

As E11, a linear alkanediyl group having 1 to 12 carbon atoms is preferred. _{The -CH 2} -constituting the alkanediyl group may be substituted by -O-. Specifically, examples include: methylene, ethylene, 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-, and -O-CO- are preferable, and among them, -CO-O- is more preferable. As B12 and B13, it is preferable to independently be -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O). ) -O-, among them, -O- or -OC(=O)-O- is more preferred.

[式(P-11)～(P-15)中， R¹⁷ ～R²¹ 分別獨立地表示碳數1～6之烷基或氫原子]The polymerizable group represented by P11 is preferably a radical polymerizable group or a cation polymerizable group in terms of higher polymerization reactivity, especially photopolymerization reactivity, which is easy to handle and can be used for the production of liquid crystal compounds In terms of being easy by itself, the polymerizable group is preferably a group represented by the following formulas (P-11) to (P-15). [化6]

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

As a specific example of the group represented by formula (P-11)-formula (P-15), the group represented by the following formula (P-16)-formula (P-20) can be mentioned. [化7]

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

As the polymerizable liquid crystal compound (Y), a compound represented by formula (I), formula (II), formula (III), formula (IV), formula (V) or formula (VI) may be mentioned. 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, A11, B11～B13 and P11 are synonymous with those in the above formula (A), A12～A14 are independently synonymous with A11, B14～B16 are independently synonymous with B12, B17 and B11 are synonymous, E12 and E11 are synonymous , P12 has the same meaning as P11. F11 represents a hydrogen atom, a C1-C13 alkyl group, a C1-C13 alkoxy group, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxyl group, a hydroxymethyl group Group, formyl group, sulfo group (-SO ₃ H), carboxyl group, alkoxycarbonyl group with 1 to 10 carbons or halogen atom, -CH ₂ -constituting the alkyl group and alkoxy group may be substituted by -O-)

As a specific example of the polymerizable liquid crystal compound (Y), one may cite: Liquid Crystal Handbook (Edited by the Liquid Crystal Handbook Compilation Committee, issued by Maruzen Co., Ltd. on October 30, 2000) "3.8.6 Net Structure (Completely Crosslinked Type) )", "6.5.1 Liquid crystal material b. Polymeric nematic liquid crystal material", among the compounds having a polymerizable group, Japanese Patent Laid-Open No. 2010-31223, Japanese Patent Laid-Open No. 2010-270108, A polymerizable liquid crystal described in Japanese Patent Laid-Open No. 2011-6360 and Japanese Patent Laid-Open No. 2011-207765.

Specific examples of the polymerizable liquid crystal compound (Y) include the following formula (I-1) to formula (I-4), formula (II-1) to formula (II-4), and formula (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 compound represented. In addition, in the following formula, k1 and k2 each independently represent an integer of 2-12. These polymerizable liquid crystal compounds (Y) are preferable in terms of ease of synthesis or ease of obtaining.

[化8]

[化9]

[化10]

[化11]

[化12]

[化13]

[化14]

[化15]

[化16]

The content of the polymerizable liquid crystal compound in the composition for forming a vertical alignment liquid crystal cured film forming a vertical alignment liquid crystal cured film is 70-99.5 parts by mass relative to 100 parts by mass of the solid content of the composition for forming a vertical alignment liquid crystal cured film , Preferably 80-99 parts by mass, more preferably 85-98 parts by mass, and still more preferably 90-95 parts by mass. If the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of the orientation of the obtained liquid crystal cured film. Furthermore, in the present invention, the solid component of the polymerizable liquid crystal composition means all components in the polymerizable liquid crystal composition except for volatile components such as organic solvents. Moreover, when the polymerizable liquid crystal composition contains two or more types of polymerizable liquid crystal compounds, it is preferable that the total content of all polymerizable liquid crystal compounds contained in the polymerizable liquid crystal composition is within the above-mentioned range.

The adhesion between the substrate in the laminate of the present invention and the vertical alignment liquid crystal cured film can be improved, for example, by forming a substrate having a hydroxyl group or a carboxyl group on the surface that contains a function capable of reacting with the hydroxyl or carboxyl group in the molecule. A cured film of a vertically aligned liquid crystal of a compound of a group and a (meth)acryloyl group (hereinafter, also referred to as a "pre-reaction compound"). By adjusting the surface treatment state of the above-mentioned substrate or the type and content of the pre-reaction compound contained in the vertical alignment liquid crystal cured film, the substrate peeling force P of the laminate can be controlled.

Therefore, the composition for forming a vertically aligned liquid crystal cured film constituting the laminate of the present invention preferably contains a compound having a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acryloyl group in the molecule. If the pre-reaction compound is included, the (meth)acrylic group of the pre-reaction compound and the polymerizable group (especially the (meth)acrylic group) of the polymerizable liquid crystal compound when forming a vertical alignment liquid crystal cured film react. In addition, the functional groups of the pre-reacted compound that can react with the hydroxyl group or the carboxyl group will also react with the hydroxyl group and/or the carboxyl group present on the surface of the substrate. Through the above two reactions, a cross-linked structure or a network structure is formed between the base material and the polymerizable liquid crystal compound, which is the main component of the vertical alignment liquid crystal cured film, through the pre-reacted compound, and the vertical alignment liquid crystal cured film and the base can be improved. The tightness of the material.

As a functional group which can react with a hydroxyl group or a carboxyl group which a pre-reaction compound has, as long as it is a functional group which can react with a hydroxyl group or a carboxyl group easily, it will not specifically limit. For example, an isocyanate group, an epoxy group, an oxetanyl group, a silanol group, an alkoxysilyl group, a carboxyl group, a hydroxyl group, an amino group, a chloro group, a hydroxysilyl group, etc. can be mentioned. The pre-reaction compound has at least one functional group capable of reacting with a hydroxyl group or a carboxyl group in the molecule, and when it contains two or more of the above-mentioned functional groups, the functional groups may be the same or different. Among them, in terms of relatively high reactivity and easy handling, it is preferably selected from the group consisting of isocyanate groups, epoxy groups, oxetanyl groups, silanol groups, alkoxysilyl groups, and hydroxysilyl groups. At least one of the group consisting, more preferably at least one selected from the group consisting of alkoxysilyl group and hydroxysilyl group.

The molecular weight of the pre-reaction compound is preferably 10,000 or less, more preferably 5,000 or less, and still more preferably 3,000 or less. If the molecular weight of the pre-reacted compound is below the above upper limit, the alignment of the polymerizable liquid crystal compound forming the vertical alignment film is not easily disturbed, and the higher alignment accuracy of the polymerizable liquid crystal compound can be ensured, and the adhesion to the substrate can be improved. On the other hand, the greater the number of covalent bonds between the functional group that can react with the hydroxyl or carboxyl group in the pre-reacted compound and the (meth)acrylic acid group, the easier it is to improve the adhesion between the substrate and the vertical alignment liquid crystal cured film Therefore, the molecular weight of the pre-reaction compound is preferably 50 or more, more preferably 100 or more, and still more preferably 300 or more.

In the present invention, a compound having a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acryloyl group in the molecule as a pre-reaction compound can be added to prepare a composition for forming a vertically aligned liquid crystal cured film. In addition, the pre-reaction compound can also be prepared at the same time as the composition for forming a vertically aligned liquid crystal cured film is prepared. As the pre-reaction compound, only one type may be used, or two or more types may be used in combination.

In the case of preparing the pre-reaction compound while preparing the composition for forming a vertically aligned liquid crystal cured film, it is preferable to form the pre-reaction compound by a chemical reaction that is easy to react quantitatively at room temperature, for example, a hydroxyl group or an amine group and A chemical reaction in which isocyanate groups react to form urethane bonds or urea bonds. For example, by adding a first compound having a functional group and an amino group that can react with a hydroxyl group or a carboxyl group, and a (meth)acrylic acid group and The second compound of the isocyanate group can obtain a pre-reacted compound having a functional group reactive with a hydroxyl group or a carboxyl group derived from the first compound and a (meth)acryloyl group derived from the second compound. The compound as a forming material of the pre-reaction compound may be added to the composition for forming a vertical alignment liquid crystal cured film if necessary after being mixed in a suitable solvent or the like in advance, or it may be directly mixed with other components constituting the composition for forming a vertical alignment liquid crystal cured film.

The greater the number of covalent bonds between the functional group that can react with the hydroxyl group or the carboxyl group and the (meth)acrylic acid group in the pre-reacted compound, the easier it is to improve the adhesion between the substrate and the vertical alignment liquid crystal cured film. By adjusting the number of covalent bonds, it is easy to control the adhesion between the substrate and the vertical alignment liquid crystal cured film. In this regard, in the present invention, the pre-reaction compound is more preferably used in the vertical alignment liquid crystal cured film forming composition. Or it is manufactured by chemical reaction in the manufacturing process.

As a compound suitable for the preparation of such a pre-reaction compound, for example, a compound having an alkoxysilyl group and an amino group as the first compound described above can be exemplified [e.g., KBE-903, KBM-602, KBM-903 (all of the above) Manufactured by Shin-Etsu Chemical Industry Co., Ltd.), etc. In addition, as the second compound mentioned above, a compound having a (meth)acryloyl group and an isocyanate group (for example, Karenz MOI-EG, Karenz MOI, Karenz AOI, Karenz BEI (all above are Showa Denko Co., Ltd.) Company manufacturing) etc.] etc. By appropriately combining these compounds, a pre-reacted compound can be obtained. The mixing ratio of each compound used to prepare the pre-reaction compound may be appropriately selected according to the structure of the compound used, etc., based on the chemical reaction used.

The content of the pre-reaction compound in the composition for forming a vertically aligned liquid crystal cured film is preferably 0.1 parts by mass or more, and more preferably at least 0.1 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film 0.2 part by mass or more, more preferably 0.3 part by mass or more. If the content of the pre-reaction compound is above the above lower limit, the functional group or (meth)acrylic group that the pre-reaction compound has that can react with the hydroxyl or carboxyl group and the hydroxyl or carboxyl group or polymerizable liquid crystal present on the surface of the substrate The polymerizable group (especially the (meth)acryl group) of the compound fully reacts, and the adhesion between the substrate and the vertical alignment liquid crystal cured film can be improved. In addition, the content of the pre-reaction compound is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 100 parts by mass of the polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film 5 parts by mass or less. If the content of the pre-reaction compound is less than the above upper limit, the substrate and the vertical alignment liquid crystal cured film are laminated with a moderate adhesive force, so that the substrate can be completely peeled off from the laminate with a small force. In addition, it is possible to control the adhesiveness while ensuring high alignment accuracy of the polymerizable liquid crystal compound constituting the vertical alignment liquid crystal cured film.

In a preferred aspect of the present invention, hydroxyl and/or carboxyl groups are present on the surface of the substrate forming the vertical alignment liquid crystal cured film, and the composition for forming the vertical alignment liquid crystal cured film includes the following components: Compounds of functional groups and (meth)acrylic groups that react with hydroxyl and/or carboxyl groups, polymerizable liquid crystal compounds having (meth)acrylic groups as polymerizable groups, and ionic compounds containing non-metal atoms. If the substrate surface and the composition for forming a vertical alignment liquid crystal cured film have the above constitution, a vertical alignment liquid crystal cured film can be formed without forming a vertical alignment film on the substrate, and it is easy to control the substrate and the vertical alignment liquid crystal cured film The adhesiveness, so it can achieve the best adhesiveness and substrate peeling force between the substrate and the vertical alignment liquid crystal cured film. Furthermore, the hydroxyl group or carboxyl group on the surface of the substrate can be provided by a known surface treatment method as described below.

In the present invention, the vertical alignment liquid crystal cured film preferably contains at least one polymerizable non-liquid crystal compound having two or more (meth)acrylic groups (hereinafter, also referred to as "multifunctional (meth)acrylate). Compound"). By including the polyfunctional (meth)acrylate compound, the (meth)acrylic group possessed by the polyfunctional (meth)acrylate compound and the polymerizable group possessed by the polymerizable liquid crystal compound in the vertical alignment liquid crystal cured film (Especially (meth)acryloyl) can form a cross-linked structure. Thereby, the network structure formed by the pre-reaction compound and the polymerizable liquid crystal compound can be strengthened, and the adhesion between the substrate and the vertical alignment liquid crystal cured film can be further improved.

The polyfunctional (meth)acrylate compound means a compound having two or more (meth)acryloyl groups in the molecule. As an example, a bifunctional (meth)acryloyl group having two (meth)acryloyl groups in the molecule can be mentioned. Meth)acrylate monomers, trifunctional or more (meth)acrylate monomers having 3 or more (meth)acrylic groups in the molecule, etc. In the present invention, the vertical alignment liquid crystal cured film may contain one or more types of polyfunctional (meth)acrylate compounds, and when it contains more than two types of polyfunctional (meth)acrylate compounds, etc. Can be the same or different.

As the bifunctional (meth)acrylate monomer, for example, ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol Di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, etc. Alkylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di (Meth) acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate and polytetramethylene glycol di(meth)acrylate, etc. Alcohol di(meth)acrylate; tetrafluoroethylene glycol di(meth)acrylate and other halogen-substituted alkylene glycol di(meth)acrylates; trimethylolpropane bis(methyl) Aliphatic polyol di(meth)acrylate such as acrylate, di-trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, etc.; hydrogenated dicyclopentadienyl di(meth)acrylate Di(meth)acrylate such as hydrogenated dicyclopentadiene or tricyclodecanediol di(meth)acrylate, such as acrylate, tricyclodecane dimethanol di(meth)acrylate, etc.; 1,3-diethane- 2,5-Diyl di(meth)acrylate [alias: dioxanediol di(meth)acrylate] such as dioxanediol or dioxanediol di(meth)acrylate ; Bisphenol A ethylene oxide adduct diacrylate, bisphenol F ethylene oxide adduct diacrylate and other bisphenol A or bisphenol F alkylene oxide adducts two (methyl ) Acrylic ester; acrylic acid adduct of bisphenol A diglycidyl ether, acrylic acid adduct of bisphenol F diglycidyl ether, bisphenol A or epoxy di(meth)acrylate of bisphenol F; polysilicon Oxydi(meth)acrylate; neopentyl glycol hydroxypivalate di(meth)acrylate; 2,2-bis[4-(meth)acryloyloxyethoxyethoxybenzene Yl]propane; 2,2-bis[4-(meth)propenyloxyethoxyethoxycyclohexyl]propane; 2-(2-hydroxy-1,1-dimethylethyl)-5 -Ethyl-5-hydroxymethyl-1,3-dioxane] di(meth)acrylate; tris(hydroxyethyl)isocyanurate di(meth)acrylate, etc.

A monomer having three (meth)acrylic acid groups in the molecule of a trifunctional (meth)acrylate single system. Examples of such monomers include: glycerol tri(meth)acrylate, trimethylolpropane tri (Meth)acrylate, di-trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, reactant of pentaerythritol tri(meth)acrylate and acid anhydride, modified by caprolactone Sexual trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate modified by caprolactone, trimethylolpropane tri(meth)acrylate modified by ethylene oxide Ester, pentaerythritol tri(meth)acrylate modified with ethylene oxide, trimethylolpropane tri(meth)acrylate modified with propylene oxide, pentaerythritol tri(meth)acrylate modified with propylene oxide Base) acrylate, isocyanurate tri(meth)acrylate, caprolactone modified pentaerythritol tri(meth)acrylate and acid anhydride reactant, ethylene oxide modified pentaerythritol tri(meth) The reactant of meth)acrylate and acid anhydride, the reactant of pentaerythritol tri(meth)acrylate and acid anhydride modified by propylene oxide, etc.

A monomer having 4 (meth)acrylic acid groups in the molecule of a tetrafunctional (meth)acrylate single system. As an example, there may be mentioned: di-trimethylolpropane tetra(meth)acrylate, Pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate modified by caprolactone, modified by caprolactone Three pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate modified with ethylene oxide, tripentaerythritol tetra (meth) acrylate modified with ethylene oxide, epoxy Propane-modified pentaerythritol tetra(meth)acrylate, propylene oxide-modified tripentaerythritol tetra(meth)acrylate, etc.

Examples of the 5-functional (meth)acrylate monomer include: dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate, reaction of dipentaerythritol penta(meth)acrylate and acid anhydride Dipentaerythritol penta(meth)acrylate modified with caprolactone, tripentaerythritol penta(meth)acrylate modified with caprolactone, dipentaerythritol penta(meth)acrylate modified with ethylene oxide )Acrylate, tripentaerythritol penta(meth)acrylate modified with ethylene oxide, dipentaerythritol penta(meth)acrylate modified with propylene oxide, tripentaerythritol penta(meth)acrylate modified with propylene oxide Meth) acrylate, the reactant of dipentaerythritol penta(meth)acrylate modified with caprolactone and acid anhydride, the reactant of dipentaerythritol penta(meth)acrylate modified with ethylene oxide and acid anhydride , The reactant of dipentaerythritol penta(meth)acrylate modified by propylene oxide and acid anhydride, etc.

As the hexafunctional (meth)acrylate monomer, for example, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate modified with caprolactone, )Acrylate, tripentaerythritol hexa(meth)acrylate modified with caprolactone, dipentaerythritol hexa(meth)acrylate modified with ethylene oxide, tripentaerythritol hexamodified with ethylene oxide (Meth) acrylate, dipentaerythritol hexa(meth)acrylate modified with propylene oxide, tripentaerythritol hexa(meth)acrylate modified with propylene oxide, etc.

As the 7-functional (meth)acrylate monomer, for example, tripentaerythritol hepta (meth)acrylate, the reaction product of tripentaerythritol hepta (meth)acrylate and acid anhydride, the third modified with caprolactone Pentaerythritol hepta (meth) acrylate, the reaction product of tripentaerythritol hepta (meth) acrylate modified with caprolactone and acid anhydride, the tripentaerythritol hepta (meth) acrylate modified with ethylene oxide, The reactant of ethylene oxide modified tripentaerythritol hepta (meth) acrylate and acid anhydride, tripentaerythritol hepta (meth) acrylate modified with propylene oxide, and tripentaerythritol hepta (meth) acrylate modified with propylene oxide The reactant of meth)acrylate and acid anhydride, etc.

An 8-functional (meth)acrylate monomer system has 8 (meth)acrylic acid groups in the molecule. As an example, it can be exemplified: tripentaerythritol octa(meth)acrylate, modified by caprolactone Sexual tripentaerythritol octa (meth) acrylate, tripentaerythritol octa (meth) acrylate modified with ethylene oxide, tripentaerythritol octa (meth) acrylate modified with propylene oxide, etc.

The number of (meth)acrylic groups in the polyfunctional (meth)acrylate compound is preferably 2-6. If the number of (meth)acrylic acid groups in the polyfunctional (meth)acrylate compound is within the above range, it will interact with the polymerizable liquid crystal compound constituting the vertical alignment liquid crystal cured film, especially having (methyl) as the polymerizable group. ) The acryl-based polymerizable liquid crystal compound forms a cross-linked structure to increase the cross-link density, so it can strengthen the network structure between the substrate and the vertical alignment liquid crystal cured film through the pre-reaction compound, and can improve the substrate and the vertical alignment liquid crystal Adhesion of hardened film.

The multifunctional (meth)acrylate compound can adjust the crosslinking density in the vertical alignment liquid crystal cured film by controlling the molecular weight between the crosslinking points and the number of crosslinking points of the compound. In more detail, the smaller the molecular weight between crosslinking points, the higher the crosslinking density, and the more the number of crosslinking points, the denser the crosslinking density and the higher the adhesion.

The molecular weight of the polyfunctional (meth)acrylate compound is preferably 1000 or less, more preferably 900 or less, and still more preferably 850 or less. If the molecular weight of the polyfunctional (meth)acrylate is below the above upper limit, the alignment of the polymerizable liquid crystal compound forming the vertical alignment film will not be easily disturbed, and the higher alignment accuracy of the polymerizable liquid crystal compound can be ensured. The tightness of the material. The lower limit of the molecular weight of the polyfunctional (meth)acrylate compound is not particularly limited, but it is usually 100 or more, preferably 200 or more.

The content of the polyfunctional (meth)acrylate compound in the composition for forming a vertically aligned liquid crystal cured film is preferably 0.05 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film Parts or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 5 parts by mass or less. If the content of the polyfunctional (meth)acrylate compound is within the above-mentioned range, it is not easy to disturb the alignment of the polymerizable liquid crystal compound forming the vertical alignment film, and the higher alignment accuracy of the polymerizable liquid crystal compound can be ensured while realizing the fundamentals. The best adhesion between the material and the vertical alignment liquid crystal cured film and the peeling force of the substrate.

In a preferred aspect of the present invention, hydroxyl and/or carboxyl groups are present on the surface of the substrate forming the vertical alignment liquid crystal cured film, and the composition for forming the vertical alignment liquid crystal cured film includes the following components: Compounds and polyfunctional (meth)acrylate compounds with functional groups reacted with hydroxyl and/or carboxyl groups and (meth)acrylic groups, and polymerizable liquid crystal compounds having (meth)acrylic groups as polymerizable groups And ionic compounds containing non-metal atoms. If the substrate surface and the composition for forming a vertical alignment liquid crystal cured film have the above constitution, a vertical alignment liquid crystal cured film can be formed without forming a vertical alignment film on the substrate, and it is easy to control the substrate and the vertical alignment liquid crystal cured film The adhesion can achieve better adhesion between the substrate and the vertical alignment liquid crystal cured film and the peeling force of the substrate.

The composition for forming a vertical alignment liquid crystal cured film (polymerizable liquid crystal composition) for forming a vertical alignment liquid crystal cured film except for the vertical alignment promoter and polymerizable liquid crystal compound, the above-mentioned pre-reaction compound and/or multifunctional (meth)acrylic acid In addition to the ester compound, additives such as a solvent, a polymerization initiator, a leveling agent, an antioxidant, and a photosensitizer may be further included. These components may be used individually by only 1 type, and may be used in combination of 2 or more types.

The composition for forming a vertically aligned liquid crystal cured film is usually applied to a substrate in a state of being dissolved in a solvent, and therefore preferably contains a solvent. As the solvent, a solvent that can dissolve the polymerizable liquid crystal compound is preferred, and a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound is preferred. As the solvent, for example, water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butanol Alcohol solvents such as oxyethanol and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Acetone , Methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone and other ketone solvents; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; ethyl cyclohexane, etc. Alicyclic hydrocarbon solvents; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; Amine-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 them, preferred are alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents, and aromatic hydrocarbon solvents.

The content of the solvent in the product for forming a vertically aligned liquid crystal cured film is preferably 50 to 98 parts by mass, and more preferably 70 to 95 parts by mass relative to 100 parts by mass of the composition. Therefore, the solid content in 100 parts by mass of the composition for forming a vertically aligned liquid crystal cured film is preferably 2-50 parts by mass. If the solid content is 50 parts by mass or less, the viscosity of the composition for forming a vertically aligned liquid crystal cured film decreases. In this respect, the thickness of the film tends to become substantially uniform, and unevenness is unlikely 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 reactive species by means of heat or light to initiate polymerization reactions such as polymerizable liquid crystal compounds. The reactive species may, for example, be free radicals, cations, or anions. Among them, from the viewpoint of easy control of the reaction, a photopolymerization initiator that generates radicals by light irradiation is preferred.

As the photopolymerization initiator, for example, a benzoin compound, a benzophenone compound, a benzyl ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, an oxime compound, a tris compound, and a salt And glutinous salt. Specifically, examples include: Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure BASF379, Irgacure BASF379 Co., Ltd.), Seikuol BZ, Seikuol Z, Seikuol BEE (the above are manufactured by Seiko Chemical Co., Ltd.), kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.), kayacure UVI-6992 (manufactured by Dow), Adeka Optomer SP- 152, Adeka Optomer SP-170, Adeka Optomer N-1717, Adeka Optomer N-1919, Adeka Arkls NCI-831, Adeka Arkls NCI-930 (above are manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (above It is manufactured by Nihon SiberHegner Company) and TAZ-104 (manufactured by Sanwa Chemical Company).

The photopolymerization initiator can make full use of the energy emitted from the light source and has excellent productivity. Therefore, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and among them, α-acetophenone is preferred System polymerization initiator, oxime-based photopolymerization initiator.

Examples of the α-acetophenone compound include: 2-methyl-2-N-𠰌line-1-(4-methylmercaptophenyl)propan-1-one, 2-dimethylamino- 1-(4-N-𠰌olinylphenyl)-2-benzylbutan-1-one and 2-dimethylamino-1-(4-N-𠰌olinylphenyl)-2-( 4-methylphenylmethyl)butan-1-one, etc., more preferably 2-methyl-2-N-𠰌line-1-(4-methylmercaptophenyl)propane-1 -Ketone and 2-dimethylamino-1-(4-N-𠰌olinylphenyl)-2-benzylbutan-1-one. As commercial products of the α-acetophenone compound, Irgacure 369, 379EG, 907 (manufactured by BASF JAPAN Co., Ltd.), Seikuol BEE (manufactured by Seiko Chemical Co., Ltd.) and the like can be mentioned.

The oxime-based photopolymerization initiator can generate radicals such as phenyl radicals or methyl radicals by irradiating light. With this radical, the polymerizable liquid crystal compound is polymerized well. Among them, in terms of higher initiation efficiency of the polymerization reaction, an oxime-based photopolymerization initiator that generates methyl radicals is preferred. Moreover, from the viewpoint of making the polymerization reaction proceed more efficiently, it is preferable to use a photopolymerization initiator capable of efficiently using ultraviolet rays with a wavelength of 350 nm or more. As a photopolymerization initiator capable of efficiently using ultraviolet rays with a wavelength of 350 nm or more, a tri-compound or a carbazole compound containing an oxime structure is preferable, and from the viewpoint of sensitivity, a carbazole compound containing an oxime ester structure is more preferable. Azole compounds. As a carbazole compound containing an oxime structure, examples include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzyl oxime)], 1-[9-ethyl Base-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethanone-1-(O-acetoxime) and the like. Commercial products of the oxime ester-based photopolymerization initiator include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (the above are made by BASF JAPAN Co., Ltd.), Adeka Optomer N-1919, Adeka Arkls NCI-831 (the above are manufactured by ADEKA Co., Ltd.), etc.

The content of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. If it is in the above range, the reaction of the polymerizable group proceeds sufficiently, and the alignment of the polymerizable liquid crystal compound is not easily disturbed.

The leveling agent refers to an additive that has the function of adjusting the fluidity of the composition for forming a vertically aligned liquid crystal cured film to make the coating film obtained from the coating composition more flat. For example, polysiloxane-based and polyacrylate-based additives can be mentioned. And perfluoroalkyl leveling agent. As the leveling agent, commercially available products can be used, specifically, for example: DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of the above are Toray Dow Corning Co., Ltd.) Manufacturing), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001 (the above are all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 , TSF4460 (the above are all manufactured by Momentive Advanced Materials Japan Contract Company), fluorinert (registered trademark) FC-72, fluorinert FC-40, fluorinert FC-43, fluorinert FC-3283 (all the above are manufactured by Sumitomo 3M (shares)) , 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 (all above are manufactured by DIC (Stock)), Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (all above are Mitsubishi Integrated Materials Electronics (Stock) Manufacturing), 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 Institute of Fine Chemicals), BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (trade name, all manufactured by BM Chemie) and the like. The leveling agent can be used alone or in combination of two or more kinds.

The content of the leveling agent is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. If the content of the leveling agent is within the above range, it is easy to align the polymerizable liquid crystal compound, and the obtained liquid crystal cured film tends to be smoother, which is preferable.

By blending antioxidants, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. As the antioxidant, it may be a primary antioxidant selected from phenol-based antioxidants, amine-based antioxidants, quinone-based antioxidants, and nitroso-based antioxidants, or may be selected from phosphorus-based antioxidants and sulfur-based 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 relative to 100 parts by mass of the polymerizable liquid crystal compound is usually 0.01-10 parts by mass, preferably 0.1-5 parts by mass , And more preferably 0.1 to 3 parts by mass. Antioxidants can be used alone or in combination of two or more kinds.

等𠮿酮類；蒽及具有烷基醚等取代基之蒽類；啡噻𠯤；紅螢烯。光增感劑可單獨使用，或者將2種以上組合使用。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。In addition, by using a photosensitizer, the photopolymerization initiator can be highly sensitive. As a photosensitizer, for example, ketone, 9-oxysulfur 𠮿

And other ketones; anthracene and anthracene with alkyl ether and other substituents; phenanthrene; red fluorene. The photosensitizer can be used alone or in combination of two or more kinds. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound.

The composition for forming a vertical alignment liquid crystal cured film can be initiated by starting a vertical alignment promoter, a polymerizable liquid crystal compound, a pre-reaction compound and/or a polyfunctional (meth)acrylate compound, a solvent, or photopolymerization at a specific temperature. It can be obtained by stirring the components other than the vertical alignment accelerator and the polymerizable liquid crystal compound. Furthermore, in the case of forming a pre-reaction compound in the composition for forming a vertical alignment liquid crystal cured film, for example, it can be prepared by the following method: preparing a mixture of the components required to form the pre-reaction compound, and combining the mixture with the vertical alignment The accelerator, the polymerizable liquid crystal compound, etc. are stirred together at a specific temperature.

In the present invention, the vertical alignment liquid crystal cured film is preferably aligned in the vertical direction of the liquid crystal cured film with a higher degree of order. In the vertical alignment liquid crystal cured film, by aligning the polymerizable liquid crystal compound with a higher degree of order, when the laminate including the vertical alignment liquid crystal cured film is assembled in an organic EL display device, the black display tends to be oblique. The effect of suppressing the change in the reflected hue is excellent. As an index indicating the higher alignment state of the polymerizable liquid crystal compound in the vertical alignment liquid crystal cured film and the degree of the oblique optical compensation effect during black display, the vertical alignment liquid crystal cured film preferably satisfies the following formula (2) . -150 nm≦RthC(550)≦-30 nm (2) In formula (2), RthC(550) represents the retardation value in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of 550 nm. From the viewpoint of further improving the oblique reflection hue during black display, the retardation value RthC(550) in the thickness direction of the vertical alignment liquid crystal cured film is more preferably -130 nm or more, and more preferably -100 nm or more , Particularly preferably -90 nm or more, more preferably -40 nm or less, and still more preferably -50 nm or less.

Furthermore, in one aspect of the present invention, the vertical alignment liquid crystal cured film satisfies the following formula (3). RthC(450)/RthC(550)≦1.0 (3) [In formula (3), RthC (450) represents the phase difference in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of 550 nm Phase difference value] By satisfying the above-mentioned formula (3), it is possible to suppress the decrease in the ellipticity on the short-wavelength side in the laminate including the vertically aligned liquid crystal cured film, and it is possible to improve the oblique reflection hue during black display. The value of RthC(450)/RthC(550) in the vertical alignment liquid crystal cured film is more preferably 0.95 or less, more preferably 0.92 or less, particularly preferably 0.9 or less, more preferably 0.7 or more, more preferably 0.75 or more , And more preferably 0.8 or more.

The retardation value RthC(λ) of the film thickness direction of the vertical alignment liquid crystal cured film can be adjusted according to the thickness dC of the vertical alignment liquid crystal cured film. The in-plane phase difference value is determined by the following formula: RthC(λ)=((nxC(λ)＋nyC(λ))/2－nzC(λ))×dC (Where, in the formula, nxC(λ) represents the principal refractive index of the vertical alignment liquid crystal cured film at the wavelength λ nm, and nyC(λ) represents the direction orthogonal to nxC(λ) in the plane at the wavelength λ nm Refractive index, nzC(λ) represents the refractive index in the thickness direction of the vertical alignment liquid crystal cured film at wavelength λ nm. When nxC(λ)=nyC(λ), nxC(λ) can be set to any value in the film surface The refractive index in the direction, dC represents the film thickness of the vertical alignment 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.

As the base material constituting the laminate of the present invention, for example, a glass base material or a film base material may be mentioned, but from the viewpoint of processability, a resin film base material is preferred. As the resin constituting the film substrate, for example, polyolefins such as polyethylene, polypropylene, and norene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate ; Polymethacrylate; Polyacrylate; Triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate such as cellulose esters; Polyethylene naphthalate; Polycarbonate; Polycarbonate ; Polyether stubble; polyether ketone; polyphenylene sulfide and polyphenylene ether and other plastics. Such a resin can be formed into a film by a known method such as a solvent casting method and a melt extrusion method to form a substrate.

As the substrate, commercially available products can be used. Examples of commercially available cellulose ester substrates include: cellulose ester substrates manufactured by Fuji Film Co., Ltd. such as Fujituck film; Konica Minolta such as "KC8UX2M", "KC8UY", and "KC4UY" Cellulose ester substrate manufactured by Co., Ltd., etc. As commercially available cyclic olefin resins, for example, "Topas (registered trademark)" cyclic olefin resins manufactured by Ticona (independent); "ARTON (registered trademark)" and other JSR shares Cyclic olefin resins manufactured by Co., Ltd.; "ZEONOR (registered trademark)" and "ZEONEX (registered trademark)" Cyclic olefin resins manufactured by Zeon Corporation; "APEL" (registered trademark) Such as the cyclic olefin resin manufactured by Mitsui Chemicals Co., Ltd. Commercially available cyclic olefin resin substrates can also be used. Examples of commercially available cyclic olefin-based resin base materials include: "S-SINA (registered trademark)" and "SCA40 (registered trademark)" cyclic olefin-based resin bases manufactured by Sekisui Chemical Industry Co., Ltd. Materials; "ZeonorFilm (registered trademark)" cyclic olefin resin base materials manufactured by Optes Co., Ltd.; "Arton film (registered trademark)" cyclic olefin resin base materials manufactured by JSR Co., Ltd. .

If there are hydroxyl groups and/or carboxyl groups on the surface of the substrate, the pre-reaction compound contained in the vertical alignment liquid crystal cured film can improve the adhesion between the substrate and the vertical alignment liquid crystal cured film, and the best adhesion and base can be obtained. Laminated body with material peeling force P. Therefore, it is preferable that a hydroxyl group and/or a carboxyl group exist on the surface of the substrate constituting the laminate of the present invention. In order to provide a hydroxyl group or a carboxyl group on the surface of the substrate, for example, corona treatment or plasma treatment may be performed on the surface of the substrate to form a hydroxyl group or a carboxyl group by oxidation of the substrate surface. In addition, for example, for a triacetyl cellulose film, a saponification treatment or the like may be used to post-process the film to form a hydroxyl group or a carboxyl group. In order to ensure good adhesion with the vertical alignment liquid crystal cured film, it is preferable that the surface of the substrate uniformly has a hydroxyl group and/or a carboxyl group. Surface treatment methods such as corona treatment and plasma treatment or saponification treatment methods for forming hydroxyl groups or carboxyl groups on the surface of the substrate are not particularly limited, and can be performed by known methods previously used for substrate surface treatment and the like. In addition, a commercially available substrate with the surface of the substrate previously treated as described above can also be selected.

In the present invention, the substrate is usually finally peeled off from the laminate of the present invention. By making the base material peeling force P of the laminate satisfy the above formula (1), in the laminate, the base material and the vertical alignment liquid crystal cured film are laminated with the best adhesion, and when the laminate is cut and processed, the vertical The oriented liquid crystal cured film and the substrate are not easily peeled off, but when the substrate is peeled from the laminate, it can be completely peeled off with a small force.

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

The laminate of the present invention may include layers other than the base material and the vertical alignment liquid crystal cured film within a range that does not affect the effects of the present invention. As such other layers, for example, a hardened resin layer and a hard coat layer for improving or reinforcing the mechanical strength of the horizontal alignment retardation film (horizontal alignment liquid crystal cured film), horizontal alignment film, and liquid crystal cured film are mentioned.

When forming a layered body by forming a cured film of a vertically aligned liquid crystal on a substrate, it is suitable for manufacturing the substrate peeling force P that satisfies the above formula (1) easily, and when cutting the layered body, etc., the vertically aligned liquid crystal The cured film and the base material are not easily peeled off, but when the base material is peeled from the laminate, the laminate can be completely peeled off with a small amount of force. In this respect, the present invention also includes a composition selected from the following components At least one vertical alignment liquid crystal cured film forming composition in the group is targeted: (a1) polymerizable liquid crystal compounds, (a2) ionic compounds containing non-metal atoms as vertical alignment promoters, and (a3) A compound having a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acrylic group in the molecule, and a polymerizable non-liquid crystal compound having two or more (meth)acrylic groups.

As a polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film, an ionic compound containing a non-metal atom, and a molecule having a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acryloyl group The compound and the polymerizable non-liquid crystal compound having two or more (meth)acrylic groups can be the same as the above-mentioned examples that can be included in the vertical alignment liquid crystal cured film constituting the laminate of the present invention. The polymerizable liquid crystal compound may be either a reverse wavelength dispersive polymerizable liquid crystal compound or a positive wavelength dispersive polymerizable liquid crystal compound. However, from the viewpoint that the adhesiveness can be further improved, it preferably has (methyl) Acrylic polymerizable liquid crystal compound. Furthermore, the composition for forming a vertical alignment liquid crystal cured film may further include a vertical alignment accelerator other than the non-metal atom-containing ionic compound, or a solvent, a polymerization initiator, a leveling agent, an antioxidant, a photosensitizer, etc. additive. As these components, the same thing as the above-mentioned example which can be contained in the vertical alignment liquid crystal cured film which comprises the laminated body of this invention can be used.

〔Method of manufacturing laminated body〕 The laminate of the present invention can be manufactured by, for example, the following method, The method includes the following steps: The step of coating a polymerizable liquid crystal composition for forming a vertical alignment liquid crystal cured film containing a polymerizable liquid crystal compound on a substrate to obtain a coating film; The step of drying the above-mentioned coating film to form a dry coating film; and The step of irradiating the dried coating film with active energy rays to form a vertical alignment liquid crystal cured film.

The formation of the coating film of the composition for forming a vertically-aligned liquid crystal cured film can be performed, for example, by coating the composition for forming a vertically-aligned liquid crystal cured film on a substrate.

As a method of applying the composition for forming a vertically aligned liquid crystal cured film on a substrate, there may be mentioned: spin coating method, extrusion method, gravure coating method, die nozzle coating method, bar coating method, Well-known methods such as coating methods such as dressing method and printing methods such as soft plate method.

Then, the solvent is removed by drying or the like, thereby forming a dry coating film. The drying method may, for example, be a natural drying method, an air drying method, a heat drying method, and a reduced pressure drying method. At this time, by heating the coating film obtained from the composition for forming a vertically aligned liquid crystal cured film, the solvent can be dried and removed from the coating film, and the polymerizable liquid crystal compound can be aligned in the vertical direction with respect to the coating film plane. In addition, by including a pre-reaction compound or a multifunctional (meth)acrylate compound, the hydroxyl group or carboxyl group present on the surface of the substrate reacts with the functional group of the pre-reaction compound that can react with the hydroxyl group or the carboxyl group, and the pre-reaction compound The (meth)acrylic group contained in it reacts with the (meth)acrylic group contained in the polymerizable liquid crystal compound or the polyfunctional (meth)acrylate compound forming the vertical alignment liquid crystal cured film, thereby forming the substrate It forms a network structure between it and the dried 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. However, in order to make the polymerizable liquid crystal compound phase transition into the liquid crystal phase state, the liquid crystal phase transition temperature or higher is usually required的温度。 The temperature. In order to remove the solvent contained in the composition for forming a vertical-aligned liquid crystal cured film, while bringing the polymerizable liquid crystal compound into a vertically aligned state, for example, it can be heated to the polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film The temperature above the liquid crystal phase transition temperature (smectic 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 analysis device (TG-DTA), or the like. In addition, 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 composition for forming a vertically aligned liquid crystal cured film are combined with the composition for forming a vertically aligned liquid crystal cured film. The composition is mixed in the same ratio, and the mixture of the polymerizable liquid crystal compound is used, and the temperature is measured in the same way as when one polymerizable liquid crystal compound is used. Furthermore, it is generally known that the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the composition for forming a vertically aligned liquid crystal cured film is sometimes lower than the liquid crystal phase transition temperature of the individual 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, etc., but it is usually 15 seconds to 10 minutes, preferably 0.5 to 5 minutes.

The removal of the solvent from the coating film may be performed while heating the polymerizable liquid crystal compound to a liquid crystal phase transition temperature or higher, or may be performed separately, but from the viewpoint of improving productivity, it is preferably performed simultaneously. Before heating the polymerizable liquid crystal compound to a liquid crystal phase transition temperature or higher, a pre-drying step may also be provided to prevent the polymerizable liquid crystal compound contained in the coating film obtained from the composition for forming a vertically aligned liquid crystal cured film. Under polymerization conditions, moderately remove the solvent in the coating film. The drying method in the pre-drying step may, for example, be a natural drying method, a vent drying method, a heat drying method, and a reduced pressure drying method. The drying temperature (heating temperature) in the drying step can be based on the polymerizable liquid crystal compound used The type of solvent, the type of solvent, its boiling point and its amount, etc. are appropriately determined.

Next, with regard to the obtained dry coating film, a vertical alignment liquid crystal cured film is formed by polymerizing the polymerizable liquid crystal compound while maintaining the vertical alignment state of the polymerizable liquid crystal compound. The polymerization method may, for example, be a thermal polymerization method or a photopolymerization method, but from the viewpoint of easy control of the polymerization reaction, a photopolymerization method is preferred. In photopolymerization, as the light irradiated to the dry coating film, the type of polymerization initiator contained in the dry coating film, the type of polymerizable liquid crystal compound (especially the polymerizable group of the polymerizable liquid crystal compound) The type) and its amount are appropriately selected. As a specific example, one or more types of light or active electron beams selected from the group consisting of visible light, ultraviolet light, infrared light, X-ray, α-ray, β-ray, and γ-ray can be mentioned. Among them, in terms of easy control of the progress of the polymerization reaction, or the use of those widely used as photopolymerization devices in this field, ultraviolet light is preferred, and the composition for forming a vertical alignment liquid crystal cured film is preferred. The type of polymerizable liquid crystal compound or polymerization initiator contained so that it can be photopolymerized by ultraviolet light. In addition, during polymerization, it is also possible to control the polymerization temperature by irradiating light while cooling the dried coating film with an appropriate cooling mechanism. If such a cooling mechanism is used to perform polymerization of the polymerizable liquid crystal compound at a lower temperature, even if a substrate with relatively low heat resistance is used, a vertical alignment liquid crystal cured film can be appropriately formed. In addition, the polymerization temperature may be increased within a range that does not cause abnormalities due to heat (deformation caused by the heat of the base material, etc.) during light irradiation, thereby promoting the polymerization reaction. During photopolymerization, a patterned cured film can also be obtained by masking or developing.

As the light source of the above-mentioned active energy rays, for example, low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, xenon lamp, halogen lamp, carbon arc lamp, tungsten lamp, gallium lamp, excimer laser, emission LED (Light Emitting Diode) light source, chemical lamp, black light lamp, microwave excited mercury lamp, metal halide lamp, etc. for light with a wavelength range of 380 ~ 440 nm.

The intensity of ultraviolet radiation is usually 10 to 3,000 mW/cm ² . The intensity of ultraviolet irradiation is preferably the intensity in the wavelength region effective for the activation of the photopolymerization initiator. The light irradiation time is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and still more preferably 0.1 second to 1 minute. If irradiated with such ultraviolet radiation intensity once or multiple times, the cumulative light intensity is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , and more preferably 100 to 1,000 mJ/cm ² .

The thickness of the vertical alignment liquid crystal cured film can be appropriately selected according to the applied display device, and is preferably 0.3 μm or more and 5.0 μm or less, more preferably 3.0 μm or less, and even more preferably 2.0 μm or less.

〔Horizontal Alignment Retardation Film〕 The laminate of the present invention may include a horizontally-aligned retardation film. The horizontally-aligned retardation film that can constitute the laminate of the present invention means a retardation film that is aligned in the horizontal direction with respect to the in-plane direction of the vertically-aligned liquid crystal cured film. For example, it may be a stretched film or a cured product (hereinafter, also referred to as "Horizontal alignment liquid crystal cured film") etc., the cured product is a cured product of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is cured in a state where the phase difference film plane is aligned in the horizontal direction Become.

In the present invention, the horizontally aligned retardation film preferably satisfies the following formula (6). ReA(450)/ReA(550)≦1.0 (6) [In formula (6), ReA(λ) represents the in-plane retardation value of the horizontally aligned retardation film at a wavelength of λ nm, ReA(λ)=(nxA(λ)－nyA(λ))×dA(where ，NxA(λ) represents the principal refractive index at the wavelength λ nm in the horizontal alignment retardation film plane, nyA(λ) represents the refractive index at the wavelength λ nm in the same plane as nxA in the direction orthogonal to the direction of nxA , DA represents the film thickness of the horizontally aligned retardation film)]

When the horizontally aligned retardation film satisfies the formula (6), the horizontally aligned retardation film exhibits so-called inverse wavelength dispersion, that is, the in-plane retardation value at the short wavelength is smaller than the in-plane retardation value at the long wavelength. By combining such a horizontally-aligned retardation film with the above-mentioned vertical-aligned liquid crystal cured film, it is possible to obtain a laminate having an excellent effect of improving the front and oblique reflection hue during black display when assembled in an organic EL display device. Since the inverse wavelength dispersion is improved, the effect of improving the reflection hue in the front direction of the horizontal alignment retardation film can be further improved. Therefore, ReA(450)/ReA(550) is preferably 0.70 or more, more preferably 0.78 or more, and more It is preferably 0.95 or less, more preferably 0.92 or less.

The above-mentioned in-plane retardation value can be adjusted according to the thickness dA of the horizontally aligned retardation film. The in-plane retardation value is determined by the above formula ReA(λ)=(nxA(λ)-nyA(λ))×dA, therefore, the desired in-plane retardation value (ReA(λ): wavelength λ (nm) the in-plane retardation value of the horizontally aligned retardation film), as long as the three-dimensional refractive index and the film thickness dA are adjusted.

In addition, the horizontally aligned retardation film preferably satisfies the following formula (7). 120 nm≦ReA(550)≦170 nm (7) [In formula (7), ReA(λ) has the same meaning as above] If the in-plane retardation ReA(550) of the horizontally-aligned retardation film is within the range of formula (7), then when the laminate (elliptical polarizer) containing the horizontally-aligned retardation film is applied to the organic EL display device When displaying black, the improvement effect of the front reflection hue (the effect of suppressing coloration) becomes remarkable. A more preferable range of the in-plane retardation value is 130 nm≦ReA(550)≦150 nm.

The horizontal alignment retardation film is preferably a horizontal alignment liquid crystal cured film in terms of easily controlling the desired retardation of the retardation film and making it possible to thin the film. As the polymerizable liquid crystal compound for forming the horizontally aligned liquid crystal cured film, a polymerizable liquid crystal compound previously known in the field of retardation film can be used. Specifically, an example of a polymerizable liquid crystal compound that can be used to form a vertical alignment liquid crystal cured film, that is, a compound represented by formula (X) and/or (Y) can be used. Among them, it is preferable to exhibit so-called reverse wavelength dispersion. As the polymerizable liquid crystal compound, for example, the compound represented by the above formula (X) can be preferably used. In the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film, the polymerizable liquid crystal compound may be used alone or in combination of two or more kinds.

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

In addition to the polymerizable liquid crystal compound, the polymerizable liquid crystal composition used to form the horizontally aligned liquid crystal cured film may further contain additives such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, and a photosensitizer. As these components, the same thing as the example of the component which can be used for the above-mentioned vertical alignment liquid crystal cured film can be mentioned, and each may use only 1 type, and may use 2 or more types together.

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

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

The formation of the coating film of the polymerizable liquid crystal composition can be performed, for example, by coating the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film on a substrate or a horizontally aligned film as described below. As the substrate that can be used here, the same as the above examples of substrates that can be used to form a vertical alignment liquid crystal cured film can be used.

Then, the solvent is removed by drying or the like, thereby forming a dry coating film. The drying method may, for example, be a natural drying method, an air drying method, a heat drying method, and a reduced pressure drying method. In terms of productivity, heating and drying are preferable. In this case, the heating temperature is preferably a temperature higher than the phase transition temperature of the polymerizable liquid crystal compound that can remove the solvent. Regarding the steps or conditions in this step, the same ones as those that can be used in the manufacturing method of the vertical alignment liquid crystal cured film can be exemplified.

By irradiating the obtained dry coating film with active energy rays (more specifically, ultraviolet rays, etc.), the polymerizable liquid crystal compound is polymerized while keeping the state of the polymerizable liquid crystal compound aligned in the horizontal direction with respect to the plane of the coating film , And the formation of a horizontally aligned liquid crystal cured film. As the polymerization method, the same method as the method that can be used in the manufacturing method of the vertical alignment liquid crystal cured film can be exemplified.

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

By forming the coating film of the polymerizable liquid crystal compound on the horizontal alignment film, the alignment of the polymerizable liquid crystal compound in the horizontal direction can be further improved. For example, when a horizontal alignment film is formed on the vertically aligned liquid crystal cured film constituting the laminate of the present invention, and the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film is coated thereon to obtain a horizontally aligned liquid crystal cured film, Compared with the method of forming a horizontal alignment liquid crystal cured film on a substrate or a horizontal alignment film set on the substrate, and then pasting it with a vertical alignment liquid crystal cured film through an adhesive layer or the like, it is also possible to simplify the laminate Advantages of manufacturing steps. The horizontal alignment film can be appropriately selected from materials having a horizontal alignment regulating force that aligns the polymerizable liquid crystal compound in a horizontal direction with respect to the plane of the coating film. The alignment regulating force can be arbitrarily adjusted according to the type of alignment film, surface condition, rubbing conditions, etc., and when it is formed of a photo-alignable polymer, it can be arbitrarily adjusted according to polarized light irradiation conditions and the like.

As a horizontal alignment film, it is preferable to have solvent resistance, that is, it will not be dissolved by the coating of the polymerizable liquid crystal composition, etc., and has a heat treatment for removing the solvent or aligning the polymerizable liquid crystal compound described below. Those with heat tolerance. Examples of alignment films include alignment films containing alignment polymers, photo-alignment films, groove alignment films with concave and convex patterns or grooves on the surface, and stretched films extending in the alignment direction. Regarding the accuracy and quality of the alignment angle From a viewpoint, a photo-alignment film is preferable.

As the alignment polymer, for example, polyamides or gelatins having an amide bond in the molecule, polyimines having an amide bond in the molecule, and polyamides and polyethylene as hydrolysates thereof can be mentioned. Alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, polyazole, 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 kinds.

An alignment film containing an alignment polymer is usually obtained by the following method: a composition (hereinafter, sometimes referred to as "alignment polymer composition") formed by dissolving an alignment polymer in a solvent is applied to a substrate And remove the solvent, or apply the aligning polymer composition to the substrate and remove the solvent to perform rubbing (rubbing method). The solvent may be the same as the solvents exemplified above that can be used for the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film.

The concentration of the aligning polymer in the aligning polymer composition may be within a range where the aligning polymer material can be completely dissolved in the solvent, but it is preferably 0.1 to 20% in terms of solid content relative to the solution, and further Preferably it is about 0.1-10%.

As the alignment polymer composition, commercially available alignment film materials can be used directly. As a commercially available alignment film material, Sunever (registered trademark, manufactured by Nissan Chemical Industry Co., Ltd.), Optomer (registered trademark, manufactured by JSR Co., Ltd.), etc. can be mentioned.

As a method of applying the aligning polymer composition to the substrate, the same method as the method of applying the polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film to the substrate can be mentioned.

As a method of removing the solvent contained in the aligning polymer composition, a natural drying method, a ventilation drying method, a heat drying method, a reduced-pressure drying method, etc. may be mentioned.

In order to impart an alignment regulating force to the alignment film, a rubbing treatment (rubbing method) may be performed as necessary. As a method of imparting alignment regulation force by the friction method, the following method can be exemplified: the alignment polymer composition is coated on a substrate and annealed to form an alignment polymer film on the surface of the substrate, and the alignment is polymerized The object film is in contact with a friction roller wound with a friction cloth and rotating. When performing the rubbing treatment, if masking is performed, a plurality of regions (patterns) with different alignment directions can also be formed on the alignment film.

The photo-alignment film is usually obtained by the following method: a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as "photo-alignment film forming composition") is applied to a substrate , After removing the solvent, irradiate polarized light (preferably polarized light UV (ultraviolet, ultraviolet)). The direction of the alignment regulatory force can be arbitrarily controlled by selecting the polarization direction of the irradiated polarization. In this respect, the optical alignment film is also advantageous.

The photoreactive group refers to a group that generates liquid crystal alignment energy by light irradiation. Specifically, it can be exemplified to participate in the light reaction that is the origin of the alignment energy of liquid crystals, such as the alignment induction or isomerization reaction of molecules produced by light irradiation, dimerization reaction, photocrosslinking reaction, or photolysis reaction, etc. base. Among them, the group participating in the dimerization reaction or the photocrosslinking reaction is preferable in terms of excellent alignment. As the photoreactive group, a group having an unsaturated bond, especially a double bond is preferred, and a group having a carbon-carbon double bond (C=C bond) and a carbon-nitrogen double bond (C=N bond) is particularly preferred. , Nitrogen-nitrogen double bond (N=N bond) and carbon-oxygen double bond (C=O bond) group consisting of at least one group.

As the photoreactive group having a C=C bond, a vinyl group, a polyalkenyl group, a stilbene group, a stilbazole group, a stilazolium group, a chalcone group, and a cinnamyl group may be mentioned. The photoreactive group having a C=N bond may, for example, be a group having a structure such as an aromatic Schiff base and an aromatic hydrazone. Examples of photoreactive groups having N=N bonds include: azophenyl, azonaphthyl, aromatic heterocyclic azo, bisazo, formazan, and oxyazobenzene structure The base and so on. The photoreactive group having a C=O bond may, for example, be a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group, and the like. These groups may have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

Among them, the photoreactive group that participates in the photodimerization reaction is preferable. In terms of the amount of polarized light irradiation required for photoalignment is relatively small, and it is easy to obtain a photoalignment film with excellent thermal stability or stability over time, Preferably, they are cinnamon base and chalcone base. As a polymer having a photoreactive group, it is particularly preferable that the end of the side chain of the polymer has a cinnamic acid structure and has a cinnamon base.

By coating the composition for forming a photo-alignment film on a substrate, a photo-alignment inducing layer can be formed on the substrate. The solvent contained in the composition may be the same as the solvents exemplified above for the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film. The solvent may be based on a polymer or monomer having a photoreactive group. The solubility of the body is appropriately selected.

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

As a method of applying the composition for forming a photo-alignment film to the substrate, the same method as the method of applying the aligning polymer composition to the substrate can be exemplified. As a method of removing the solvent from the applied composition for forming a photo-alignment film, for example, a natural drying method, an air drying method, a heat drying method, and a reduced-pressure drying method may be mentioned.

Polarized light irradiation can be a form in which the solvent is removed from the composition for forming a photo-alignment film coated on a substrate, and the resultant is directly irradiated with polarized light UV, or it can be irradiated by irradiating polarized light from the substrate side and allowing the polarized light to pass through. form. Furthermore, it is particularly preferable that the polarized light is substantially parallel light. Regarding the wavelength of the polarized light to be irradiated, a wavelength range in which the photoreactive group of a polymer or monomer having a photoreactive group can absorb light energy is suitable. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferred. As the light source used for the polarized light irradiation, a xenon lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, KrF, ArF and other ultraviolet lasers, etc. can be exemplified, more preferably a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide light. Among them, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferred because of the higher luminous intensity of ultraviolet light with a wavelength of 313 nm. By irradiating light from the above-mentioned light source through an appropriate polarizing element, polarized UV can be irradiated. As the polarizing element, a polarizing filter or a polarizing element such as a Glan-Thompson-Thompson or a wire grid type polarizing element such as Glenn-Taylor or the like can be used.

Furthermore, when rubbing or polarized light irradiation is performed, if masking is performed, a plurality of regions (patterns) with different liquid crystal alignment directions can also be formed.

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

As a method of obtaining a groove-aligned film, the following method may be exemplified: After exposure is performed through an exposure mask having pattern-shaped slits on the surface of the photosensitive polyimide film, development and rinsing are performed to form a concave-convex pattern. Method; forming a layer of UV-curing resin before hardening on a plate-shaped master with grooves on the surface, and then moving the formed resin layer to the base material and then hardening; and pressing the roller-shaped master with a plurality of grooves against it A method of forming a UV curable resin film before curing of the substrate to form unevenness, and then curing.

In the laminate of the present invention, the vertical alignment liquid crystal cured film and the horizontal alignment retardation film can be laminated via an adhesive layer or an adhesive layer, for example. As the adhesive or bonding agent, those previously known in the field can be used. Moreover, the polymerizable liquid crystal composition for forming a horizontally-aligned liquid crystal cured film can be applied to the vertically-aligned liquid crystal cured film by interposing or not intervening the horizontally-aligned film on the vertically-aligned liquid crystal cured film constituting the laminate of the present invention. Overlay horizontally aligned retardation film (horizontal-aligned liquid crystal cured film).

〔Elliptical Polarizing Plate〕 The present invention includes an elliptical polarizing plate having the laminate and polarizing film of the present invention. The polarizing film is a film having a polarization function, and examples thereof include a stretched film in which a pigment having absorption anisotropy is adsorbed, or a film coated with a dye having absorption anisotropy as a polarizing element. As a dye having absorption anisotropy, for example, a dichroic dye may be mentioned.

A film containing a stretched film adsorbed with a pigment with absorption anisotropy as a polarizing element is usually produced by the following steps: a step of uniaxially stretching a polyvinyl alcohol-based resin film; using a dichroic pigment to convert the polyvinyl alcohol-based resin The step of film dyeing to adsorb the dichroic pigment; the step of treating the polyvinyl alcohol resin film with the dichroic pigment adsorbed by an aqueous solution of boric acid; and the step of washing with the aqueous solution of boric acid to produce a polarizing element , The step of sandwiching at least one surface of the polarizing element with a transparent protective film through an adhesive.

The polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to the homopolymer of vinyl acetate, that is, polyvinyl acetate, a copolymer of vinyl acetate and other monomers copolymerizable therewith is also 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 an ammonium group.

The degree of saponification of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol 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.

A film made of such a polyvinyl alcohol-based resin is used as a blank film of a polarizing film. The film forming method of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The film thickness of the polyvinyl alcohol-based green film can be about 10 to 150 μm, 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. In the case of uniaxial stretching after dyeing, the uniaxial stretching may be performed before the boric acid treatment or may be performed during the boric acid treatment. In addition, uniaxial stretching may be performed in these plural stages. In the case of uniaxial extension, uniaxial extension can be performed between rollers with different peripheral speeds, or a heated roller can be used for uniaxial extension. In addition, the uniaxial stretching may be dry stretching in the atmosphere, or wet stretching in the swelled state of the polyvinyl alcohol-based resin film using a solvent. The stretching ratio is usually about 3 to 8 times.

The dyeing of the polyvinyl alcohol-based resin film with the dichroic dye is performed, for example, by the following method: the polyvinyl alcohol-based resin film is immersed in an aqueous solution containing the dichroic dye.

As the dichroic dye, specifically, iodine or a dichroic organic dye is used. Examples of dichroic organic dyes include C.I. DIRECT RED 39 and other dichroic direct dyes containing bisazo compounds, and dichroic direct dyes containing compounds such as trisazo and tetrasazo. The polyvinyl alcohol resin film is preferably immersed in water before the dyeing treatment.

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

On the other hand, when a dichroic organic dye is used 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 usually adopted. The content of the dichroic organic dye in the aqueous solution per 100 parts by mass of water is usually about 1×10 ^-4 to 10 parts by mass, preferably 1×10 ^-3 to 1 part by mass, and more preferably 1×10 ^-3 ～1×10 ^-2 parts by mass. The aqueous solution may also contain inorganic salts such as sodium sulfate as a dyeing auxiliary. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80°C. In addition, the time for immersion in the aqueous solution (dyeing time) is usually about 10 to 1,800 seconds.

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

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

After washing with water, a drying process was performed to obtain a polarizing element. The drying treatment can be performed with a hot air dryer or a far-infrared heater, for example. The temperature of the drying treatment is usually about 30 to 100°C, preferably 50 to 80°C. The drying treatment time is usually about 60 to 600 seconds, preferably 120 to 600 seconds. Through the drying process, the moisture content of the polarizing element is reduced to a practical level. The moisture content is usually about 5-20% by mass, preferably 8-15% 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 the drying. In addition, if the moisture content is higher than 20% by weight, the thermal stability of the polarizing element may deteriorate.

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

As a film coated with a pigment having absorption anisotropy, a film obtained by coating a composition containing a dichroic pigment having liquid crystallinity, or a composition containing a dichroic pigment and a polymerizable liquid crystal, etc. . The film preferably has a protective film on one or both sides. As this protective film, the same thing as the example resin film of the base material which can be used for the above-mentioned vertical alignment liquid crystal cured film manufacture can be mentioned.

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

As the film coated with a dye having absorption anisotropy, specifically, the film described in JP 2012-33249 A and the like can be mentioned.

A transparent protective film can be layered on at least one area of the polarizing element obtained in this way, for example via an adhesive layer. As the transparent protective film, the same transparent film as the exemplified resin film of the base material that can be used in the above-mentioned vertical alignment liquid crystal cured film can be used.

The elliptically polarizing plate of the present invention is composed of the laminate of the present invention or the laminate after removing the base material from the laminate of the present invention, and a polarizing film. For example, the elliptically polarizing plate of the present invention can be obtained by laminating the laminate of the present invention and the polarizing film through an adhesive layer or the like. In addition, the elliptically polarizing plate of the present invention can be obtained by bonding the laminate with the polarizing film after removing the base material from the laminate of the present invention.

In one aspect of the present invention, when the laminate of the present invention including the horizontally aligned retardation film and the polarizing film are laminated, it is preferable to use the late axis (optical axis) of the horizontally aligned retardation film constituting the laminate Laminate in such a way that the angle formed by the absorption axis of the polarizing film is 45±5°.

The elliptical polarizing plate of the present invention may have the conventional general elliptical polarizing plate, or the structure of the polarizing film and the retardation film. As such a structure, for example, an adhesive layer (sheet) used to bond an ellipsoidal polarizing plate to a display element such as an organic EL or the like, to protect the surface of a polarizing film or a liquid crystal cured film to prevent scratches or damage. Dirty and used protective film, etc.

The laminated body and the elliptically polarizing plate of the present invention can be used in various display devices. A 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, for example, 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 electrophoresis element, plasma display device, projection display device (such as grating light valve imaging system (GLV) display device, digital display device) Micromirror device (DMD) display device) and piezoelectric ceramic display, etc. Liquid crystal display devices include transmissive liquid crystal display devices, semi-transmissive liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices, and projection liquid crystal displays Any of the devices, etc. The display devices may be display devices that display two-dimensional images, or stereoscopic display devices that display three-dimensional images. In particular, the elliptical polarizer of the present invention has fewer alignment defects and excellent optical properties Therefore, it can be preferably used in organic electroluminescence (EL) display devices, and the laminate of the present invention can be preferably used in liquid crystal display devices and touch panel display devices. By using the laminate or elliptically polarized light of the present invention The board is easy to realize the thinning of the display device, and a display device with excellent optical characteristics and good image display characteristics can be obtained. [Example]

Hereinafter, the present invention will be described in more detail with examples. In addition, the "%" and "parts" in the examples refer to mass% and mass parts, respectively, as long as there is no special description.

1. Example 1 (1) Preparation of polymerizable liquid crystal compound The polymerizable liquid crystal compound (X1) and the polymerizable liquid crystal compound (X2) having the following molecular structures were respectively prepared. The polymerizable liquid crystal compound (X1) is produced according to the method described in Japanese Patent Application Laid-Open No. 2010-31223. In addition, the polymerizable liquid crystal compound (X2) is produced in accordance with the method described in JP 2009-173893 A.

Polymerizable liquid crystal compound (X1) [Chemical 17]

1 mg of the polymerizable liquid crystal compound (X1) was dissolved in 50 mL of tetrahydrofuran to obtain a solution. The solution obtained as the measurement sample is placed in a measurement cell with an optical path length of 1 cm, and the measurement sample is placed in an ultraviolet-visible spectrophotometer ("UV-2450" manufactured by Shimadzu Corporation) and The absorption spectrum is measured, and the maximum absorption wavelength is read from the obtained absorption spectrum. As a result, the maximum absorption wavelength λ _{max in the} wavelength range of 300 to 400 nm is 350 nm.

Polymeric liquid crystal compound (X2) [Chemical 18]

(2) Preparation of a composition for forming a vertical alignment liquid crystal cured film A mixture of 13 parts by mass of "KBE-903" manufactured by Shin-Etsu Chemical Co., Ltd. and 87 parts by mass of cyclopentanone, and 13 parts by mass of "Karenz MOI-EG" manufactured by Showa Denko Co., Ltd. and 87 parts by mass of cyclopentanone The mixture of parts by mass is mixed in the manner of KBE-903: Karenz MOI-EG = 1.00: 1.35 (mass ratio), and then kept at 30°C for 16 hours to obtain functional groups that can react with hydroxyl or carboxyl groups in the molecule. (Hydroxysilyl group) and (meth)acryloyl (acryloyl) compound (pre-reaction compound) mixed liquid (hereinafter, may be referred to as mixed liquid (1)). Then, 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) is added, referring to the ionic compound A (molecular weight: 645) prepared in Japanese Patent Application No. 2016-514802 2.0 parts by mass, 6 parts by mass of Irgacure 369E (manufactured by BASF JAPAN Co., Ltd.) as a photopolymerization initiator, Shinnakamura Chemical Industry Co., Ltd. as a polymerizable non-liquid crystal compound having two or more (meth)acrylic groups 0.5 parts by mass of "APG-700" (bifunctional, molecular weight: 808) manufactured by Co., Ltd., and N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. Furthermore, a compound having a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acryloyl group in the molecule (pre-reaction compound) relative to 100 parts by mass of the mixture of the polymerizable liquid crystal compounds (X1) and (X2) is The mixed solution (1) was added in 2.35 parts by mass to obtain a mixture. The obtained mixture was stirred at 80° C. for 1 hour, thereby obtaining a composition for forming a vertically aligned liquid crystal cured film.

Ionic compound A: [化19]

(3) Manufacturing of vertical alignment liquid crystal cured film After corona treatment is applied to the COP (Cycloolefin polymer, cycloolefin polymer) film (ZF14-50) manufactured by Zeon Corporation, the above vertical alignment is coated with a bar coater The composition for forming a liquid crystal cured film is self-coated with the composition for forming a vertical alignment liquid crystal cured film using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Electric Co., Ltd.) after heating at 120°C for 90 seconds The surface is irradiated with ultraviolet rays (accumulated light quantity at 365 nm wavelength under nitrogen atmosphere: 500 mJ/cm ² ), thereby forming a vertical alignment liquid crystal cured film. The film thickness of the obtained vertical alignment liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Corporation), and the result was 1.2 μm.

＜Rth measurement of vertical alignment liquid crystal cured film＞ Perform corona treatment on the vertical alignment liquid crystal hardened film surface of the laminate including the substrate and the vertical alignment liquid crystal hardened film made in the above steps, and bond it to the glass with a 25 μm pressure sensitive adhesive made by LINTEC. , The substrate is peeled off. For the obtained laminate containing glass, adhesive, and vertical alignment liquid crystal cured film, KOBRA-WPR manufactured by Oji Measuring Instruments Co., Ltd. was used to measure the frontal retardation value by changing the incident angle of the sample for measuring the optical characteristics of the light direction. And the phase difference value when tilting 40° with the phase advance axis as the center. The average refractive index at each wavelength was measured using an ellipsometer M-220 manufactured by JASCO Corporation. In addition, the film thickness was measured using an Optical NanoGauge film thickness meter C12562-01 manufactured by Hamamatsu Photonics Co., Ltd. Based on the above-mentioned frontal retardation value, retardation value when tilted at 40° with the phase advance axis as the center, average refractive index, and film thickness values, refer to the Oji Measurement Machine Technical Data (http://www.oji-keisoku.co. jp/products/kobra/reference.html) Calculate the three-dimensional refractive index. The optical properties of each vertical alignment liquid crystal cured film are calculated from the obtained three-dimensional refractive index according to the following formula. The results are shown in Table 1. RthC(λ)=((nxC(λ)＋nyC(λ))/2－nzC(λ))×dC Furthermore, RthC(λ) represents the retardation value in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of λ nm. In addition, nxC(λ) represents the principal refractive index of the vertical alignment liquid crystal cured film at the wavelength λ nm, nyC(λ) represents the refractive index in the direction orthogonal to nxC(λ) in the plane at the wavelength λ nm, nzC (λ) represents the refractive index in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of λ nm. When nxC(λ)=nyC(λ), nxC(λ) can be set as the refractive index in any direction within the film plane , DC represents the film thickness of the vertical alignment liquid crystal cured film.

＜Measurement of the peeling force of substrate＞ After corona treatment is applied to the vertical alignment liquid crystal hardened film side of the laminate containing the above-mentioned vertical alignment liquid crystal hardened film and substrate, it is pasted on the vertical 12 cm x horizontal with a 15 μm pressure sensitive adhesive manufactured by LINTEC. 10 cm×0.7 mm thick glass (composition: substrate/vertical alignment liquid crystal cured film/adhesive layer/glass). For the obtained sample, a notch with a width of 2.5 cm was made from the side of the substrate using a cutter. The prepared sample was placed in the Autograph "EZ-L" manufactured by Shimadzu Corporation, and the peeling force when peeling a 2.5 cm wide substrate in a parallel direction with respect to the glass surface was confirmed at a speed of 300 mm/min. The results are shown in Table 1.

＜Evaluation of the edge during cutting and processing＞ After corona treatment is applied to the vertical alignment liquid crystal hardened film side of the laminate containing the above-mentioned vertical alignment liquid crystal hardened film and substrate, it is pasted on the vertical 12 cm x horizontal with a 15 μm pressure sensitive adhesive manufactured by LINTEC. 10 cm×0.7 mm thick glass (composition: substrate/vertical alignment liquid crystal cured film/adhesive layer/glass). For the obtained sample, a 10 cm wide notch was made from the side of the substrate with a cutter, and the cut surface obtained was observed with a microscope (“BX-51” manufactured by Olympus Co., Ltd.), and 11 places were observed every 1 cm , Measure the shortest distance from the cut surface to the raised point of the base material, set the average value of the data at 11 locations as the end raised length, and evaluate the end during cutting according to the following criteria. The results are shown in Table 1. Evaluation criteria ○: Less than 100 μm △: more than 100 μm and less than 200 μm ×: 200 μm or more

2. Examples 2～4 When preparing the composition for forming a vertically-aligned liquid crystal cured film, the addition amount of "APG-700" as a polyfunctional (meth)acrylate compound was changed as described in Table 1, except that it was produced in the same manner as in Example 1 Samples and evaluate them. The results are shown in Table 1.

3. Example 5 When preparing the composition for forming a vertically aligned liquid crystal cured film, in place of APG-700, 3.0 parts by mass of "A-DPH" (hexafunctional, molecular weight: 578) manufactured by Shinnakamura Chemical Co., Ltd. were added. Other than that, the same as in the examples 1 In the same way, samples were prepared and evaluated. The results are shown in Table 1.

4. Example 6 When preparing the composition for forming a vertically-aligned liquid crystal cured film, except that APG-700 was not added (that is, a polyfunctional (meth)acrylate was not blended), a sample was prepared and evaluated in the same manner as in Example 1 except that APG-700 was not added. The results are shown in Table 1.

5. Comparative Example 1 Except for preparing the composition for forming a vertical alignment liquid crystal cured film as follows, a sample was prepared in the same manner as in Example 1, and evaluated. The results are shown in Table 1. (1) Preparation of vertical alignment liquid crystal cured film forming composition 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, 2.0 parts by mass of ionic compound A (molecular weight: 645) prepared with reference to Japanese Patent Application No. 2016-514802 and silane coupling agent "KBE-9103" (Shin-Etsu Chemical Co., Ltd. Co., Ltd.) 0.5 parts by mass, as a photopolymerization initiator, 2-dimethylamino-2-benzyl-1-(4-N-𠰌linylphenyl)butan-1-one (BASF JAPAN 6 parts by mass of "Irgacure (registered trademark) 369 (Irg369)" manufactured by Co., Ltd. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%. The mixture was stirred at 80°C for 1 hour, thereby obtaining a composition for forming a vertically aligned liquid crystal cured film.

[Table 1] Vertical alignment liquid crystal hardened film Characteristic evaluation Rth550 (nm) Rth(450)/Rth(550) Pre-reaction compound (parts by mass) Multifunctional (meth)acrylate compound Substrate peeling force P (N/25 mm) End evaluation during cutting species Adding amount (parts by mass) Example 1 -70 0.85 2.35 APG-700 0.5 0.05 ○ Example 2 -70 0.85 2.35 APG-700 1.0 0.07 ○ Example 3 -70 0.85 2.35 APG-700 2.5 0.14 ○ Example 4 -70 0.85 2.35 APG-700 3.0 0.23 ○ Example 5 -70 0.85 2.35 A-DPH 3.0 0.15 ○ Example 6 -70 0.85 2.35 - - 0.03 △ Comparative example 1 -70 0.85 - - - 0.01 X

According to the present invention, it is possible to directly form a vertical alignment liquid crystal cured film without forming a vertical alignment film on the substrate. In addition, it was confirmed that the substrate and the vertical alignment liquid crystal cured film have the best adhesion. Therefore, when the laminate including the vertical alignment liquid crystal cured film is cut, the vertical alignment liquid crystal cured film is not easily peeled from the substrate. And when peeling off the base material from the laminate, it can be peeled off with a small amount of force.

1: Substrate 2: Vertical alignment liquid crystal hardened film 11: Laminated body a: Substrate side interface b: Non-substrate side interface

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

Claims (19)

A laminated body comprising a substrate and a vertical alignment liquid crystal cured film adjacent to the substrate, The vertical alignment liquid crystal cured film is a cured product of a polymerizable liquid crystal composition containing at least one vertical alignment accelerator and at least one polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is positioned perpendicular to the plane of the liquid crystal cured film. The liquid crystal cured film is cured in the state of alignment in the direction, and The above-mentioned layered body satisfies formula (1): 0.02＜P＜1.00 (N/25 mm) (1) [In formula (1), P is the substrate peeling force (N/25 mm) when peeling the substrate at a speed of 300 mm/min at the interface between the vertically aligned liquid crystal cured film constituting the laminate and the substrate]. Such as the laminate of claim 1, wherein the thickness of the vertical alignment liquid crystal cured film is 0.3 μm or more and 5.0 μm or less. Such as the laminate of claim 1 or 2, wherein the vertical alignment liquid crystal cured film satisfies the formula (2): -150 nm≦RthC(550)≦-30 nm (2) [In formula (2), RthC(550) represents the retardation value in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of 550 nm]. The laminate according to any one of claims 1 to 3, wherein the polymerizable liquid crystal compound has a (meth)acryloyl group as a polymerizable group. The laminate according to any one of claims 1 to 4, wherein the vertical alignment liquid crystal cured film contains an ionic compound containing a non-metal atom as a vertical alignment promoter. The laminate of claim 5, wherein the molecular weight of the ionic compound containing non-metal atoms is 100 or more and 10,000 or less. The laminate according to any one of claims 1 to 6, wherein the polymerizable liquid crystal composition forming the vertical alignment liquid crystal cured film contains at least one vertical alignment promoter, and at least one polymerizable having a (meth)acryloyl group Liquid crystal compound and at least one polymerizable non-liquid crystal compound having two or more (meth)acrylic groups. The laminate according to any one of claims 1 to 7, wherein the vertical alignment liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter. The laminate of claim 8, wherein the nonionic silane compound is a silane coupling agent. The laminate according to any one of claims 1 to 4, wherein the vertical alignment liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter and an ionic compound containing non-metal atoms. The laminate according to any one of claims 1 to 10, wherein the vertically aligned liquid crystal cured film contains a compound having a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acryloyl group in the molecule. The laminate according to any one of claims 1 to 11, wherein the vertical alignment liquid crystal cured film satisfies the following relationship (3): RthC(450)/RthC(550)≦1.0 (3) [In formula (3), RthC (450) represents the phase difference in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the phase difference in the thickness direction of the vertical alignment liquid crystal cured film at a wavelength of 550 nm Difference]. The laminate according to any one of claims 1 to 12, which further includes a horizontally-aligned retardation film. The laminate of claim 13, wherein the horizontally-aligned retardation film is a horizontally-aligned liquid crystal cured film formed by curing at least one polymerizable liquid crystal compound in a state where it is horizontally aligned with respect to the in-plane direction of the retardation film. An elliptical polarizing plate comprising a laminate as claimed in claim 13 or 14, and a polarizing film. Such as the elliptical polarizing plate of claim 15, wherein the angle formed by the retardation axis of the horizontally aligned retardation film and the absorption axis of the polarizing film is 45±5°. An organic EL display device comprising the elliptical polarizer as claimed in claim 15 or 16. A composition for forming a vertically aligned liquid crystal cured film, comprising: a compound selected from the group consisting of a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acrylic acid group in the molecule, and a (meth)acrylic acid having two or more (meth)acrylic groups At least one of the group consisting of polymerizable non-liquid crystal compounds, Polymerizable liquid crystal compound, and An ionic compound containing non-metal atoms as a vertical alignment promoter. The composition for forming a vertically aligned liquid crystal cured film according to claim 18, wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound having a (meth)acryloyl group.

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