JP7368103B2 - Composition for forming laminates and vertically aligned liquid crystal cured films - Google Patents

Description

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

An elliptically polarizing plate is an optical member in which a polarizing plate and a retardation plate are laminated.For example, in a device that displays an image in a flat state, such as an organic EL image display device, the elliptically polarizing plate is used to prevent light reflection at the electrodes that constitute the device. It is used to prevent As a retardation plate constituting this elliptical polarizing plate, a so-called λ/4 plate is generally used. As such a retardation plate, a retardation plate made of a horizontally oriented liquid crystal cured film in which a polymerizable liquid crystal compound is polymerized and cured while oriented horizontally with respect to the plane of the retardation plate is known. . Furthermore, by further incorporating a vertically aligned liquid crystal cured film into an elliptical polarizing plate equipped with a horizontally aligned liquid crystal cured film, it is possible to suppress orthorhombic hue change during black display when the elliptically polarized plate is used in an organic EL display device. known to obtain. Patent Document 1 describes a method for forming a vertically aligned liquid crystal cured film by forming a vertically aligned film on a base material and applying a composition containing a polymerizable liquid crystal compound onto the vertically aligned film. . A laminate including a vertically aligned liquid crystal cured film and a horizontally aligned liquid crystal cured film formed on a horizontally aligned film is described.

Japanese Patent Application Publication No. 2015-57646

However, conventionally, in order to generally produce a vertically aligned cured liquid crystal film, a vertically aligned film for vertically aligning a polymerizable liquid crystal compound is required. Therefore, it is necessary to form a vertical alignment film before forming a vertically aligned liquid crystal cured film, and at least two coatings are required to obtain coating films from the composition for forming an alignment film and the composition for forming a cured liquid crystal film. There is a problem that a film forming step is required and productivity tends to decrease. On the other hand, in order to improve productivity, there is a need for a method of forming a vertically aligned liquid crystal cured film without forming a vertically aligned film, and the present inventors have developed a method for forming a vertically aligned liquid crystal cured film without forming a vertically aligned film. We have developed and proposed a laminate containing a vertically aligned liquid crystal cured film formed directly on a substrate. In such development, in order to directly form a vertically aligned liquid crystal cured film on a substrate without a vertical alignment film, when a compound having vertical alignment regulating power is blended into the vertically aligned liquid crystal cured film, the vertical alignment cured film is It has been newly discovered that the adhesion between the film and the base material tends to decrease, and the base material can become more easily peeled off than necessary.

The present invention provides a novel solution to the above problem, in which a vertically aligned liquid crystal cured film formed without a vertically aligned film and a base material are laminated with optimal adhesion strength, and the base material is peeled off optimally. The purpose is to provide a laminate that exhibits force.

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention includes the following aspects.
[1] A laminate including a base material and a vertically aligned liquid crystal cured film adjacent to the base material,
The vertical alignment cured liquid crystal 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 in a plane of the cured liquid crystal film. It is a liquid crystal cured film that is cured in a state perpendicular to the
A laminate that satisfies formula (1).
0.02<P<1.00 (N/25mm) (1)
[In formula (1), P is the base material peeling force (N/25 mm) when the base material is peeled off at a speed of 300 mm/min at the interface between the vertically aligned liquid crystal cured film and the base material constituting the laminate. be. ]
[2] The laminate according to [1] above, wherein the vertically aligned liquid crystal cured film has a thickness of 0.3 μm or more and 5.0 μm or less.
[3] The laminate according to [1] or [2] above, wherein the vertically aligned liquid crystal cured film satisfies formula (2).
-150nm≦RthC(550)≦-30nm (2)
[In formula (2), RthC (550) represents the retardation value in the thickness direction at a wavelength of 550 nm of the vertically aligned liquid crystal cured film. ]
[4] The laminate according to 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 according to any one of [1] to [4] above, wherein the vertically aligned liquid crystal cured film contains an ionic compound consisting of nonmetallic atoms as a vertical alignment promoter.
[6] The laminate according to [5] above, which contains an ionic compound made of the nonmetallic atom, and the ionic compound has a molecular weight of 100 or more and 10,000 or less.
[7] The polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains at least one vertical alignment promoter, at least one polymerizable liquid crystal compound having a (meth)acryloyl group, and two or more (meth)acryloyl groups. ) The laminate according to any one of [1] to [6] above, which contains at least one polymerizable non-liquid crystal compound having an acryloyl group.
[8] The laminate according to any one of [1] to [7], wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter.
[9] The laminate according to [8], which includes the nonionic silane compound, and the nonionic silane compound is a silane coupling agent.
[10] The laminate according to any one of [1] to [9], wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound and an ionic compound as vertical alignment promoters.
[11] 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, according to any one of [1] to [10] above. laminate.
[12] The laminate according to any one of [1] to [11] above, wherein the vertically aligned liquid crystal cured film satisfies the following relational expression (3).
RthC(450)/RthC(550)≦1.0 (3)
[In formula (3), RthC (450) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. represents. ]
[13] The laminate according to any one of [1] to [12], further comprising a horizontally oriented retardation film.
[14] The horizontally oriented liquid crystal cured film, wherein the horizontally oriented retardation film is a horizontally oriented liquid crystal cured film obtained by curing at least one polymerizable liquid crystal compound oriented horizontally with respect to the in-plane direction of the retardation film. ] The laminate described in .
[15] An elliptically polarizing plate comprising the laminate according to [13] or [14] above, and a polarizing film.
[16] The elliptically polarizing plate according to [15] above, wherein the angle between the slow axis of the horizontally oriented retardation film and the absorption axis of the polarizing film is 45±5°.
[17] An organic EL display device comprising the elliptically polarizing plate according to [15] or [16].
[18] A compound selected from the group consisting of 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, and a polymerizable non-liquid crystal compound having two or more (meth)acryloyl groups. at least one type of
a polymerizable liquid crystal compound;
A composition for forming a vertically aligned liquid crystal cured film, comprising an ionic compound consisting of nonmetallic atoms as a vertical alignment promoter.
[19] The composition for forming a vertically aligned liquid crystal cured film according to [18] above, wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound having a (meth)acryloyl group.

According to the present invention, it is possible to provide a laminate in which a vertically aligned liquid crystal cured film formed without a vertically aligned film and a base material are laminated with optimal adhesion strength, and exhibit optimal base material peeling force.

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

The laminate of the present invention includes a vertically aligned liquid crystal cured film and a base material. In the present invention, the vertically aligned liquid crystal cured film is laminated on the base material without interposing the vertically aligned film, and the base material and the vertically aligned liquid crystal cured film are adjacent to each other. In the present invention, since the vertically aligned liquid crystal cured film can be formed without a vertically aligned film in the laminate of the present invention, the number of manufacturing steps for the laminate is reduced, resulting in a laminate that can be manufactured with high productivity.

FIG. 1 shows one embodiment of the laminate of the present invention, although it is not limited thereto, and shows the most basic layer configuration of the laminate of the present invention. The laminate 11 shown in FIG. 1 is formed by laminating a base material 1 and a vertically aligned liquid crystal cured film 2. In the laminate 11 shown in FIG. 1, the vertical alignment liquid crystal cured film 2 is formed directly on the base material 1 without using a layer having vertical alignment regulating force (hereinafter also referred to as "vertical alignment film"). , a base material 1 and a vertically aligned liquid crystal cured film 2 are adjacent to each other. The laminate of the present invention may further include other layers in addition to the base material and the vertically aligned liquid crystal cured film. Other layers include a horizontally oriented retardation film (horizontally oriented liquid crystal cured film), a horizontally oriented film, a cured resin layer such as a protective layer or a hard coat layer, and a adhesive for adhering the laminate of the present invention to a polarizing film, etc. Examples include an adhesive layer.

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

In the present invention, the vertically aligned liquid crystal cured film is formed directly on the substrate without using a vertically aligned film. The polymerizable liquid crystal composition for forming the vertically aligned liquid crystal cured film (hereinafter also referred to as "composition for forming a vertically aligned liquid crystal cured film") contains a vertical alignment accelerator, and when applied onto a substrate, It is designed to exert a vertical alignment regulating force for aligning the polymerizable liquid crystal compound contained in the composition in a direction perpendicular to the plane of the coating film. In the present invention, the composition for forming a vertically aligned liquid crystal cured film is used at the interface on the substrate side (interface a in FIG. 1: hereinafter referred to as interface a in FIG. , also referred to as the "substrate-side interface") may contain a component (for example, an ionic compound consisting of a non-metallic atom as described below) that generates an electrostatic repulsion force against the polymerizable liquid crystal compound as a vertical alignment promoter. . However, components that generate electrostatic repulsion tend to segregate at the substrate-side interface when the composition for forming a vertically aligned liquid crystal cured film is applied onto the substrate. In addition, components that generate electrostatic repulsion generally do not have polymerizable groups, and form a network structure with each other and with the polymerizable liquid crystal compound that forms the vertically aligned liquid crystal cured film. Therefore, cohesive failure tends to occur easily at the substrate side interface of the vertically aligned cured liquid crystal film that segregates. In a laminate containing a vertically aligned cured liquid crystal film formed directly on a base material, cohesive failure tends to occur near the interface on the base material side where the vertical alignment promoter segregates during cutting. It is necessary to improve the adhesion between the vertically aligned liquid crystal cured film and the base material because it becomes easy to peel off from the material and this causes lifting or peeling at the end of the laminate, leading to product defects.

If the base material peeling force P in the laminate of the present invention is 0.02 or less, the adhesion between the base material and the vertically aligned liquid crystal cured film will be insufficient, and the laminate will be separated from the base material during cutting, etc. It becomes difficult to sufficiently suppress peeling of the vertically aligned liquid crystal cured film. On the other hand, if the base material peeling force is 1.00 or more, the adhesion between the base material and the vertically aligned liquid crystal cured film becomes too high, and a large force is required to peel the base material from the laminate. It becomes difficult to cleanly peel the substrate and the vertically aligned liquid crystal cured film from each other without leaving any residue. When the laminate of the present invention satisfies the above formula (1), the base material and the vertically aligned liquid crystal cured film adjacent thereto are laminated with appropriate adhesion, and the laminate It is difficult for the vertically aligned liquid crystal cured film to peel off from the base material when cutting, etc. This results in a laminate that can be peeled off. In the present invention, the base material peeling force P is preferably 0.03 N/25 mm or more, more preferably 0.035 N/25 mm or more, even more preferably 0.04 N/25 mm or more, and preferably 0.8 N/25 mm or more. It is 25 mm or less, more preferably 0.6 N/25 mm or less, even more preferably 0.5 N/25 mm or less.
In addition, the said base material peeling force P can be measured according to the method described in the Example mentioned later.

The base material peeling force P in the laminate can be controlled by selecting the composition of the vertically aligned liquid crystal cured film forming composition and the type of the base material, particularly the surface condition of the base material. can.
Hereinafter, each structure of the laminate of the present invention will be explained in detail.

[Vertical alignment liquid crystal cured film]
The vertically aligned liquid crystal cured film constituting the laminate of the present invention is a cured product of a polymerizable liquid crystal composition containing at least one vertical alignment promoter and at least one polymerizable liquid crystal compound. The vertically aligned cured liquid crystal film is a cured liquid crystal film in which the polymerizable liquid crystal compound is oriented in a direction perpendicular to the plane of the cured liquid crystal film. In the present invention, the vertical alignment cured liquid crystal film includes a vertical alignment promoter. That is, in the present invention, the composition for forming a vertically aligned liquid crystal cured film (polymerizable liquid crystal composition) that forms the vertically aligned liquid crystal cured film contains a vertical alignment promoter. In the present invention, the vertical alignment promoter refers to a material that promotes liquid crystal alignment of a polymerizable liquid crystal compound in a direction perpendicular to the film plane. Since the vertically aligned liquid crystal cured film contains the vertical alignment promoter, the vertically aligned liquid crystal cured film can be formed without a vertical alignment film. As a result, in the laminate of the present invention, there is no need to form a vertically aligned liquid crystal cured film, the manufacturing process of the laminate is simplified, and the laminate can be manufactured with high productivity.

In the present invention, the composition for forming a vertically aligned liquid crystal cured film is used as a vertical alignment promoter that promotes alignment of a polymerizable liquid crystal compound in the vertical direction. It is preferable to include a component that generates an electrostatic repulsion force with respect to the polymerizable liquid crystal compound. Examples of such components include ionic compounds. From the viewpoint of suppressing the occurrence of alignment defects in the vertically aligned cured liquid crystal film, it is preferable that the vertical alignment promoter contains an ionic compound consisting of nonmetallic atoms. When the composition for forming a vertically aligned liquid crystal cured film contains an ionic compound consisting of non-metallic atoms, the dry coating film formed from the composition has a vertical alignment regulating force on the polymerizable liquid crystal compound due to electrostatic interaction. is expressed, and the polymerizable liquid crystal compound can be oriented in the direction perpendicular to the film plane within the dried coating film. Thereby, a cured liquid crystal film can be formed while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned.

Ionic compounds consisting of nonmetallic atoms (hereinafter also simply referred to as "ionic compounds") include, for example, onium salts (more specifically, quaternary ammonium salts in which the nitrogen atom has a positive charge, tertiary (class sulfonium salts, quaternary phosphonium salts in which the phosphorus atom has a positive charge, etc.). Among these onium salts, quaternary onium salts are preferred from the viewpoint of further improving the vertical alignment of the polymerizable liquid crystal compound, and quaternary phosphonium salts or quaternary onium salts are preferred from the viewpoint of improving availability and mass production. Ammonium salts are more preferred. The onium salt may have two or more quaternary onium salt sites in the molecule, and may be an oligomer or a polymer.

The molecular weight of the ionic compound is preferably 100 or more and 10,000 or less. When the molecular weight is within the above range, it is easy to improve the vertical alignment of the polymerizable liquid crystal compound while ensuring the coatability of the composition for forming a vertically aligned liquid crystal cured film. The molecular weight of the ionic compound is more preferably 5,000 or less, still more preferably 3,000 or less.

Examples of the cation component of the ionic compound include inorganic cations and organic cations. Among these, organic cations are preferred because they are less likely to cause alignment defects in the polymerizable liquid crystal compound. Examples of organic cations include imidazolium cations, pyridinium cations, ammonium cations, sulfonium cations, and phosphonium cations.

Ionic compounds generally have a counteranion. Examples of the anion component serving as a counter ion to the cation component include inorganic anions and organic anions. Among these, organic anions are preferred because they are less likely to cause alignment defects in the polymerizable liquid crystal compound. Note that cations and anions do not necessarily have to have a one-to-one correspondence.

Specific examples of the anion component include the following.
Chloride anion [Cl ^- ],
Bromide anion [Br ^- ],
Iodide anion [ ^I- ],
Tetrachloroaluminate anion [AlCl ₄ ^- ],
heptachlorodialuminate anion [Al ₂ Cl ₇ ⁻ ],
Tetrafluoroborate anion [BF ₄ ^- ],
hexafluorophosphate anion [PF ₆ ^- ],
perchlorate anion [ClO ₄ ^- ],
Nitrate anion [NO ₃ ^- ],
Acetate anion [CH ₃ COO ⁻ ],
trifluoroacetate anion [CF ₃ COO ⁻ ],
Fluorosulfonate anion [FSO ₃ ^- ],
methanesulfonate anion [CH ₃ SO ₃ ^- ],
trifluoromethanesulfonate anion [CF ₃ SO ₃ ^- ],
p-toluenesulfonate anion [p-CH ₃ C ₆ H ₄ SO ₃ ⁻ ],
Bis(fluorosulfonyl)imide anion [(FSO ₂ ) ₂ N ⁻ ],
Bis(trifluoromethanesulfonyl)imide anion [(CF ₃ SO ₂ ) ₂ N ⁻ ],
Tris(trifluoromethanesulfonyl)methanide anion [(CF ₃ SO ₂ ) ₃ C ⁻ ],
hexafluoroarsenate anion [AsF ₆ ^- ],
hexafluoroantimonate anion [SbF ₆ ^- ],
hexafluoroniobate anion [NbF ₆ ^- ],
hexafluorotantalate anion [TaF ₆ ^- ],
dimethylphosphinate anion [(CH ₃ ) ₂ POO ⁻ ],
(Poly)hydrofluorofluoride anion [F(HF) _n ⁻ ] (for example, n represents an integer from 1 to 3),
Dicyanamide anion [(CN) ₂ N ^- ],
Thiocyananion [SCN ^- ],
perfluorobutanesulfonate anion [C ₄ F ₉ SO ₃ ^- ],
Bis(pentafluoroethanesulfonyl)imide anion [(C ₂ F ₅ SO ₂ ) ₂ N ⁻ ],
perfluorobutanoate anion [C ₃ F ₇ COO ^- ], and (trifluoromethanesulfonyl)(trifluoromethanecarbonyl)imide anion [(CF ₃ SO ₂ ) (CF ₃ CO) N ^- ].

Specific examples of the ionic compound can be appropriately selected from the above combinations of cationic components and anionic components. Specific examples of compounds that are a combination of a cation component and an anion component include the following.

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

(imidazolium salt)
1-ethyl-3-methylimidazolium hexafluorophosphate,
1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide,
1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide,
1-ethyl-3-methylimidazolium p-toluenesulfonate,
1-Butyl-3-methylimidazolium methanesulfonate, etc.

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

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

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

From the viewpoint of further improving the vertical alignment of the polymerizable liquid crystal compound, it is preferable that the ionic compound has Si element and/or F element in the molecular structure of the cation site. When the ionic compound has Si element and/or F element in the molecular structure of the cation site, the ionic compound is likely to be segregated on the surface of the vertically aligned liquid crystal cured film. Among these, the following ionic compounds (i) to (iii) are preferred as ionic compounds whose constituent elements are all nonmetallic elements.

（イオン性化合物（ｉｉ））

（イオン性化合物（ｉｉｉ））

(Ionic compound (i))

(Ionic compound (ii))

(Ionic compound (iii))

For example, a method of treating the surface of a substrate with a surfactant having an alkyl group having a relatively long chain length to improve the orientation of liquid crystals (for example, see Chapter 2 of "Liquid Crystal Handbook", "Orientation and Physical Properties of Liquid Crystals" (Maruzen)) Co., Ltd.), etc.), the vertical alignment of the polymerizable liquid crystal compound can be further improved. That is, by treating the surface of the substrate with an ionic compound having an alkyl group with a relatively long chain length, the vertical alignment of the polymerizable liquid crystal compound can be effectively improved.

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

In addition, when there are two or more positively charged atoms in the molecule of an ionic compound, substituents having two or more positively charged atoms are counted from the positively charged atom considered as the base point. The number of covalent bonds from the nearest other positively charged atom to the nearest other positively charged atom is defined as the "number of covalent bonds from the positively charged atom to the end of the molecular chain" described in the definition of M above. Furthermore, when the ionic compound is an oligomer or polymer having two or more repeating units, the above M is calculated by considering the constituent unit as one molecule. If an atom with a positive charge is incorporated into a ring structure, the number of covalent bonds through the ring structure to the atom with the same positive charge, or to the end of a substituent bonded to the ring structure. Among the numbers of covalent bonds, the one with the larger number of covalent bonds is defined as "the number of covalent bonds from the positively charged atom to the end of the molecular chain" described in the definition of M above.

When the composition for forming a vertically aligned liquid crystal cured film contains an ionic compound consisting of nonmetallic atoms, the content is usually 100 parts by mass of the polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film. The amount is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass or less, More preferably, it is 3 parts by mass or less. When the content of the ionic compound consisting of nonmetallic atoms is within the above range, the vertical alignment of the polymerizable liquid crystal compound can be effectively improved while maintaining good coating properties of the composition for forming a vertically aligned liquid crystal cured film. It can be promoted.

The composition for forming a vertically aligned liquid crystal cured film is used as a vertical alignment accelerator when the composition is applied onto a substrate to form a vertically aligned liquid crystal cured film at an interface opposite to the substrate (interface b in FIG. 1). It is preferable to include a component that can exert a vertical alignment regulating force that aligns the polymerizable liquid crystal compound in a direction perpendicular to the film plane by lowering the surface energy at the non-substrate side interface (hereinafter also referred to as "non-substrate side interface"). . Examples of such components include nonionic silane compounds. When the composition for forming a vertically aligned liquid crystal cured film contains a nonionic silane compound, the nonionic silane compound lowers the surface tension of the composition for forming a vertically aligned liquid crystal cured film, and the dry coating formed from the composition decreases. In the film, nonionic silane compounds tend to be unevenly distributed at the interface between the dry paint film and the air, increasing the ability to regulate the vertical alignment of the polymerizable liquid crystal compound, and directing the polymerizable liquid crystal compound against the film plane within the dry paint film. It can be oriented vertically. Thereby, a cured liquid crystal film can be formed while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned.

A nonionic silane compound is a compound that is nonionic and contains Si element. Nonionic silane compounds include, for example, silicon polymers such as polysilanes, silicone resins such as silicone oils and silicone resins, as well as organic and inorganic silane compounds (more specifically is a silane coupling agent, etc.). These nonionic silane compounds may be used alone or in combination of two or more. Among these, silane coupling agents are preferred from the viewpoint of further improving adhesion with adjacent layers.

The nonionic silane compound may be of the silicone monomer type or may be of the silicone oligomer (polymer) type. Silicone oligomers are expressed in the form of (monomer)-(monomer) copolymers: 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltrimethoxysilane-tetraethoxysilane copolymer, Copolymers containing mercaptopropyl groups, such as propyltriethoxysilane-tetramethoxysilane copolymers and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymers; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymers, mercaptomethyltrimethoxysilane-tetra Copolymers containing mercaptomethyl groups, such as ethoxysilane copolymers, mercaptomethyltriethoxysilane-tetramethoxysilane copolymers and mercaptomethyltriethoxysilane-tetraethoxysilane copolymers; 3-methacryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymers, 3 -Methacryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetramethoxysilane copolymer, 3-methacryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane- Tetramethoxysilane copolymer, 3-methacryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloyloxypropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-methacryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymer Copolymers containing methacryloyloxypropyl groups such as 3-acryloyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyltriethoxysilane-tetramethoxy Silane copolymer, 3-acryloyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-acryloyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloyloxypropyl Copolymers containing acryloyloxypropyl groups, such as methyldiethoxysilane-tetramethoxysilane copolymers and 3-acryloyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymers; vinyltrimethoxysilane-tetramethoxysilane copolymers, vinyltrimethoxysilane- Tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane - Copolymers containing vinyl groups such as tetramethoxysilane copolymers and vinylmethyldiethoxysilane-tetraethoxysilane copolymers; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymers, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymers , 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetraethoxy Examples include amino group-containing copolymers such as silane copolymers, 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymers, and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymers.

The silane coupling agent has a terminal group selected from the group consisting of vinyl group, epoxy group, styryl group, methacrylic group, acrylic group, amino group, isocyanurate group, ureido group, mercapto group, isocyanate group, carboxyl group, and hydroxyl group. It is a compound containing an Si element and having at least one functional group such as the above, and at least one alkoxysilyl group or silanol group. By appropriately selecting these functional groups, specific properties such as improving the mechanical strength of the cured vertically aligned liquid crystal film, modifying the surface of the cured vertically aligned liquid crystal film, and improving the adhesion between the cured vertically aligned liquid crystal film and adjacent layers can be achieved. This makes it possible to impart a unique effect. From the viewpoint of adhesion, the silane coupling agent is preferably a silane coupling agent having an alkoxysilyl group and another different reactive group (for example, the above-mentioned functional group). Furthermore, it is preferable that the silane coupling agent is a silane coupling agent having an alkoxysilyl group and a polar group. When the silane coupling agent has at least one alkoxysilyl group and at least one polar group in its molecule, the vertical alignment of the polymerizable liquid crystal compound can be more easily improved, and the effect of promoting vertical alignment can be significantly obtained. There is a tendency. Examples of the polar group include an epoxy group, an amino group, an isocyanurate group, a mercapto group, a carboxyl group, and a hydroxy group. Note that the polar group may have an appropriate substituent or protective group in order to control the reactivity of the silane coupling agent.

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

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

When the composition for forming a vertically aligned liquid crystal cured film contains a nonionic silane compound, the content is usually equal to or less than the amount of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition contained in the composition for forming a vertically aligned liquid crystal cured film. With respect to 100 parts by mass, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, and preferably 5 parts by mass or less, more preferably It is 4 parts by mass or less, more preferably 3 parts by mass or less. When the content of the nonionic silane compound is within the above range, vertical alignment of the polymerizable liquid crystal compound can be effectively promoted while maintaining good coating properties of the polymerizable liquid crystal composition.

In the present invention, the vertically aligned liquid crystal cured film preferably contains at least one of an ionic compound made of nonmetallic atoms and a nonionic silane compound as a vertical alignment promoter, and an ionic compound made of nonmetallic atoms. It is more preferable to contain a compound, and it is more preferable to contain both an ionic compound made of a nonmetallic atom and a nonionic silane compound. Since the vertically aligned liquid crystal cured film contains both an ionic compound consisting of non-metallic atoms and a nonionic silane compound, in the dry coating film formed from the composition for forming a vertically aligned liquid crystal cured film, the substrate side Due to the electrostatic interaction derived from the ionic compound composed of non-metallic atoms at the interface and the surface energy lowering effect derived from the non-ionic silane compound at the non-substrate side interface, the polymerizable liquid crystal compound forms at both interfaces of the cured liquid crystal film. Since a vertical alignment regulating force is generated, the vertical alignment of the polymerizable liquid crystal compound is more likely to be promoted. Thereby, a cured liquid crystal film can be formed while maintaining the state in which the polymerizable liquid crystal compound is vertically aligned with higher accuracy.

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 vertical alignment accelerator. In the present invention, the polymerizable liquid crystal compound contained in the vertical alignment liquid crystal cured film forming composition (polymerizable liquid crystal composition) that forms the vertical alignment 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, polymerizable liquid crystal compounds conventionally known in the field of retardation films can be used.

A polymerizable group refers to a group that can participate in a polymerization reaction by active radicals, acids, etc. generated from a polymerization initiator. Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, (meth)acryloyl group, oxiranyl group, and oxetanyl group. Among these, compounds having in the molecule a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acryloyl group, and/or a polymerizable non-liquid crystal compound having two or more (meth)acryloyl groups, as described below. A (meth)acryloyl group is preferable because it can form a network structure between the groups and is effective in improving adhesion to the base material. Note that (meth)acryloyl group means acryloyl group or methacryloyl group, and similarly (meth)acrylate means acrylate or methacrylate.

The liquid crystallinity exhibited by the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, but a thermotropic liquid crystal is preferable because it allows precise film thickness control. Further, the phase ordered structure of the thermotropic liquid crystal may be either a nematic liquid crystal or a smectic liquid crystal. The polymerizable liquid crystal compounds can be used alone or in combination of two or more.

Polymerizable liquid crystal compounds generally include polymerizable liquid crystal compounds that exhibit forward wavelength dispersion and polymerizable liquid crystal compounds that exhibit reverse wavelength dispersion, and it is also possible to use only one type of polymerizable liquid crystal compound. It is also possible to use a mixture of both types of polymerizable liquid crystal compounds. In a display device incorporating the resulting laminate, it is preferable to include a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion, from the viewpoint of increasing the effect of suppressing the oblique reflection hue during black display. 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) A compound capable of forming a nematic phase or a smectic phase.
(B) The polymerizable liquid crystal compound has π electrons in the long axis direction (a).
(C) It has π electrons in a direction [intersecting direction (b)] that intersects with the major axis direction (a).
(D) A polymerizable liquid crystal compound defined by the following formula (i) where the total of π electrons present in the major axis direction (a) is N (πa) and the total molecular weight present in the major axis direction is N (Aa) π electron density in the long axis direction (a):
D(πa)=N(πa)/N(Aa) (i)
and a polymerizable liquid crystal compound defined by the following formula (ii) where the total of π electrons existing in the intersecting direction (b) is N (πb), and the total molecular weight existing in the intersecting direction (b) is N (Ab) π electron density in the crossing direction (b):
D(πb)=N(πb)/N(Ab) (ii)
is the formula (iii)
0≦[D(πa)/D(πb)]<1 (iii)
[That is, the π electron density in the cross direction (b) is larger than the π electron density in the major axis direction (a)]. Further, as described above, a polymerizable liquid crystal compound having π electrons on the long axis and in a direction crossing the long axis has, for example, a T-shaped structure.

In the features (A) to (D) above, the major axis direction (a) and the number N of π electrons are defined as follows.
- For example, in the case of 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 major axis direction (a) does not include π electrons that disappear due to polymerization reaction.
・The number N (πa) of π electrons existing on the long axis direction (a) is the total number of π electrons on the long axis and π electrons conjugated with this, for example, the number N (πa) existing on the long axis direction (a). It includes the number of π electrons present in a ring that satisfies Huckel's rule.
- The number of π electrons N (πb) existing in the cross direction (b) does not include π electrons that disappear due to the polymerization reaction.
A polymerizable liquid crystal compound that satisfies the above has a mesogenic structure in the long axis direction. This mesogenic structure develops a liquid crystal phase (nematic phase, smectic phase).

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

Polymerizable liquid crystal compounds having the above characteristics generally exhibit reverse wavelength dispersion in many cases. Specifically, for example, a compound represented by the following formula (X) may be mentioned.

In formula (X), Ar represents a divalent group having an aromatic group which may have a substituent. The aromatic group here refers to a ring structure in which the number of π electrons is [4n+2] according to Huckel's rule, and is exemplified by (Ar-1) to (Ar-23) described below. It may have two or more such Ar groups via a divalent linking group. Here n represents an integer. In the case where a ring structure is formed containing heteroatoms such as -N= and -S-, it also satisfies Huckel's rule including non-covalently bonded electron pairs on these heteroatoms and has aromaticity. Preferably, the aromatic group contains at least one of a nitrogen atom, an oxygen atom, and a sulfur atom. The number of aromatic groups contained in the divalent group Ar may be one, or two or more. When there is one aromatic group, the divalent group Ar may be a divalent aromatic group which may have a substituent. When the divalent group Ar contains two or more aromatic groups, the two or more aromatic groups are bonded to each other through a single bond or a divalent bonding group such as -CO-O- or -O-. You can leave it there.
G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or divalent alicyclic hydrocarbon group is a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or a fluoroalkyl group having 1 to 4 carbon atoms. The carbon atoms constituting the divalent aromatic group or divalent alicyclic hydrocarbon group may be substituted with 1 to 4 alkoxy groups, cyano groups, or nitro groups, and oxygen atoms, sulfur atoms Alternatively, it may be substituted with a nitrogen atom.
L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group.
k and l each independently represent an integer from 0 to 3, and satisfy the relationship 1≦k+l. Here, when 2≦k+l, B ¹ and B ² and G ¹ and G ² may be the same or different from each other.
E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms, with an alkanediyl group having 4 to 12 carbon atoms being more preferred. Furthermore, the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and the -CH ₂ - contained in the alkanediyl group is replaced by -O-, -S-, -SiH ₂ -, -C (=O)- may be substituted.
P ¹ and P ² each independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

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

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

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

From the viewpoint of expressing reverse wavelength dispersion, k and l preferably have a range of 2≦k+l≦6, preferably k+l=4, and more preferably k=2 and l=2. It is preferable that k=2 and l=2 because a symmetrical structure is obtained.

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

Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocycle which may have a substituent, and an electron-withdrawing group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and the like, with benzene rings and naphthalene rings being preferred. The aromatic heterocycles include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, a triazine ring, a pyrroline ring, an imidazole ring, and a pyrazole ring. , thiazole ring, benzothiazole ring, thienothiazole ring, oxazole ring, benzoxazole ring, and phenanthroline ring. Among these, it is preferable to have a thiazole ring, benzothiazole ring, or benzofuran ring, and more preferably to have a benzothiazole group. Further, when Ar includes a nitrogen atom, it is preferable that the nitrogen atom has π electrons.

In formula (X), the total number N _π of π electrons contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, and especially Preferably it is 16 or more. Further, 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.

In formulas (Ar-1) to (Ar-23), the mark * represents a connecting part, and Z ⁰ , Z ¹ and Z ² each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 12 carbon atoms. group, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, alkylsulfonyl group having 1 to 12 carbon atoms, carboxyl group, fluoroalkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, Alkylthio group having 1 to 12 carbon atoms, N-alkylamino group having 1 to 12 carbon atoms, N,N-dialkylamino group having 2 to 12 carbon atoms, N-alkylsulfamoyl group having 1 to 12 carbon atoms, or carbon Represents an N,N-dialkylsulfamoyl group having numbers 2 to 12. Moreover, Z ⁰ , Z ¹ and Z ² may contain a polymerizable group.

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

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

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

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

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

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

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

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

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

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

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

P11-B11-E11-B12-A11-B13- (Y)
[In formula (Y), P11 represents a polymerizable group.
A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group.
B11 is -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹⁶ -, -NR ¹⁶ -CO-, -CO-, - CS- or a single bond. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
B12 and B13 each 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)- Represents O-, -OC(=O)-CH=CH-, -H, -C≡N or a single bond.
E11 represents an alkanediyl group having 1 to 12 carbon atoms, the hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atom contained in the alkoxy group may be substituted with a halogen atom. Furthermore, -CH ₂ - constituting the alkanediyl group may be replaced with -O- or -CO-. ]

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

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

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

[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. ]

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

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.
More preferably, the group represented by P11-B11- is an acryloyloxy group or a methacryloyloxy group.

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

A specific example of the polymerizable liquid crystal compound (Y) is "3.8.6 Network (fully crosslinked)" in the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd. on October 30, 2000). , Compounds having a polymerizable group among the compounds described in "6.5.1 Liquid crystal material b. Polymerizable nematic liquid crystal material", JP 2010-31223 A, JP 2010-270108 A, JP 2010-270108 A, Examples include polymerizable liquid crystals described in JP-A No. 2011-6360 and JP-A No. 2011-207765.

Specific examples of the polymerizable liquid crystal compound (Y) include the following formulas (I-1) to (I-4), formulas (II-1) to (II-4), and formulas (III-1) to (III-26), represented by formula (IV-1) to formula (IV-26), formula (V-1) to formula (V-2), and formula (VI-1) to formula (VI-6) Examples include compounds. Note that in the following formula, k1 and k2 each independently represent an integer of 2 to 12. These polymerizable liquid crystal compounds (Y) are preferable in terms of their ease of synthesis or availability.

The content of the polymerizable liquid crystal compound in the composition for forming a vertically aligned liquid crystal cured film, which forms a vertically aligned liquid crystal cured film, is, for example, 70 to 100 parts by mass based on 100 parts by mass of the solid content of the composition for forming a vertically aligned liquid crystal cured film. The amount is 99.5 parts by weight, preferably 80 to 99 parts by weight, more preferably 85 to 98 parts by weight, and even more preferably 90 to 95 parts by weight. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of orientation of the resulting cured liquid crystal film. In the present invention, the solid content of the polymerizable liquid crystal composition means all components of the polymerizable liquid crystal composition excluding volatile components such as organic solvents. Further, 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 range.

The adhesion between the base material and the vertically aligned liquid crystal cured film in the laminate of the present invention is determined, for example, by the presence of a functional group on the base material having a hydroxyl group or carboxyl group on its surface that can react with the hydroxyl group or carboxyl group. This can be improved by forming a vertically aligned liquid crystal cured film containing a compound having a (meth)acryloyl group in its molecule (hereinafter also referred to as a "pre-reaction compound"). The base material peeling force P of the laminate can be controlled by adjusting the surface treatment state of the base material and the type and content of the pre-reaction compound contained in the vertically aligned liquid crystal cured film.

Therefore, the composition for forming a vertically aligned liquid crystal cured film constituting the laminate of the present invention preferably contains a compound having in its molecule a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acryloyl group. . If a pre-reactive compound is included, when a vertically aligned liquid crystal cured film is formed, the (meth)acryloyl group of the pre-reactive compound and the polymerizable group (especially (meth)acryloyl group) of the polymerizable liquid crystal compound will react. do. Furthermore, the functional group that can react with the hydroxyl group or carboxyl group of the pre-reacted compound also reacts with the hydroxyl group and/or carboxyl group present on the surface of the base material. Through the above two reactions, a crosslinked structure or network structure is formed between the base material and the polymerizable liquid crystal compound, which is the main component of the vertically aligned liquid crystal cured film, through the pre-reacted compound, and the vertically aligned liquid crystal cured film and the polymerizable liquid crystal compound are formed. It becomes possible to improve the adhesion with the base material.

The functional group that can react with the hydroxyl group or carboxyl group that the pre-reacted compound has is not particularly limited as long as it is a functional group that can easily react with the hydroxyl group or carboxyl group. Examples include isocyanate groups, epoxy groups, oxetanyl groups, silanol groups, alkoxysilyl groups, carboxyl groups, hydroxyl groups, amino groups, acyl chloride groups, and hydroxysilyl groups. The pre-reactive compound has at least one functional group capable of reacting with a hydroxyl group or a carboxyl group in its molecule, and when it contains two or more of the functional groups, even if the functional groups are the same, May be different. Among these, at least one selected from the group consisting of isocyanate group, epoxy group, oxetanyl group, silanol group, alkoxysilyl group and hydroxysilyl group is preferable from the viewpoint of relatively high reactivity and ease of handling. More preferably, it is at least one selected from the group consisting of hydroxysilyl group and hydroxysilyl group.

The molecular weight of the pre-reacted compound is preferably 10,000 or less, more preferably 5,000 or less, even more preferably 3,000 or less. When the molecular weight of the pre-reacted compound is below the above upper limit, it is difficult to disturb the alignment of the polymerizable liquid crystal compound forming the vertical alignment film, and while ensuring high alignment accuracy of the polymerizable liquid crystal compound, the adhesion to the base material can be improved. can be improved. On the other hand, the greater the number of covalent bonds between the (meth)acryloyl group and the functional group that can react with the hydroxyl group or carboxyl group in the pre-reacted compound, the easier it is to improve the adhesion between the substrate and the vertically aligned liquid crystal cured film. Therefore, the molecular weight of the pre-reacted compound is preferably 50 or more, more preferably 100 or more, and still more preferably 300 or more.

In the present invention, a composition for forming a vertically aligned liquid crystal cured film is prepared by adding 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. It's okay. Further, the pre-reaction compound may be prepared simultaneously with the preparation of the composition for forming a vertically aligned liquid crystal cured film. As the pre-reaction compound, only one type may be used, or two or more types may be used in combination.

When preparing a pre-reaction compound together with the preparation of a composition for forming a vertically aligned liquid crystal cured film, for example, reacting a hydroxyl group or an amino group with an isocyanate group to form a urethane bond or a urea bond, it is possible to quantitatively react even at room temperature. It is preferable to form the pre-reacted compound using a chemical reaction that progresses easily. For example, a first compound having a functional group capable of reacting with a hydroxyl group or a carboxyl group and an amino group, and a second compound having a (meth)acryloyl group and an isocyanate group are combined into a composition for forming a vertically aligned liquid crystal cured film. A preform having a functional group that can react with a hydroxyl group or a carboxyl group derived from the first compound and a (meth)acryloyl group derived from the second compound by being added to the product or during its preparation process. A reaction compound can be obtained. The compound serving as the material for forming the pre-reaction compound may be mixed in advance in an appropriate solvent, if necessary, and then added to the composition for forming a vertically aligned liquid crystal cured film. It may be directly mixed with other components constituting the composition for use.

The greater the number of covalent bonds between the (meth)acryloyl group and the functional group capable of reacting with the hydroxyl group or carboxyl group in the pre-reaction compound, the more likely it is that the adhesion between the substrate and the vertically aligned liquid crystal cured film will improve. Therefore, in the present invention, the pre-reaction compound is used in the composition for forming a vertically aligned liquid crystal cured film, since the number of covalent bonds can be adjusted and the adhesion between the substrate and the vertically aligned liquid crystal cured film can be easily controlled. It is more preferable to manufacture using a chemical reaction in a product or in the manufacturing process.

Examples of compounds suitable for preparing such a pre-reaction compound include compounds having an alkoxysilyl group and an amino group [for example, KBE-903, KBM-602, KBM-903 (all of the above). Shin-Etsu Chemical Co., Ltd.), etc.). Further, as the second compound, a compound having a (meth)acryloyl group and an isocyanate group [for example, Karenz MOI-EG, Karenz MOI, Karenz AOI, Karenz BEI (all from Showa Denko K.K.), etc. Can be mentioned. By appropriately combining these compounds, a pre-reacted compound can be obtained. The mixing ratio of each compound used to prepare the pre-reacted compound may be appropriately selected based on the structure of the compound used and the chemical reaction to be used.

The content of the pre-reacted compound in the composition for forming a vertically aligned liquid crystal cured film is preferably 0.1 part by mass or more based on 100 parts by weight of the polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film. , more preferably 0.2 parts by mass or more, still more preferably 0.3 parts by mass or more. If the content of the pre-reaction compound is equal to or higher than the above lower limit, the pre-reaction may occur with respect to the hydroxyl group or carboxyl group present on the surface of the substrate or the polymerizable group (especially (meth)acryloyl group) possessed by the polymerizable liquid crystal compound. The functional group or (meth)acryloyl group that can react with the hydroxyl group or carboxyl group of the compound reacts sufficiently, and the adhesion between the substrate and the vertically aligned liquid crystal cured film can be improved. Further, the content of the pre-reaction compound is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably is 5 parts by mass or less. When the content of the pre-reacted compound is below the above upper limit, the base material and the vertically aligned liquid crystal cured film are laminated with appropriate adhesion strength, so that the base material can be cleanly peeled off from the laminate with a small force. Furthermore, adhesion can be controlled while ensuring high alignment precision of the polymerizable liquid crystal compound constituting the vertically aligned liquid crystal cured film.

In a preferred embodiment of the present invention, a hydroxyl group and/or a carboxyl group is present on the surface of the substrate forming the vertically aligned liquid crystal cured film, and the composition for forming the vertically aligned liquid crystal cured film is present on the substrate surface. A compound having a (meth)acryloyl group and a functional group that can react with a hydroxyl group and/or a carboxyl group, a polymerizable liquid crystal compound having a (meth)acryloyl group as a polymerizable group, and an ionic compound consisting of a nonmetallic atom. include. When the base material surface and the composition for forming a vertically aligned liquid crystal cured film have the above configuration, a vertically aligned liquid crystal cured film can be formed without forming a vertically aligned film on the base material, and the vertically aligned liquid crystal cured film can be formed on the base material. Since the adhesion with the oriented liquid crystal cured film can be easily controlled, optimal adhesion between the substrate and the vertically oriented liquid crystal cured film and substrate peeling force can be achieved. Note that the hydroxyl group or carboxyl group on the surface of the base material can be provided using a known surface treatment method as described below.

In the present invention, the vertically aligned liquid crystal cured film preferably contains at least one polymerizable non-liquid crystal compound having two or more (meth)acryloyl groups (hereinafter also referred to as "polyfunctional (meth)acrylate compound"). . By including the polyfunctional (meth)acrylate compound, the (meth)acryloyl group possessed by the polyfunctional (meth)acrylate compound and the polymerizable group (especially (meth)acryloyl group possessed by the polymerizable liquid crystal compound in the vertically aligned liquid crystal cured film) group) may form a crosslinked structure. Thereby, the network structure formed by the pre-reacted compound and the polymerizable liquid crystal compound can be strengthened, and the adhesion between the substrate and the vertically aligned liquid crystal cured film can be further improved.

A polyfunctional (meth)acrylate compound means a compound having two or more (meth)acryloyl groups in the molecule, and examples include a bifunctional (meth)acrylate compound having two (meth)acryloyl groups in the molecule. Examples include acrylate monomers and trifunctional or higher-functional (meth)acrylate monomers having three or more (meth)acryloyl groups in the molecule. In the present invention, the vertically aligned liquid crystal cured film may contain one or more types of polyfunctional (meth)acrylate compounds, and if it contains two or more types of polyfunctional (meth)acrylate compounds, they are the same. It may be different or different.

Examples of difunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate. (meth)acrylate, alkylene glycol di(meth)acrylate such as 1,9-nonanediol di(meth)acrylate and neopentyl 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. Di(meth)acrylate; di(meth)acrylate of halogen-substituted alkylene glycol such as tetrafluoroethylene glycol di(meth)acrylate; trimethylolpropane di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, pentaerythritol di( Di(meth)acrylates of aliphatic polyols such as meth)acrylate; hydrogenated dicyclopentadiene or tricyclodecane di(meth)acrylate such as hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate; Di(meth)acrylate of alkanol; Di(meth)acrylate of dioxane glycol or dioxane dialkanol such as 1,3-dioxane-2,5-diyl di(meth)acrylate [also known as dioxane glycol di(meth)acrylate]; Bisphenol Di(meth)acrylate of alkylene oxide adducts of bisphenol A or bisphenol F, such as A ethylene oxide adduct diacrylate, bisphenol F ethylene oxide adduct diacrylate; acrylic acid adduct of bisphenol A diglycidyl ether, bisphenol F Epoxy di(meth)acrylate of bisphenol A or bisphenol F such as acrylic acid adduct of diglycidyl ether; silicone di(meth)acrylate; di(meth)acrylate of hydroxypivalic acid neopentyl glycol ester; 2,2-bis[4 -(meth)acryloyloxyethoxyethoxyphenyl]propane; 2,2-bis[4-(meth)acryloyloxyethoxyethoxycyclohexyl]propane; 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl- 5-hydroxymethyl-1,3-dioxane] di(meth)acrylate; tris(hydroxyethyl)isocyanurate di(meth)acrylate, and the like.

Trifunctional (meth)acrylate monomers are monomers that have three (meth)acryloyl groups in the molecule; examples thereof include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, and ditrimethylolpropane. tri(meth)acrylate, pentaerythritol tri(meth)acrylate, reaction product of pentaerythritol tri(meth)acrylate and acid anhydride, caprolactone-modified trimethylolpropane tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, Ethylene oxide modified trimethylolpropane tri(meth)acrylate, ethylene oxide modified pentaerythritol tri(meth)acrylate, propylene oxide modified trimethylolpropane tri(meth)acrylate, propylene oxide modified pentaerythritol tri(meth)acrylate, isocyanurate tri(meth)acrylate meth)acrylate, reaction product of caprolactone-modified pentaerythritol tri(meth)acrylate and acid anhydride, reaction product of ethylene oxide-modified pentaerythritol tri(meth)acrylate and acid anhydride, propylene oxide-modified pentaerythritol tri(meth)acrylate Examples include reaction products of acrylate and acid anhydride.

Tetrafunctional (meth)acrylate monomers are monomers having four (meth)acryloyl groups in the molecule, examples of which include ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipenta Erythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified tripentaerythritol tetra(meth)acrylate, ethylene oxide modified pentaerythritol tetra(meth)acrylate, ethylene oxide Examples include modified tripentaerythritol tetra(meth)acrylate, propylene oxide modified pentaerythritol tetra(meth)acrylate, propylene oxide modified tripentaerythritol tetra(meth)acrylate, and the like.

Examples of pentafunctional (meth)acrylate monomers include dipentaerythritol penta(meth)acrylate, tripentaerythritol penta(meth)acrylate, reaction product of dipentaerythritol penta(meth)acrylate and acid anhydride, caprolactone-modified dipenta Erythritol penta(meth)acrylate, caprolactone modified tripentaerythritol penta(meth)acrylate, ethylene oxide modified dipentaerythritol penta(meth)acrylate, ethylene oxide modified tripentaerythritol penta(meth)acrylate, propylene oxide modified dipentaerythritol penta(meth)acrylate meth)acrylate, propylene oxide-modified tripentaerythritol penta(meth)acrylate, reaction product of caprolactone-modified dipentaerythritol penta(meth)acrylate and acid anhydride, ethylene oxide-modified dipentaerythritol penta(meth)acrylate and acid anhydride and a reaction product of propylene oxide-modified dipentaerythritol penta(meth)acrylate and an acid anhydride.

Examples of hexafunctional (meth)acrylate monomers include dipentaerythritol hexa(meth)acrylate, tripentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and caprolactone-modified tripentaerythritol hexa(meth)acrylate. , ethylene oxide modified dipentaerythritol hexa(meth)acrylate, ethylene oxide modified tripentaerythritol hexa(meth)acrylate, propylene oxide modified dipentaerythritol hexa(meth)acrylate, propylene oxide modified tripentaerythritol hexa(meth)acrylate, etc. Can be mentioned.

Examples of the heptafunctional (meth)acrylate monomer include tripentaerythritol hepta(meth)acrylate, a reaction product of tripentaerythritol hepta(meth)acrylate and an acid anhydride, caprolactone-modified tripentaerythritol hepta(meth)acrylate, and caprolactone-modified tripentaerythritol hepta(meth)acrylate. Reaction product of tripentaerythritol hepta(meth)acrylate and acid anhydride, ethylene oxide modified tripentaerythritol hepta(meth)acrylate, reaction product of ethylene oxide modified tripentaerythritol hepta(meth)acrylate and acid anhydride, propylene Examples include oxide-modified tripentaerythritol hepta(meth)acrylate, a reaction product of propylene oxide-modified tripentaerythritol hepta(meth)acrylate and an acid anhydride, and the like.

The 8-functional (meth)acrylate monomer is a monomer having 8 (meth)acryloyl groups in the molecule; examples thereof include tripentaerythritol octa(meth)acrylate, caprolactone-modified tripentaerythritol octa(meth)acrylate. , ethylene oxide-modified tripentaerythritol octa(meth)acrylate, propylene oxide-modified tripentaerythritol octa(meth)acrylate, and the like.

The number of (meth)acryloyl groups in the polyfunctional (meth)acrylate compound is preferably 2 to 6. When the number of (meth)acryloyl groups in the polyfunctional (meth)acrylate compound is within the above range, the polymerizable liquid crystal compound constituting the vertically aligned liquid crystal cured film, especially the polymerizable liquid crystal compound having a (meth)acryloyl group as a polymerizable group, In order to form a crosslinked structure with the liquid crystal compound and increase the crosslinking density, the network structure built through the pre-reaction compound between the substrate and the vertically aligned liquid crystal cured film can be strengthened, and the network structure built between the substrate and the vertically aligned liquid crystal cured film can be strengthened. Adhesion to the film can be improved.

By controlling the molecular weight between crosslinking points and the number of crosslinking points of the polyfunctional (meth)acrylate compound, the crosslinking density in the vertically aligned liquid crystal cured film can be adjusted. More specifically, the smaller the molecular weight between crosslinking points, the higher the crosslinking density, and the larger 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, still more preferably 850 or less. When the molecular weight of the polyfunctional (meth)acrylate is below the above upper limit, it is difficult to disturb the alignment of the polymerizable liquid crystal compound forming the vertical alignment film, and while ensuring high alignment accuracy of the polymerizable liquid crystal compound, it is difficult to disturb the alignment with the base material. Adhesion can be improved. The lower limit of the molecular weight of the polyfunctional (meth)acrylate compound is not particularly limited, and 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 based on 100 parts by mass of the polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film. The amount is at least 0.1 parts by mass, more preferably at least 0.3 parts by mass, preferably at most 10 parts by mass, more preferably at most 8 parts by mass, even more preferably at most 5 parts by mass. . When the content of the polyfunctional (meth)acrylate compound is within the above range, it is difficult to disturb the alignment of the polymerizable liquid crystal compound forming the vertical alignment film, and while ensuring high alignment accuracy of the polymerizable liquid crystal compound, Optimum adhesion between the cured vertically aligned liquid crystal film and substrate peeling force can be achieved.

In a preferred embodiment of the present invention, hydroxyl groups and/or carboxyl groups are present on the surface of the substrate forming the vertically aligned liquid crystal cured film, and the composition for forming the vertically aligned liquid crystal cured film is present on the substrate surface. Compounds and polyfunctional (meth)acrylate compounds that have a functional group and (meth)acryloyl group that can react with hydroxyl and/or carboxyl groups, and polymerizable liquid crystal compounds and non-polymerizable liquid crystal compounds that have (meth)acryloyl groups as polymerizable groups. Contains ionic compounds consisting of metal atoms. When the base material surface and the composition for forming a vertically aligned liquid crystal cured film have the above configuration, a vertically aligned liquid crystal cured film can be formed without forming a vertically aligned film on the base material, and the vertically aligned liquid crystal cured film can be formed on the base material. Adhesion with the oriented liquid crystal cured film can be easily controlled, and more optimal adhesion between the base material and the vertically aligned liquid crystal cured film and base material peeling force can be realized.

The composition for forming a vertically aligned liquid crystal cured film (polymerizable liquid crystal composition) used to form a vertically aligned liquid crystal cured film contains a vertical alignment accelerator, a polymerizable liquid crystal compound, the above-mentioned pre-reaction compound and/or a polyfunctional (meth)acrylate. In addition to the compound, the composition may further contain additives such as a solvent, a polymerization initiator, a leveling agent, an antioxidant, and a photosensitizer. These components may be used alone or in combination of two or more.

Since the composition for forming a vertically aligned liquid crystal cured film is usually applied to a substrate in a state dissolved in a solvent, it preferably contains a solvent. The solvent is preferably a solvent that can dissolve the polymerizable liquid crystal compound, and is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound. Examples of solvents include alcohols such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether. Solvents: Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone Ketone solvents; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; cycloaliphatic hydrocarbon solvents such as ethylcyclohexane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; such as tetrahydrofuran and dimethoxyethane. Ether solvents; chlorine-containing solvents such as chloroform and chlorobenzene; amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone, etc. It will be done. These solvents can be used alone or in combination. Among these, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are preferred.

The content of the solvent in the composition for forming a vertically aligned liquid crystal cured film is preferably 50 to 98 parts by weight, more preferably 70 to 95 parts by weight, based on 100 parts by weight 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 to 50 parts by mass. When the solid content is 50 parts by mass or less, the viscosity of the composition for forming a vertically aligned liquid crystal cured film becomes low, so that the thickness of the film tends to be substantially uniform and unevenness is less likely to occur. The solid content can be determined as appropriate in consideration of the thickness of the cured liquid crystal film to be produced.

A polymerization initiator is a compound that generates reactive species by the contribution of heat or light and can initiate a polymerization reaction of a polymerizable liquid crystal compound or the like. Examples of the reactive species include radicals, cations, anions, and the like. Among these, a photopolymerization initiator that generates radicals upon irradiation with light is preferred from the viewpoint of easy reaction control.

Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, oxime compounds, triazine compounds, iodonium salts, and sulfonium salts. Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (the above, BASF Japan Ltd. ), Seiqual BZ, Seiqual Z, Seiqual BEE (manufactured by Seiko Kagaku 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 ARCLES NCI-831, ADEKA ARCLES NCI-930 (manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ -PP (manufactured by Nippon Siberhegner Co., Ltd.) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.).

The photopolymerization initiator can fully utilize the energy emitted from the light source and has excellent productivity, so it is preferable that the maximum absorption wavelength is 300 nm to 400 nm, more preferably 300 nm to 380 nm. Among them, α-acetophenone type Polymerization initiators and oxime photopolymerization initiators are preferred.

As α-acetophenone compounds, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1 -one and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, and more preferably 2-methyl-2-morpholino-1-( Mention may be made of 4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one. Commercially available α-acetophenone compounds include Irgacure 369, 379EG, 907 (manufactured by BASF Japan Co., Ltd.) and Seiqual BEE (manufactured by Seiko Kagaku Co., Ltd.).

Oxime-based photopolymerization initiators generate radicals such as phenyl radicals and methyl radicals when irradiated with light. The polymerization of the polymerizable liquid crystal compound progresses suitably with these radicals, and among them, oxime-based photopolymerization initiators that generate methyl radicals are preferred because they have a high initiation efficiency of the polymerization reaction. Furthermore, from the viewpoint of allowing the polymerization reaction to proceed more efficiently, it is preferable to use a photopolymerization initiator that can efficiently utilize ultraviolet light having a wavelength of 350 nm or more. As a photopolymerization initiator that can efficiently utilize ultraviolet light with a wavelength of 350 nm or more, triazine compounds and carbazole compounds containing an oxime structure are preferred, and carbazole compounds containing an oxime ester structure are more preferred from the viewpoint of sensitivity. Carbazole compounds containing an oxime structure include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methyl) Benzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like. Commercially available oxime ester photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (manufactured by BASF Japan Co., Ltd.), Adeka Optomer N-1919, and Adeka Arcles NCI-831. (All of the above are manufactured by ADEKA Co., Ltd.).

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, per 100 parts by mass of the polymerizable liquid crystal compound. It is. Within the above range, the reaction of the polymerizable groups will proceed sufficiently and the orientation of the polymerizable liquid crystal compound will not be easily disturbed.

The leveling agent is an additive that has the function of adjusting the fluidity of the composition for forming a vertically aligned liquid crystal cured film and making the coating film obtained by applying the composition more flat. Examples include acrylate-based and perfluoroalkyl-based leveling agents. Commercial products may be used as the leveling agent, and specifically, DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all manufactured by Dow Corning Toray Co., Ltd.) , KP321, KP323, KP324, KP326, KP340, KP341, SF4452, TSF4460 Fluorinert (registered trademark) FC-72, fluorinert FC-40, FC-43, FC-3283 (all manufactured by Sumitomo 3M Ltd.) ), Megafac (registered trademark) R-08, R-30, R-90, F-410, F-411, F-443, F-445, F-470, F- 477, F-479, F-482, F-483, F-556 (all manufactured by DIC Corporation), F-TOP (product name) EF301, EF303, EF351, EF352 ( All of the above are manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S-381, Surflon S-382, Surflon S-383, Surflon S-393, Surflon SC-101, Surflon SC-105, KH-40 , SA-100 (all manufactured by AGC Seimi Chemical Co., Ltd.), product name E1830, E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N (all product names: manufactured by BM Chemie) and the like. Leveling agents can be used alone or in combination of two or more.

The content of the leveling agent is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the polymerizable liquid crystal compound. It is preferable that the content of the leveling agent is within the above range because it is easy to orient the polymerizable liquid crystal compound and the resulting cured liquid crystal film tends to be smoother.

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

Furthermore, by using a photosensitizer, the sensitivity of the photopolymerization initiator can be increased. Examples of the photosensitizer include xanthone such as xanthone and thioxanthone; anthracenes having substituents such as anthracene and alkyl ether; phenothiazine; and rubrene. The photosensitizers can be used alone or in combination of two or more. The content of the photosensitizer is usually 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the polymerizable liquid crystal compound. 3 parts by mass.

The composition for forming a vertically aligned liquid crystal cured film includes a vertical alignment accelerator, a polymerizable liquid crystal compound, a pre-reaction compound and/or a polyfunctional (meth)acrylate compound, a vertical alignment accelerator such as a solvent and a photopolymerization initiator, and a polymerizable liquid crystal compound. It can be obtained by stirring the components other than the liquid crystal compound at a predetermined temperature. In addition, when forming a pre-reaction compound in a composition for forming a vertical alignment liquid crystal cured film, for example, a mixture of components necessary for forming the pre-reaction compound is prepared, and the mixture is mixed with a vertical alignment accelerator or a vertical alignment accelerator. It can be prepared by stirring or the like at a predetermined temperature with a polymerizable liquid crystal compound or the like.

In the present invention, the vertically aligned cured liquid crystal film is preferably oriented with a high degree of order in the vertical direction of the cured liquid crystal film. In the vertically aligned cured liquid crystal film, the polymerizable liquid crystal compound is oriented with a high degree of order, so that when a laminate containing the vertically aligned cured liquid crystal film is incorporated into an organic EL display device, the oblique angle during black display is It tends to have an excellent effect of suppressing changes in reflection hue. As an indicator of the highly aligned state of the polymerizable liquid crystal compound in the vertically aligned liquid crystal cured film and the degree of the oblique optical compensation effect during black display, the vertically aligned liquid crystal cured film satisfies the following formula (2). preferable.
-150nm≦RthC(550)≦-30nm (2)
In formula (2), RthC(550) represents the retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. From the viewpoint of further improving the oblique reflection hue during black display, the retardation value RthC (550) in the film thickness direction of the vertically aligned liquid crystal cured film is more preferably −130 nm or more, still more preferably −100 nm or more, and particularly It is preferably -90 nm or more, more preferably -40 nm or less, and even more preferably -50 nm or less.

Further, in one embodiment of the present invention, the vertically aligned liquid crystal cured film satisfies the following formula (3).
RthC(450)/RthC(550)≦1.0 (3)
[In formula (3), RthC (450) represents the retardation value in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the position in the film thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. Represents the phase difference value. ]
By satisfying the above formula (3), it is possible to suppress a decrease in 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 vertically aligned liquid crystal cured film is more preferably 0.95 or less, further preferably 0.92 or less, particularly preferably 0.9 or less, and is 0.7 or more, more preferably 0.75 or more, even more preferably 0.8 or more.

The retardation value RthC (λ) in the film thickness direction of the vertically aligned liquid crystal cured film can be adjusted by the thickness dC of the vertically aligned liquid crystal cured film. The in-plane phase difference value is calculated using the following formula:
RthC(λ)=((nxC(λ)+nyC(λ))/2-nzC(λ))×dC
(Here, in the formula, nxC(λ) is the in-plane principal refractive index of the vertically aligned liquid crystal cured film at the wavelength λnm, and nyC(λ) is the refraction in the direction orthogonal to nxC(λ) in the plane at the wavelength λnm. nzC(λ) indicates the refractive index in the thickness direction of a vertically aligned liquid crystal cured film at a wavelength of λnm, and when nxC(λ)=nyC(λ), nxC(λ) is an arbitrary (dC indicates the thickness of the vertically aligned liquid crystal cured film)
Therefore, in order to obtain a desired retardation value RthC(λ) in the film thickness direction, the three-dimensional refractive index and the film thickness dC may be adjusted. Note that the three-dimensional refractive index depends on the molecular structure and orientation state of the above-mentioned polymerizable liquid crystal compound.

Examples of the base material constituting the laminate of the present invention include glass base materials and film base materials, but resin film base materials are preferred from the viewpoint of processability. Examples of the resin constituting the film base material include polyolefins such as polyethylene, polypropylene, and norbornene polymers; cyclic olefin resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate ester; polyacrylate ester; triacetyl cellulose; Cellulose esters such as diacetyl cellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyether sulfone; polyether ketone; plastics such as polyphenylene sulfide and polyphenylene oxide. Such a resin can be used as a base material by forming a film by known means such as a solvent casting method and a melt extrusion method.

Commercially available products may be used as the base material. Commercially available cellulose ester base materials include, for example, cellulose ester base materials manufactured by Fuji Photo Film Co., Ltd. such as Fuji Tac Film; manufactured by Konica Minolta Opto Co., Ltd. such as "KC8UX2M", "KC8UY", and "KC4UY"; Examples include cellulose ester base materials. Commercially available cyclic olefin resins include, for example, cyclic olefin resins manufactured by Ticona (Germany) such as "Topas (registered trademark)"; cyclic olefin resins manufactured by JSR Corporation such as "Arton (registered trademark)"; Cyclic olefin resins manufactured by Nippon Zeon Co., Ltd. such as “ZEONOR (registered trademark)” and “ZEONEX (registered trademark)”; Mitsui resins such as “APEL” (registered trademark) Examples include cyclic olefin resin manufactured by Kagaku Corporation. A commercially available cyclic olefin resin base material can also be used. Commercially available cyclic olefin resin base materials include cyclic olefin resin base materials manufactured by Sekisui Chemical Co., Ltd. such as "Escina (registered trademark)" and "SCA40 (registered trademark)"; "Zeonor Film (registered trademark)" Examples include cyclic olefin resin base materials manufactured by Optes Co., Ltd.; and cyclic olefin resin base materials manufactured by JSR Corporation such as "Arton Film (registered trademark)".

When a hydroxyl group and/or a carboxyl group are present on the surface of the substrate, the adhesion between the substrate and the vertically aligned liquid crystal cured film can be improved through the pre-reaction compound contained in the vertically aligned liquid crystal cured film, A laminate having optimal adhesion and base material peeling force P can be obtained. Therefore, it is preferable that hydroxyl groups and/or carboxyl groups exist on the surface of the base material constituting the laminate of the present invention. In order to provide a hydroxyl group or a carboxyl group on the surface of the base material, for example, the surface of the base material can be subjected to corona treatment or plasma treatment, and the hydroxyl group or carboxyl group can be formed using oxidation of the base material surface. Further, for example, in a triacetyl cellulose film, hydroxyl groups or carboxyl groups may be formed by post-treating the film by saponification treatment or the like. In order to ensure good adhesion with the cured vertically aligned liquid crystal film, it is preferable that hydroxyl groups and/or carboxyl groups are uniformly present on the surface of the substrate. Surface treatment methods such as corona treatment and plasma treatment and saponification treatment methods for forming hydroxyl groups and carboxyl groups on the surface of the base material are not particularly limited, and may be any of the methods conventionally used for surface treatment of base materials. This can be done by any known method. Alternatively, a commercially available base material whose surface has been previously subjected to the above treatment may be selected and used.

In the present invention, the base material is usually finally peeled off from the laminate of the present invention. When the base material peeling force P of the laminate satisfies the above formula (1), the base material and the vertically aligned liquid crystal cured film are laminated with optimal adhesion, and the vertically aligned liquid crystal cures during cutting of the laminate, etc. Peeling between the film and the base material is difficult to occur, but when the base material is peeled off from the laminate, the laminate can be peeled cleanly with a small force.

From the viewpoints of thinning the laminate, ease of peeling the base material, handleability of the base material, etc., the thickness of the base material is usually 5 to 300 μm, preferably 10 to 150 μm.

The laminate of the present invention may contain layers other than the base material and the vertically aligned liquid crystal cured film as long as the effects of the present invention are not affected. Examples of such other layers include, for example, a horizontally oriented retardation film (horizontally oriented liquid crystal cured film), a horizontally oriented film, and a cured resin intended to enhance or reinforce the mechanical strength of the liquid crystal cured film. layer, hard coat layer, etc.

When a laminate is constructed by forming a vertically aligned liquid crystal cured film on a base material, it is easy to obtain a base material peeling force P that satisfies the above formula (1), and the vertically aligned liquid crystal cured film is easily obtained during cutting of the laminate. The present invention is suitable for producing a laminate in which peeling between the film and the base material is difficult to occur, but the base material can be peeled cleanly with a small force when peeling the base material from the laminate. a liquid crystal compound, (a2) an ionic compound consisting of a non-metallic atom as a vertical alignment promoter, and (a3) a compound having in its molecule a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acryloyl group; Also targeted is a composition for forming a vertically aligned liquid crystal cured film, which contains at least one member selected from the group consisting of polymerizable non-liquid crystal compounds having two or more (meth)acryloyl groups.

A polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film, an ionic compound consisting of a nonmetallic atom, and a functional group that can react with a hydroxyl group or a carboxyl group and a (meth)acryloyl group in the molecule. As the compound and the polymerizable non-liquid crystal compound having two or more (meth)acryloyl groups, the same compounds as those exemplified above as those that can be included in the vertically aligned liquid crystal cured film constituting the laminate of the present invention are used. Can be used. The polymerizable liquid crystal compound may be either a reverse wavelength dispersion polymerizable liquid crystal compound or a forward wavelength dispersion polymerizable liquid crystal compound, but from the viewpoint of further improving adhesion, a (meth)acryloyl group is used. A polymerizable liquid crystal compound having the following is preferred. Furthermore, the composition for forming a vertically aligned liquid crystal cured film contains additives such as vertical alignment accelerators other than ionic compounds consisting of nonmetallic atoms, solvents, polymerization initiators, leveling agents, antioxidants, and photosensitizers. may further include. As these components, the same components as those exemplified above that can be included in the vertically aligned liquid crystal cured film constituting the laminate of the present invention can be used.

[Method for manufacturing laminate]
The laminate of the present invention includes, for example,
a step of applying a polymerizable liquid crystal composition for forming a vertically aligned liquid crystal cured film containing a polymerizable liquid crystal compound onto a substrate to obtain a coating film;
drying the coating film to form a dry coating film, and
It can be manufactured by a method including a step of irradiating a dry coating film with active energy rays to form a vertically aligned liquid crystal cured film.

Formation of a coating film of the composition for forming a vertically aligned liquid crystal cured film can be performed, for example, by applying the composition for forming a vertically aligned liquid crystal cured film onto a substrate.

Methods for applying the composition for forming a vertically aligned liquid crystal cured film onto a substrate include coating methods such as spin coating, extrusion, gravure coating, die coating, bar coating, and applicator methods, and flexography. Examples of known methods include printing methods such as .

Next, a dry coating film is formed by removing the solvent by drying or the like. Examples of the drying method include natural drying, ventilation drying, heating drying, and reduced pressure drying. At this time, by heating the coating film obtained from the composition for forming a vertically aligned liquid crystal cured film, the solvent is dried and removed from the coating film, and the polymerizable liquid crystal compound is aligned in a direction perpendicular to the plane of the coating film. be able to. In addition, by including a pre-reactive compound or a polyfunctional (meth)acrylate compound, the hydroxyl or carboxyl groups present on the surface of the base material react with the functional groups that can react with the hydroxyl or carboxyl groups of the pre-reacted compound. , the (meth)acryloyl group of the pre-reacted compound reacts with the (meth)acryloyl group of the polymerizable liquid crystal compound or polyfunctional (meth)acrylate compound that forms the vertically aligned liquid crystal cured film, thereby forming a dry coating film with the base material. A network structure is formed between them. The heating temperature of the coating film can be determined as appropriate, taking into account the polymerizable liquid crystal compound used and the material of the base material forming the coating film. A temperature above the phase transition temperature is usually required. In order to bring the polymerizable liquid crystal compound into a vertically aligned state while removing the solvent contained in the composition for forming a vertically aligned liquid crystal cured film, for example, the liquid crystal of the polymerizable liquid crystal compound contained in the composition for forming a vertically aligned liquid crystal cured film is removed. It is possible to heat to a temperature approximately equal to or higher than the phase transition temperature (smectic phase transition temperature or nematic phase transition temperature).
Note that the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like. In addition, when using a combination of two or more types of polymerizable liquid crystal compounds, the above phase transition temperature is such that all polymerizable liquid crystal compounds constituting the composition for forming a vertically aligned liquid crystal cured film are used in the composition for forming a vertically aligned liquid crystal cured film. It means the temperature measured using a mixture of polymerizable liquid crystal compounds mixed in the same ratio as the composition in the same manner as when one type of polymerizable liquid crystal compound is used. 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 may be lower than the liquid crystal phase transition temperature of the polymerizable liquid crystal compound alone.

The heating time can be appropriately determined depending on the heating temperature, the type of polymerizable liquid crystal compound used, the type of solvent, its boiling point, its amount, etc., but is usually 15 seconds to 10 minutes, preferably 0.5 to 10 minutes. It's 5 minutes.

Removal of the solvent from the coating film may be performed simultaneously with heating the polymerizable liquid crystal compound to a temperature equal to or higher than the liquid crystal phase transition temperature, or may be performed separately, but it is preferably performed simultaneously from the viewpoint of improving productivity. Before heating the polymerizable liquid crystal compound to a temperature higher than the liquid crystal phase transition temperature, the polymerizable liquid crystal compound contained in the coating film obtained from the composition for forming a vertically aligned liquid crystal cured film is heated under conditions such that the polymerizable liquid crystal compound contained in the coating film is not polymerized. A preliminary drying step may be provided to appropriately remove the solvent. Drying methods in this pre-drying step include natural drying, ventilation drying, heating drying, reduced pressure drying, etc. The drying temperature (heating temperature) in this drying step depends on the type of polymerizable liquid crystal compound used and the solvent. It can be determined as appropriate depending on the type, boiling point, amount, etc.

Next, in the obtained dry coating film, a vertically aligned liquid crystal cured film is formed by polymerizing the polymerizable liquid crystal compound while maintaining the vertically aligned state of the polymerizable liquid crystal compound. Examples of the polymerization method include a thermal polymerization method and a photopolymerization method, and the photopolymerization method is preferable from the viewpoint of easy control of the polymerization reaction. In photopolymerization, the light irradiated to the dry coating film depends on the type of polymerization initiator contained in the dry coating film, the type of polymerizable liquid crystal compound (in particular, the type of polymerizable group possessed by the polymerizable liquid crystal compound), and the type of polymerizable liquid crystal compound contained in the dry coating film. It is selected appropriately depending on the amount. Specific examples include one or more types of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays, and active electron beams. Among these, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and it is possible to use photopolymerization equipment that is widely used in the field. It is preferable to select the type of polymerizable liquid crystal compound and polymerization initiator contained in the composition for forming a vertically aligned liquid crystal cured film. Moreover, during polymerization, the polymerization temperature can also be controlled by irradiating the dry coating film with light while cooling it with an appropriate cooling means. By employing such a cooling means and polymerizing the polymerizable liquid crystal compound at a lower temperature, a vertically aligned cured liquid crystal film can be appropriately formed even if a base material with relatively low heat resistance is used. It is also possible to promote the polymerization reaction by increasing the polymerization temperature within a range that does not cause problems due to heat during light irradiation (such as deformation of the base material due to heat). A patterned cured film can also be obtained by performing masking or development during photopolymerization.

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

The ultraviolet irradiation intensity is usually 10 to 3,000 mW/cm ² . The ultraviolet irradiation intensity is preferably an intensity in a wavelength range effective for activating the photopolymerization initiator. The time for irradiating the light is usually 0.1 seconds to 10 minutes, preferably 0.1 seconds to 5 minutes, more preferably 0.1 seconds to 3 minutes, and even more preferably 0.1 seconds to 1 minute. be. When irradiated once or multiple times with such ultraviolet irradiation intensity, the cumulative amount of light is 10 to 3,000 mJ/cm ² , preferably 50 to 2,000 mJ/cm ² , more preferably 100 to 1,000 mJ/cm It is ² .

The thickness of the vertically aligned liquid crystal cured film can be appropriately selected depending on the display device to which it is applied, 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. be.

[Horizontally aligned retardation film]
The laminate of the present invention may include a horizontally oriented retardation film. The horizontally oriented retardation film that can constitute the laminate of the present invention means a retardation film oriented in the horizontal direction with respect to the in-plane direction of a vertically oriented liquid crystal cured film, and includes, for example, a stretched film and a polymerizable liquid crystal compound. A cured product of a polymerizable liquid crystal composition comprising: a cured product obtained by curing the polymerizable liquid crystal compound in a state in which the polymerizable liquid crystal compound is aligned horizontally with respect to the plane of the retardation film (hereinafter referred to as "horizontally aligned liquid crystal cured film") ), etc.

In the present invention, it is preferable that the horizontally oriented retardation film 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 oriented retardation film at the wavelength λ nm, and ReA (λ) = (nxA (λ) - nyA (λ)) × dA ( In the formula, nxA(λ) represents the principal refractive index at wavelength λnm in the plane of the horizontally aligned retardation film, and nyA(λ) represents the principal refractive index at wavelength λnm in the same plane as nxA in the direction orthogonal to the direction of nxA. (represents the refractive index of the film, and dA indicates the thickness of the horizontally oriented retardation film)]

When the horizontally oriented retardation film satisfies formula (6), the horizontally oriented retardation film has so-called reverse wavelength dispersion, in which the in-plane retardation value at short wavelengths is smaller than the in-plane retardation value at long wavelengths. Show your gender. By combining such a horizontally oriented retardation film with the vertically oriented liquid crystal cured film, it is possible to obtain a laminate that is excellent in improving frontal and oblique reflection hues during black display when incorporated into an organic EL display device. can. ReA(450)/ReA(550) is preferably 0.70 or more, more preferably is 0.78 or more, and preferably 0.95 or less, more preferably 0.92 or less.

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

Further, it is preferable that the horizontally oriented retardation film satisfies the following formula (7).
120nm≦ReA(550)≦170nm (7)
[In formula (7), ReA (λ) has the same meaning as above]
When the in-plane retardation ReA (550) of the horizontally oriented retardation film is within the range of formula (7), when a laminate (elliptically polarizing plate) containing the horizontally oriented retardation film is applied to an organic EL display device. The effect of improving the frontal reflection hue during black display (the effect of suppressing coloring) becomes remarkable. A more preferable range of the in-plane retardation value is 130 nm≦ReA(550)≦150 nm.

The horizontally oriented retardation film is preferably a horizontally oriented liquid crystal cured film because the desired retardation of the retardation film can be easily controlled and the film can be made thinner. As the polymerizable liquid crystal compound for forming the horizontally aligned liquid crystal cured film, conventionally known polymerizable liquid crystal compounds in the field of retardation films can be used. Specifically, compounds represented by formulas (X) and/or (Y), which are exemplified as polymerizable liquid crystal compounds that can be used to form a vertically aligned liquid crystal cured film, can be used, and among them, so-called reverse wavelength dispersion A polymerizable liquid crystal compound exhibiting properties is preferable, and for example, a compound represented by the above formula (X) can be suitably used. In the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film, the polymerizable liquid crystal compounds can be used alone or in combination of two or more.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition used for forming the horizontally aligned liquid crystal cured film is, for example, 70 to 99.5 parts by mass based on 100 parts by mass of the solid content of the polymerizable liquid crystal composition. , preferably 80 to 99 parts by weight, more preferably 85 to 98 parts by weight, and even more preferably 90 to 95 parts by weight. If the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of orientation of the resulting cured liquid crystal film.

In addition to the polymerizable liquid crystal compound, the polymerizable liquid crystal composition used to form the horizontally aligned liquid crystal cured film further contains additives such as a solvent, a photopolymerization initiator, a leveling agent, an antioxidant, and a photosensitizer. You can stay there. These components include those similar to those listed above as components that can be used in the vertical alignment liquid crystal cured film, and each may be used alone or in combination of two or more. .

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

The horizontal alignment liquid crystal cured film is, for example,
a step of applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film onto a base material or a horizontally aligned film to obtain a coating film;
drying the coating film to form a dry coating film, and
It can be produced by a method including a step of irradiating a dried coating film with active energy rays to form a horizontally aligned liquid crystal cured film.

Formation of a coating film of a polymerizable liquid crystal composition can be performed, for example, by applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film onto a substrate or a horizontally aligned film as described below. . As the base material that can be used here, the same materials as those exemplified above as base materials that can be used for forming the vertically aligned liquid crystal cured film can be used.

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

The obtained dry coating film is irradiated with active energy rays (more specifically, ultraviolet rays, etc.), and the polymerizable liquid crystal compound is irradiated with active energy rays (more specifically, ultraviolet rays, etc.) while maintaining the state in which the polymerizable liquid crystal compound is oriented in the horizontal direction with respect to the plane of the coating film. By polymerizing, a horizontally aligned liquid crystal cured film is formed. Examples of the polymerization method include methods similar to those that can be employed in the manufacturing method of a vertically aligned liquid crystal cured film.

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

By forming a coating film of a polymerizable liquid crystal compound on the horizontal alignment film, alignment of the polymerizable liquid crystal compound in the horizontal direction can be further improved. For example, a horizontal alignment film is formed on the vertical alignment liquid crystal cured film constituting the laminate of the present invention, and a polymerizable liquid crystal composition for forming a horizontal alignment liquid crystal cured film is applied thereon to obtain a horizontal alignment liquid crystal cured film. In this case, compared to a method in which a horizontally aligned liquid crystal cured film is formed on a base material or a horizontally aligned film provided on the base material, and then laminated with a vertically aligned liquid crystal cured film via an adhesive layer etc. Another advantage is that the manufacturing process of the laminate can be simplified. The horizontal alignment film can be appropriately selected from materials having a horizontal alignment regulating force that aligns the polymerizable liquid crystal compound in the horizontal direction with respect to the plane of the coating film. The alignment regulating force can be arbitrarily adjusted depending on the type of alignment film, surface condition, rubbing conditions, etc., and if it is formed from a photo-alignable polymer, it can be arbitrarily adjusted by changing the polarized light irradiation conditions, etc. It is possible.

As the horizontal alignment film, it is preferable that the film has a solvent resistance that does not dissolve when the polymerizable liquid crystal composition is applied, etc., and also has heat resistance in heat treatment for removing the solvent and aligning the polymerizable liquid crystal compound as described below. . Examples of the alignment film include an alignment film containing an alignment polymer, a photo-alignment film, a groove alignment film having a concavo-convex pattern or a plurality of grooves on the surface, and a stretched film stretched in the alignment direction. A photo-alignment film is preferred from the viewpoint of quality.

Examples of oriented polymers include polyamides and gelatins having an amide bond in the molecule, polyimide having an imide bond in the molecule, and polyamic acid, which is a hydrolyzate thereof, polyvinyl alcohol, alkyl-modified polyvinyl alcohol, polyacrylamide, and polyamide. Mention may be made of oxazole, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylic esters. Among them, polyvinyl alcohol is preferred. The oriented polymers can be used alone or in combination of two or more.

An oriented film containing an oriented polymer is usually prepared by applying a composition in which an oriented polymer is dissolved in a solvent (hereinafter sometimes referred to as an "oriented polymer composition") to a base material, and then removing the solvent, or It is obtained by applying an oriented polymer composition to a base material, removing the solvent, and rubbing it (rubbing method). Examples of the solvent include the same solvents as those exemplified above as solvents that can be used in the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film.

The concentration of the oriented polymer in the oriented polymer composition may be within a range that allows the oriented polymer material to be completely dissolved in the solvent, but it is preferably 0.1 to 20% in terms of solid content with respect to the solution. It is more preferably about .1 to 10%.

Commercially available alignment film materials may be used as they are as the alignment polymer composition. Commercially available alignment film materials include Sunever (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), Optomer (registered trademark, manufactured by JSR Corporation), and the like.

Examples of the method for applying the oriented polymer composition to the substrate include the same methods as those exemplified as the method for applying the polymerizable liquid crystal composition for forming a horizontally oriented liquid crystal cured film to the substrate.

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

In order to impart an alignment regulating force to the alignment film, rubbing treatment can be performed as necessary (rubbing method). As a method of imparting an orientation regulating force by the rubbing method, a rubbing cloth is wrapped around a rotating rubbing roll, and an oriented polymer composition is applied to a substrate and annealed to form an oriented polymer composition on the surface of the substrate. Examples include a method of bringing oriented polymer films into contact with each other. If masking is performed when performing the rubbing process, a plurality of regions (patterns) with different orientation directions can be formed on the alignment film.

A photo-alignment film is usually produced by coating a base material with a composition containing a polymer or monomer having a photo-reactive group and a solvent (hereinafter also referred to as "composition for forming a photo-alignment film"), and after removing the solvent, polarized light is produced. (preferably polarized UV). The photo-alignment film is also advantageous in that the direction of the alignment regulating force can be arbitrarily controlled by selecting the polarization direction of the polarized light to be irradiated.

The photoreactive group refers to a group that produces liquid crystal alignment ability when irradiated with light. Specifically, groups that are involved in molecular alignment induction caused by light irradiation or photoreactions that are the origin of liquid crystal alignment ability, such as isomerization reactions, dimerization reactions, photocrosslinking reactions, or photodecomposition reactions, can be mentioned. Among these, groups that participate in dimerization reactions or photocrosslinking reactions are preferable because they have excellent orientation. The photoreactive group is preferably a group having an unsaturated bond, especially a double bond, such as a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), or a nitrogen-nitrogen double bond. Particularly preferred is a group having at least one selected from the group consisting of a double bond (N=N bond) and a carbon-oxygen double bond (C=O bond).

Examples of the photoreactive group having a C═C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group. Examples of the photoreactive group having a C=N bond include groups having structures such as an aromatic Schiff base and an aromatic hydrazone. Examples of the photoreactive group having an N=N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazan group, and a group having an azoxybenzene structure. Examples of the photoreactive group having a C═O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have 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 these, photoreactive groups that participate in photodimerization reactions are preferred, since 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 and stability over time. Cinnamoyl and chalcone groups are preferred. As the polymer having a photoreactive group, one having a cinnamoyl group such that the end of the polymer side chain has a cinnamic acid structure is particularly preferred.

By applying the composition for forming a photo-alignment film onto a base material, a photo-alignment inducing layer can be formed on the base material. Examples of the solvent contained in the composition include those similar to those exemplified above as solvents that can be used in the polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film, and polymers or monomers having photoreactive groups. It can be appropriately selected depending on the solubility of.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be adjusted as appropriate depending on the type of polymer or monomer and the desired thickness of the photo-alignment film. The amount is preferably at least 0.2% by weight, more preferably from 0.3 to 10% by weight. The composition for forming a photo-alignment film may contain a polymeric material such as polyvinyl alcohol or polyimide, and a photosensitizer as long as the properties of the photo-alignment film are not significantly impaired.

Examples of the method for applying the photo-alignment film-forming composition to the substrate include the same method as the method for applying the alignment polymer composition to the substrate. Examples of methods for removing the solvent from the applied composition for forming a photoalignment film include natural drying, ventilation drying, heat drying, and reduced pressure drying.

In order to irradiate polarized light, polarized UV can be irradiated directly onto the composition for forming a photo-alignment film coated on the substrate, from which the solvent has been removed, or the polarized light can be irradiated from the substrate side and the polarized light can be transmitted. It may also be a form of irradiation. Moreover, it is particularly preferable that the polarized light is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in a wavelength range in which a polymer having a photoreactive group or a photoreactive group of a monomer can absorb light energy. Specifically, UV (ultraviolet light) having a wavelength in the range of 250 to 400 nm is particularly preferred. Examples of light sources used for the polarized light irradiation include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and ultraviolet lasers such as KrF and ArF. preferable. Among these, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are preferable because they emit a high intensity of ultraviolet light with a wavelength of 313 nm. Polarized UV can be irradiated by passing the light from the light source through a suitable polarizer. As such a polarizer, a polarizing filter, a polarizing prism such as Glan-Thompson or Glan-Taylor, or a wire grid type polarizer can be used.

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

A groove alignment film is a film having an uneven pattern or a plurality of grooves on its surface. When a polymerizable liquid crystal compound is applied to a film having a plurality of linear grooves arranged at equal intervals, liquid crystal molecules are aligned in the direction along the grooves.

The groove alignment film can be obtained by exposing the surface of a photosensitive polyimide film to light through an exposure mask having pattern-shaped slits, followed by development and rinsing to form a concavo-convex pattern, and by using a plate with grooves on the surface. A method of forming a layer of uncured UV curable resin on a shaped master, transferring the formed resin layer to a base material, and then curing it; Examples include a method in which a rolled master having a plurality of grooves is pressed against each other to form irregularities, and then hardened.

In the laminate of the present invention, the vertically aligned liquid crystal cured film and the horizontally aligned retardation film can be laminated, for example, via a pressure-sensitive adhesive layer or an adhesive layer. As the pressure-sensitive adhesive or adhesive, those conventionally known in the field can be used. Further, by applying a polymerizable liquid crystal composition for forming a horizontally aligned liquid crystal cured film with or without a horizontal alignment film on the vertically aligned liquid crystal cured film constituting the laminate of the present invention, it is possible to form a vertically aligned liquid crystal cured film. A horizontally oriented retardation film (horizontally oriented liquid crystal cured film) can be laminated on the surface.

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

A film containing a stretched film adsorbed with a dye having absorption anisotropy as a polarizer is usually produced by a process of uniaxially stretching a polyvinyl alcohol resin film or by dyeing the polyvinyl alcohol resin film with a dichroic dye. A polarizer manufactured through the steps of adsorbing a dichroic dye, treating the polyvinyl alcohol resin film with the dichroic dye adsorbed with an aqueous boric acid solution, and washing with water after treatment with an aqueous boric acid solution. It is made by sandwiching a transparent protective film on one side with an adhesive between them.

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

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

A film made of such a polyvinyl alcohol resin is used as a raw film of a polarizing film. The method of forming a polyvinyl alcohol resin into a film is not particularly limited, and any known method can be used to form the film. The thickness of the polyvinyl alcohol base film can be, for example, about 10 to 150 μm.

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

Staining of a polyvinyl alcohol resin film with a dichroic dye is carried out, for example, by immersing the polyvinyl alcohol resin film in an aqueous solution containing the dichroic dye.

Specifically, iodine or a dichroic organic dye is used as the dichroic dye. As a dichroic organic dye, C.I. I. Examples include dichroic direct dyes made of disazo compounds such as DIRECT RED 39, and dichroic direct dyes made of compounds such as trisazo and tetrakisazo. It is preferable that the polyvinyl alcohol resin film is immersed in water before being dyed.

When using iodine as a dichroic dye, a method is usually employed in which a polyvinyl alcohol resin film is immersed in an aqueous solution containing iodine and potassium iodide for dyeing. The content of iodine in this aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water. Further, 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 about 20 to 40°C. The immersion time (staining time) in this aqueous solution is usually about 20 to 1,800 seconds.

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

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

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

After washing with water, a drying process is performed to obtain a polarizer. The drying process can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying treatment is usually about 30 to 100°C, preferably 50 to 80°C. The drying time is usually about 60 to 600 seconds, preferably 120 to 600 seconds. The drying process reduces the moisture content of the polarizer to a practical level. Its moisture content is usually about 5 to 20% by weight, preferably 8 to 15% by weight. When the moisture content is less than 5% by mass, the flexibility of the polarizer is lost and the polarizer may be damaged or broken after drying. Furthermore, if the moisture content exceeds 20% by weight, the thermal stability of the polarizer may deteriorate.

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

Films coated with dyes having absorption anisotropy include films obtained by coating compositions containing dichroic dyes having liquid crystallinity or compositions containing dichroic dyes and polymerizable liquid crystals. Can be mentioned. The film preferably has a protective film on one or both sides thereof. The protective film may be the same as the resin film exemplified above as a base material that can be used for manufacturing a vertically aligned liquid crystal cured film.

It is preferable for a film coated with a dye having absorption anisotropy to be thin, but if it is too thin, the strength tends to decrease and processability tends to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

Specific examples of the film coated with the dye having absorption anisotropy include the films described in JP-A No. 2012-33249 and the like.

A transparent protective film may be laminated on at least one surface of the polarizer thus obtained, for example, via an adhesive layer. As the transparent protective film, a transparent film similar to the resin film exemplified above as a base material that can be used for manufacturing a vertically aligned liquid crystal cured film can be used.

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

In one embodiment of the present invention, when the laminate of the present invention including a horizontally oriented retardation film and a polarizing film are laminated, the slow axis (optical axis) of the horizontally oriented retardation film constituting the laminate and the polarized light It is preferable to laminate the films so that the angle formed with the absorption axis of the film is 45±5°.

The elliptically polarizing plate of the present invention may have a structure similar to that of a conventional general elliptically polarizing plate, or a polarizing film and a retardation film. Such structures include, for example, adhesive layers (sheets) for bonding elliptically polarizing plates to display elements such as organic EL, and adhesive layers used to protect the surfaces of polarizing films and liquid crystal cured films from scratches and dirt. Protective films and the like can be mentioned.

The laminate and elliptically polarizing plate of the present invention can be used in various display devices.
A display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. Display devices include liquid crystal displays, organic electroluminescent (EL) display devices, inorganic electroluminescent (EL) display devices, touch panel display devices, electron emission display devices (e.g. field emission display (FED), surface field emission display device). (SED)), electronic paper (display devices using electronic ink or electrophoretic elements, plasma display devices, projection display devices (e.g., grating light valve (GLV) display devices, display devices with digital micromirror devices (DMD)) ) and piezoelectric ceramic displays.Liquid crystal display devices include transmissive liquid crystal display devices, transflective liquid crystal display devices, reflective liquid crystal display devices, direct-view liquid crystal display devices, and projection type liquid crystal display devices. These display devices may be display devices that display two-dimensional images or stereoscopic display devices that display three-dimensional images.In particular, the elliptically polarizing plate of the present invention is free from alignment defects. The laminate of the present invention can be suitably used for organic electroluminescence (EL) display devices because it has excellent optical properties, and the laminate of the present invention can be suitably used for liquid crystal display devices and touch panel display devices. Alternatively, by using an elliptically polarizing plate, it is possible to easily realize a thin display device, and to obtain a display device that has excellent optical properties and can exhibit good image display characteristics.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, "%" and "parts" in the examples mean % by mass and parts by mass, respectively, unless otherwise specified.

1. Example 1
(1) Preparation of polymerizable liquid crystal compounds A polymerizable liquid crystal compound (X1) and a polymerizable liquid crystal compound (X2) having the following molecular structures were respectively prepared. Polymerizable liquid crystal compound (X1) was produced according to the method described in JP-A-2010-31223. Further, the polymerizable liquid crystal compound (X2) was produced according to the method described in JP-A-2009-173893.

Polymerizable liquid crystal compound (X1)

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

Polymerizable liquid crystal compound (X2)

(2) Preparation of a composition for forming a vertically aligned liquid crystal cured film A mixed solution of 13 parts by mass of "KBE-903" manufactured by Shin-Etsu Chemical Co., Ltd. and 87 parts by mass of cyclopentanone, and "Karens MOI" manufactured by Showa Denko Co., Ltd. -EG" 13 parts by mass and 87 parts by mass of cyclopentanone were mixed at a ratio of KBE-903:Karens MOI-EG=1.00:1.35 (mass ratio), and then heated at 30°C. The mixture (hereinafter referred to as "pre-reaction compound") containing a compound (pre-reaction compound) having in its molecule a functional group (hydroxysilyl group) and a (meth)acryloyl group (acryloyl group) that can react with a hydroxyl group or a carboxyl group is heated for 16 hours. , sometimes referred to as mixed solution (1)) was obtained.
Subsequently, 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. To 100 parts by mass of the obtained mixture, 0.25 parts by mass of the leveling agent "F-556" (manufactured by DIC), and ionic compound A (molecular weight: 645 ) 2.0 parts by mass, 6 parts by mass of Irgacure 369E (manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator, "APG" manufactured by Shin Nakamura Chemical Co., Ltd. as a polymerizable non-liquid crystal compound having two or more (meth)acryloyl groups, -700'' (bifunctional, molecular weight: 808) was added, and N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. Furthermore, a compound (pre-reaction compound) having a functional group capable of reacting with a hydroxyl group or a carboxyl group and a (meth)acryloyl group in its molecule is added to 100 parts by mass of the mixture of the polymerizable liquid crystal compounds (X1) and (X2). Mixed liquid (1) was added in an amount of 2.35 parts by mass to obtain a mixture. The resulting mixture was stirred at 80° C. for 1 hour to obtain a composition for forming a vertically aligned liquid crystal cured film.

Ionic compound A:

(3) Production of vertically aligned liquid crystal cured film After corona treatment was performed on a COP film (ZF14-50) manufactured by Nippon Zeon, the composition for forming a vertically aligned liquid crystal cured film was applied using a bar coater, and the film was heated at 120°C. After heating for 90 seconds, using a high-pressure mercury lamp (Unicure VB-15201BY-A, manufactured by Ushio Inc.), the surface coated with the composition for forming a vertically aligned liquid crystal cured film is irradiated with ultraviolet rays (in a nitrogen atmosphere, An integrated light amount at 365 nm: 500 mJ/cm ² ) was used to form a vertically aligned liquid crystal cured film. The thickness of the obtained vertically aligned liquid crystal cured film was measured with an ellipsometer (M-220 manufactured by JASCO Corporation) and was found to be 1.2 μm.

<Rth measurement of vertically aligned liquid crystal cured film>
Corona treatment was performed on the surface of the vertically aligned liquid crystal cured film of the base material and the vertically aligned cured film of the vertically aligned liquid crystal film produced in the above procedure. The material was peeled off. For the obtained laminate consisting of glass, adhesive, and vertically aligned liquid crystal cured film, the front phase difference was measured by changing the incident angle of light on the sample for measuring optical properties using KOBRA-WPR manufactured by Oji Scientific Instruments Co., Ltd. and the phase difference value when tilted by 40° around the fast axis. The average refractive index at each wavelength was measured using an ellipsometer M-220 manufactured by JASCO Corporation. Further, 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 front phase difference value, phase difference value when tilted by 40 degrees to the fast axis center, average refractive index, and film thickness values, Oji Scientific Instruments technical data (http://www.oji-keisoku.co The three-dimensional refractive index was calculated with reference to .jp/products/kobra/reference.html). From the obtained three-dimensional refractive index, the optical properties of each vertically aligned liquid crystal cured film were calculated according to the following formula. The results are shown in Table 1.
RthC(λ)=((nxC(λ)+nyC(λ))/2-nzC(λ))×dC
Note that RthC(λ) represents a retardation value in the film thickness direction of a vertically aligned liquid crystal cured film at a wavelength of λ nm. In addition, nxC(λ) is the in-plane principal refractive index of the vertically aligned liquid crystal cured film at the wavelength λnm, nyC(λ) is the refractive index in the direction orthogonal to nxC(λ) in the plane at the wavelength λnm, and nzC( λ) indicates the refractive index in the thickness direction of the vertically aligned liquid crystal cured film at the wavelength λ nm, and when nxC(λ) = nyC(λ), nxC(λ) is the refractive index in any direction within the film plane. where dC represents the thickness of the vertically aligned liquid crystal cured film.

<Measurement of base material peeling force>
After corona treatment was performed on the vertically aligned liquid crystal cured film side of the laminate consisting of the vertically aligned liquid crystal cured film and the base material, the vertically aligned liquid crystal cured film side was subjected to a corona treatment, and then a 12 cm long x 10 cm wide x 0.2 cm thick film was coated with a 15 μm pressure-sensitive adhesive manufactured by Lintec. It was bonded to 7 mm glass (composition: base material/vertically aligned liquid crystal cured film/adhesive layer/glass). A cut with a width of 2.5 cm was made in the obtained sample from the base material side using a cutter. The prepared sample was set in Autograph "EZ-L" manufactured by Shimadzu Corporation, and the peeling force when peeling a 2.5 cm wide base material at a speed of 300 mm/min in a direction parallel to the glass surface was confirmed. . The results are shown in Table 1.

<Edge evaluation during cutting process>
After performing corona treatment on the side of the vertically aligned liquid crystal cured film of the laminate consisting of the vertically aligned cured liquid crystal film and the base material, a laminate of 12 cm long x 10 cm wide x 0.5 cm thick was applied using a 15 μm pressure-sensitive adhesive manufactured by Lintec. It was bonded to 7 mm glass (composition: base material/vertically aligned liquid crystal cured film/adhesive layer/glass). A 10 cm wide incision was made in the sample from the base material side using a cutter, and the resulting cut surface was observed at 11 points every 1 cm using a microscope ("BX-51" manufactured by Olympus Corporation). The shortest distance from the point to the point where the base material was floating was measured, and the average value of the 11 points of data was taken as the edge floating length, and the edges during cutting were evaluated according to the following criteria. The results are shown in Table 1.
Evaluation criteria ○: Less than 100 μm △: 100 μm or more and less than 200 μm ×: 200 μm or more

2. Examples 2-4
Example 1 except that the amount of "APG-700", which is a polyfunctional (meth)acrylate compound, was changed as shown in Table 1 when preparing the composition for forming a vertically aligned liquid crystal cured film. Samples were prepared and evaluated in the same manner. The results are shown in Table 1.

3. Example 5
Except that 3.0 parts by mass of "A-DPH" (hexafunctional, molecular weight: 578) manufactured by Shin Nakamura Chemical Co., Ltd. was added in place of APG-700 when preparing the composition for forming a vertically aligned liquid crystal cured film. Samples were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

4. Example 6
A sample was prepared in the same manner as in Example 1, except that APG-700 was not added (that is, no polyfunctional (meth)acrylate was blended) when preparing the composition for forming a vertically aligned liquid crystal cured film, evaluated. The results are shown in Table 1.

5. Comparative example 1
Samples were prepared and evaluated in the same manner as in Example 1, except that the composition for forming a vertically aligned liquid crystal cured film was prepared as described below. The results are shown in Table 1.
(1) Preparation of composition for forming vertically aligned liquid crystal cured film Polymerizable liquid crystal compound (X1) and polymerizable liquid crystal compound (X2) were mixed at a mass ratio of 90:10 to obtain a mixture. 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, silane coupling agent "KBE-9103" (Shin-Etsu Co., Ltd.) 0.5 parts by mass (manufactured by Kagaku Kogyo Co., Ltd.), 0.5 parts by mass of 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl)butan-1-one (manufactured by BASF Japan Ltd.) as a photopolymerization initiator (Irgacure (registered trademark) manufactured by BASF Japan Ltd. ) 369 (Irg369)'') 6 parts by mass were added. Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration was 13%. This mixture was stirred at 80° C. for 1 hour to obtain a composition for forming a vertically aligned liquid crystal cured film.

According to the present invention, it is possible to directly form a vertically aligned liquid crystal cured film without forming a vertically aligned film on a base material. In addition, since the base material and the vertically aligned liquid crystal cured film have optimal adhesion, the vertically aligned liquid crystal cured film is difficult to peel off from the base material when a laminate including the vertically aligned liquid crystal cured film is cut. It was confirmed that the base material could be peeled off with a small force when peeling from the laminate.

1: Base material 2: Vertically aligned liquid crystal cured film 11: Laminated body a: Base material side interface b: Non-base material side interface

Claims (18)

A laminate comprising a base material and a vertically aligned liquid crystal cured film adjacent to the base material,
The vertical alignment cured liquid crystal 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 in a plane of the cured liquid crystal film. It is a liquid crystal cured film that is cured in a state perpendicular to the
The polymerizable liquid crystal composition includes 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 functional group capable of reacting with the hydroxyl group or carboxyl group is at least one selected from the group consisting of an isocyanate group, an epoxy group, an oxetanyl group, a silanol group, an alkoxysilyl group, and a hydroxysilyl group,
A laminate that satisfies formula (1).
0.02<P<1.00 (N/25mm) (1)
[In formula (1), P is the base material peeling force (N/25 mm) when the base material is peeled off at a speed of 300 mm/min at the interface between the vertically aligned liquid crystal cured film and the base material constituting the laminate. be. ] The laminate according to claim 1, wherein the vertically aligned liquid crystal cured film has a thickness of 0.3 μm or more and 5.0 μm or less. The laminate according to claim 1 or 2, wherein the vertically aligned liquid crystal cured film satisfies formula (2).
-150nm≦RthC(550)≦-30nm (2)
[In formula (2), RthC (550) represents the retardation value in the thickness direction at a wavelength of 550 nm of the vertically aligned liquid crystal cured film. ] 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 vertically aligned liquid crystal cured film contains an ionic compound consisting of nonmetallic atoms as a vertical alignment promoter. The laminate according to claim 5, wherein the ionic compound made of non-metallic atoms has a molecular weight of 100 or more and 10,000 or less. The polymerizable liquid crystal composition forming the vertically aligned liquid crystal cured film contains at least one vertical alignment promoter, at least one polymerizable liquid crystal compound having a (meth)acryloyl group, and two or more (meth)acryloyl groups. The laminate according to any one of claims 1 to 6, comprising at least one polymerizable non-liquid crystal compound having the following properties. The laminate according to any one of claims 1 to 7, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound as a vertical alignment promoter. The laminate according to claim 8, wherein the nonionic silane compound is a silane coupling agent. The laminate according to any one of claims 1 to 9, wherein the vertically aligned liquid crystal cured film contains a nonionic silane compound and an ionic compound as vertical alignment promoters. The laminate according to any one of claims 1 to 10 , wherein the vertically aligned liquid crystal cured film satisfies the following relational expression (3).
RthC(450)/RthC(550)≦1.0 (3)
[In formula (3), RthC (450) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 450 nm, and RthC (550) represents the retardation value in the thickness direction of the vertically aligned liquid crystal cured film at a wavelength of 550 nm. represents. ] The laminate according to any one of claims 1 to 11 , further comprising a horizontally oriented retardation film. 13. The horizontally oriented retardation film is a horizontally oriented liquid crystal cured film obtained by curing at least one polymerizable liquid crystal compound oriented horizontally with respect to the in-plane direction of the retardation film. laminate. An elliptically polarizing plate comprising the laminate according to claim 12 or 13 and a polarizing film. The elliptically polarizing plate according to claim 14 , wherein the angle between the slow axis of the horizontally oriented retardation film and the absorption axis of the polarizing film is 45±5°. An organic EL display device comprising the elliptically polarizing plate according to claim 14 or 15 . 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, a polymerizable liquid crystal compound, and an ionic compound consisting of a nonmetallic atom as a vertical alignment promoter. ,
The functional group capable of reacting with the hydroxyl group or carboxyl group is at least one selected from the group consisting of an isocyanate group, an epoxy group, an oxetanyl group, a silanol group, an alkoxysilyl group, and a hydroxysilyl group. Composition for film formation. The composition for forming a vertically aligned liquid crystal cured film according to claim 17 , wherein the polymerizable liquid crystal compound is a polymerizable liquid crystal compound having a (meth)acryloyl group.

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