JP2023181683A - Laminate, optical film, polarizing plate, and image display device - Google Patents

Abstract

To provide a laminate excellent in both peelability and liquid crystal alignment of a base material, an optical film, a polarizing plate, and an image display device.SOLUTION: A laminate has a first base material, and a first retardation layer provided adjacent to the first base material. The first base material is a temporary support for transfer. The first retardation layer is a layer obtained by fixing a liquid crystal compound that contains a polymer not having a photo-alignment group and is horizontally aligned. When the secondary ion intensity of the polymer in the first retardation layer is measured by a time-of-flight secondary ion mass spectrometry while irradiating, with an ion beam, from a surface of the first retardation layer facing the first base material toward a surface on the opposite side of the first base material, an average value IB1 of the secondary ion intensity derived from the polymer in a base material-side surface layer area is larger than an average value IA1 of the secondary ion intensity derived from the polymer in an air-side surface layer area.SELECTED DRAWING: None

Description

The present invention relates to a laminate, an optical film, a polarizing plate, and an image display device.

Optical films such as optical compensatory sheets and retardation films are used in various image display devices from the viewpoints of eliminating image coloration and expanding viewing angles.
A stretched birefringent film has been used as an optical film, but in recent years, it has been proposed to use a liquid crystal layer (retardation layer) formed using a liquid crystal compound in place of the stretched birefringent film.
For example, Patent Document 1 describes a liquid crystal film that includes a photoalignment layer and a liquid crystal layer in this order on a transparent substrate.

International Publication No. 2020/054720

The present inventors studied a known laminate having a base material and a liquid crystal layer, such as those described in Patent Document 1, and found that when attempting to peel off the base material from the viewpoint of thinning the film, transferring, etc., the peeling force increases. It has become clear that there are cases where it is difficult to peel off.
It has also been found that changing the formulation or formation method of the liquid crystal layer from the viewpoint of adjusting the releasability may result in poor liquid crystal orientation.

Therefore, an object of the present invention is to provide a laminate, an optical film, a polarizing plate, and an image display device that are excellent in both the peelability of a base material and the alignment of liquid crystals.

As a result of intensive studies to achieve the above object, the present inventors found that in a laminate including a first base material and a first retardation layer provided adjacent to the first base material, the first base material is , is a temporary support for transfer, and the first retardation layer is a layer formed by fixing a horizontally aligned liquid crystal compound containing a polymer having no photo-alignable group; The inventors have discovered that both the releasability and liquid crystal orientation of the base material are improved by unevenly distributing the polymer that does not have this on the surface of the first base material, and the present invention has been completed based on this finding.
That is, the present inventors have found that the above problem can be solved by the following configuration.

[1] A laminate including a first base material and a first retardation layer provided adjacent to the first base material,
The first base material is a temporary support for transfer,
The first retardation layer is a layer formed by fixing a horizontally aligned liquid crystal compound containing a polymer having no photoalignable group,
While irradiating an ion beam from the surface of the first retardation layer on the first base material side to the surface opposite to the first base material, the time-of-flight secondary ion mass spectrometry was performed to detect the difference in the first retardation layer. When measuring the secondary ion strength of a polymer,
A region from the surface of the first retardation layer on the first base material side to a depth position corresponding to 10% of the total thickness of the first retardation layer is defined as a base material side surface layer region,
When the area from the surface of the first retardation layer opposite to the first base material to a depth position corresponding to 10% of the total thickness of the first retardation layer is defined as the air side surface layer area,
A laminate in which the average value I _B1 of the secondary ion strength derived from the polymer in the surface layer region on the base material side is larger than the average value I _A1 of the secondary ion strength derived from the polymer in the surface layer region on the air side.
[2] The laminate according to [1], wherein the peeling force P1 between the first base material and the first retardation layer is 0.12 N/25 mm or less.
[3] The laminate according to [1] or [2], wherein the polymer has a repeating unit represented by formula (1) described below.
[4] The laminate according to [1] or [2], wherein the polymer has a repeating unit represented by formula (2) described below.
[5] X ¹ in formula (2) described below is -COOH, -PO ₃ H, {-OP(=O)(OH) ₂ }, -CO ₂ M ¹ , -SO ₃ M ¹ , -NT ¹ T ² represents an oxazoline group, -NG ¹ G ² G ³ E ¹ , or a group having a betaine structure, the laminate according to [4].
[6] The laminate according to [4], wherein X ¹ in formula (2) described below represents -NG ¹ G ² G ³ E ¹ .
[7] X ¹ in formula (2) described below represents a group having a betaine structure,
The laminate according to [4], wherein the group having a betaine structure represents a group represented by any one of formulas (BT1), (BT2), (BT3) and (BT4) described below.
[8] The laminate according to any one of [1] to [7], wherein the polymer has a repeating unit containing an alicyclic structure in its side chain.
[9] The laminate according to any one of [1] to [7], wherein the polymer has a repeating unit containing a fluorine atom in a side chain.
[10] The laminate according to [9], wherein the repeating unit containing a fluorine atom in its side chain is a repeating unit represented by formula (a) described below.
[11] The first retardation layer is an optically anisotropic layer A containing a photoalignment compound,
Furthermore, an optically anisotropic layer B is provided on the side opposite to the first base material in the optically anisotropic layer A,
The optically anisotropic layer A is measured by time-of-flight secondary ion mass spectrometry while irradiating an ion beam from the surface of the optically anisotropic layer A on the first substrate side toward the surface on the optically anisotropic layer B side. When measuring the secondary ion strength of the photoalignment compound in
The area from the surface of the optically anisotropic layer A on the first substrate side to a depth position corresponding to 10% of the total thickness of the optically anisotropic layer A is defined as a substrate side surface layer area,
The area from the surface of optically anisotropic layer A on the optically anisotropic layer B side to a depth position corresponding to 10% of the total thickness of optically anisotropic layer A was defined as the optically anisotropic layer B side surface layer area. case,
The average value I _A2 of the secondary ion intensity derived from the photo-alignment compound in the optically anisotropic layer B-side surface layer region is larger than the average value I _B2 of the secondary ion intensity derived from the photo-alignment compound in the substrate-side surface layer region. The laminate according to [1].
[12] A first base material, a first retardation layer, a second retardation layer, and a second base material in this order,
The peeling force P1 between the first base material and the first retardation layer and the peeling force P2 between the second base material and the second retardation layer satisfy the relationship of the following formula (A), [ 1] to [11].
Formula (A) P1<P2
[13] An optical film obtained by peeling the first base material from the laminate according to any one of [1] to [11].
[14] An optical film obtained by peeling the first base material and the second base material from the laminate according to [12].
[15] A polarizing plate comprising the optical film according to [13].
[16] A polarizing plate comprising the optical film according to [14].
[17] An image display device comprising the polarizing plate according to [15].
[18] An image display device comprising the polarizing plate according to [16].

According to the present invention, it is possible to provide a laminate, an optical film, a polarizing plate, and an image display device that are excellent in both base material releasability and liquid crystal orientation.

FIG. 1 is a schematic cross-sectional view of one embodiment of the laminate of the present invention. FIG. 2 is a schematic cross-sectional view of one embodiment of the laminate of the present invention. FIG. 3 is a schematic cross-sectional view of one embodiment of the laminate of the present invention. FIG. 4 is a diagram for explaining the procedure for laminating the first retardation layer and the second retardation layer in the laminate of the present invention to an object to be laminated. FIG. 5 is a diagram for explaining the procedure for laminating the first retardation layer and the second retardation layer in the laminate of the present invention to an object to be laminated. FIG. 6 is a diagram for explaining the procedure for laminating the first retardation layer and the second retardation layer in the laminate of the present invention to an object to be laminated.

The present invention will be explained in detail below.
Although the description of the constituent elements described below may be made based on typical embodiments of the present invention, the present invention is not limited to such embodiments.
Note that in this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as the lower limit and upper limit.
Moreover, in this specification, each component may be a substance corresponding to each component, which may be used alone or in combination of two or more. Here, when two or more types of substances are used together for each component, the content of the component refers to the total content of the substances used in combination, unless otherwise specified.
Further, in this specification, "(meth)acrylic" is a notation representing "acrylic" or "methacrylic".

In this specification, Re(λ) and Rth(λ) represent in-plane retardation and thickness direction retardation at wavelength λ, respectively. Note that the wavelength λ is 550 nm unless otherwise specified.
Further, in this specification, Re (λ) and Rth (λ) are values measured at a wavelength λ using AxoScan (manufactured by Axometrics).
Specifically, by inputting the average refractive index ((nx+ny+nz)/3) and film thickness (d (μm)) in AxoScan,
In-plane slow axis direction (°)
Re(λ)=R0(λ)
Rth(λ)=((nx+ny)/2-nz)×d
is calculated.
Note that R0(λ) is displayed as a numerical value calculated by AxoScan, but it means Re(λ).

In this specification, the refractive indexes nx, ny, and nz are measured using an Abbe refractometer (NAR-4T, manufactured by Atago Co., Ltd.) using a sodium lamp (λ=589 nm) as a light source. In addition, when measuring wavelength dependence, it can be measured using a multi-wavelength Abbe refractometer DR-M2 (manufactured by Atago Co., Ltd.) in combination with an interference filter.
Further, values from the Polymer Handbook (JOHN WILEY & SONS, INC.) and catalogs of various optical films can be used. The average refractive index values of the main optical films are illustrated below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).

"Light" in this specification means active rays or radiation, such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet (EUV light), X-rays, ultraviolet rays, It also means an electron beam (EB). Among these, ultraviolet rays are preferred.

The bonding direction of the divalent group (for example, -COO-) described herein is not particularly limited. For example, in the bond "L ¹ -L ² -L ³ ", L ² is -CO-O- In this case, if the position bonded to the ^L1 side is *1 and the position bonded to the ^L3 side is *2, then ^L2 may be *1-CO-O-*2, *1-O-CO-*2 may be used.

[Laminated body]
The laminate of the present invention includes a first base material and a first retardation layer provided adjacent to the first base material.
Further, the first base material is a temporary support for transfer, and the first retardation layer is a horizontally aligned polymer containing a polymer having no photoalignable group (hereinafter also abbreviated as "specific polymer"). This is a layer formed by fixing a liquid crystal compound.
Furthermore, time-of-flight secondary ion mass spectrometry was performed while irradiating the ion beam from the surface of the first retardation layer on the first base material side to the surface on the opposite side of the first base material. When measuring the secondary ion intensity of a specific polymer in the first retardation layer using Secondary Ion Mass Spectrometry (TOF-SIMS), the The area up to a depth corresponding to 10% of the total thickness is defined as the base material side surface layer area, and the area from the surface of the first retardation layer opposite to the first base material to 10% of the total thickness of the first retardation layer When the area up to the corresponding depth position is defined as the air side surface layer area, the average value of secondary ion intensity I _A1 derived from the specific polymer in the air side surface layer area is higher than the secondary ion intensity derived from the specific polymer in the base material side surface layer area. The average value of ionic strength I _B1 is large.

Here, the type of ion beam used in TOF-SIMS includes an ion beam using an argon gas cluster ion gun (Ar-GCIB gun).
Furthermore, with TOF-SIMS, it is only necessary to obtain a profile in the depth direction of the first retardation layer, and while irradiating the ion beam from the surface of the first base material in the laminate, the ion beam is directed toward the first retardation layer side. , both the first base material and the first retardation layer may be analyzed in the depth direction.

In the following explanation, the average value I _A1 of the secondary ion intensity derived from the specific polymer in the air-side surface region of the first retardation layer is higher than the The fact that the average value I _B1 of the ionic strength is large is also simply referred to as "the specific polymer is unevenly distributed on the surface of the first base material".
Furthermore, when the first retardation layer contains two or more types of specific polymers, it is sufficient that at least one type of specific polymer is unevenly distributed on the first base material side surface.

In the present invention, as described above, in the laminate including a first base material and a first retardation layer provided adjacent to the first base material, the first base material is a temporary support for transfer. , the first retardation layer is a layer formed by fixing a horizontally aligned liquid crystal compound containing at least one specific polymer, and the specific polymer is unevenly distributed on the surface of the first base material. Both the releasability and liquid crystal alignment become good.
The reason why these effects occur is not clear in detail, but the present inventors speculate as follows.
That is, because the specific polymer is unevenly distributed on the surface of the first base material, the peeling force from the first base material (transfer support) is reduced, and the specific polymer has a photo-alignable group. It is thought that this is because the alignment (horizontal alignment) of the liquid crystal compound is not affected during the formation of the first retardation layer, and thus both the peelability of the base material and the liquid crystal alignment are improved.

An example of the laminate of the present invention is shown in FIGS. 1 to 3.
As shown in FIG. 1, the laminate 10A includes a first base material 12 and a first retardation layer 14. The first retardation layer 14 contains a specific polymer, and the specific polymer is unevenly distributed on the surface on the first base material 12 side.
As shown in FIG. 2, the laminate 10B includes a first base material 12, an optically anisotropic layer A as the first retardation layer 14, and an optically anisotropic layer B15 different from the first retardation layer 14. It may have. The first retardation layer 14 (optically anisotropic layer A) may contain not only the specific polymer but also a photoalignment compound described below. In that case, it is preferable that the specific polymer is unevenly distributed on the surface on the first base material 12 side, and the photo-alignment compound is unevenly distributed on the surface on the optically anisotropic layer B15 side.
As shown in FIG. 3, the laminate 10C includes a first base material 12, a first retardation layer 14, a second retardation layer 16, and a second base material 18 in this order.
In FIG. 3, the first base material 12 and the first retardation layer 14 are in direct contact with each other, and the second retardation layer 16 and the second base material 18 are also in direct contact with each other.
Further, in FIG. 3, the first retardation layer 14 and the second retardation layer 16 are in direct contact with each other, but as will be described later, the laminate is formed between the first retardation layer and the second retardation layer. It may also have an adhesive layer or a pressure-sensitive adhesive layer.

The laminates 10A to 10C are used to bond the retardation layer to an object to be bonded (eg, a polarizer). For example, as a procedure for bonding using the laminate 10C, first, as shown in FIG. 4, the first base material 12 is peeled off from the laminate 10C. At that time, it is preferable that the second base material 18 is not peeled off. Next, as shown in FIG. 5, the first retardation layer 14 side of the laminate obtained by peeling off the first base material 12 is bonded to the object 20 to be bonded. Thereafter, as shown in FIG. 6, by peeling off the second base material 18, the first retardation layer 14 and the second retardation layer 16 are bonded to the object to be bonded 20.
As shown in the above procedure, the first base material 12 functions as a so-called light release base material, and the second base material 18 functions as a so-called heavy release base material.
In the present invention, since the specific polymer contained in the first retardation layer is unevenly distributed on the surface of the first base material, the base material can be peeled off in a predetermined order as shown in FIGS. 4 to 6 above. , can be easily carried out (in other words, with good removability).

In the present invention, the peeling force P1 between the first base material and the first retardation layer is preferably 0.12N/25mm or less, and 0.12N/25mm or less, because the peelability of the base material is further improved. It is more preferable that it is 0.09 N/25 mm or less, and even more preferably that it is 0.05 N/25 mm or less. Note that the lower limit of the peeling force P1 is not particularly limited, but is preferably 0.01 N/25 mm or more.

Here, the peel force P1 can be calculated by a 180° peel test using a so-called tensile tester.
As an example of a method for calculating the peeling force P1, an evaluation sample consisting of a portion of the first base material and the first retardation layer in the laminate may be prepared separately, and the peeling force P1 may be calculated. More specifically, an evaluation sample consisting of the first base material and the first retardation layer in the laminate was separately prepared, and the surface of the evaluation sample on the first retardation layer side was subjected to corona treatment. A UV curable adhesive composition is applied to the surface of the corona-treated first retardation layer to form a coating film. Next, the substrate and the evaluation sample are bonded together so that the formed coating film and the substrate (for example, a polarizer) are in contact with each other, and the coating film is cured by irradiation with ultraviolet rays. Next, an adhesive layer was placed on the substrate side surface of the obtained evaluation sample with a substrate, and a predetermined size (width 25 mm x length 150 mm) was cut out from the obtained evaluation sample with the adhesive layer, and the cut out evaluation sample was Laminate the sample adhesive layer to a glass substrate. Thereafter, a peeling tape (width 25 mm x length 180 mm) is bonded to the surface of the first base material side of the evaluation sample bonded to the glass substrate. Then, using a tensile tester, one end of the release tape was held and a peel test was performed at a crosshead speed of 5 m/min and a peel angle of 180° in an atmosphere of 25°C and 60% relative humidity. By doing so, the peeling force P1 between the first base material and the first retardation layer is calculated. Note that the above-mentioned peeling force P1 corresponds to the peeling force when the peeling force reaches a steady state between when the peeling tape is pulled and the first base material is completely peeled off from the first retardation layer.
In addition, although the method of separately preparing an evaluation sample was described above, by laminating a peeling tape according to the above procedure on the first base material of the laminate and carrying out the above 180° test, the peel strength can be measured. P1 may also be calculated.

Each member constituting the laminate will be described in detail below.

[First base material]
The first base material is a temporary support (removable support) for transfer, and is a member that supports the first retardation layer before peeling.
The first base material is preferably made of an organic material, more preferably a resin base material.
Materials for the resin base material include cellulose polymers; acrylic polymers such as polymethyl methacrylate and acrylic ester polymers that are lactone ring-containing polymers; thermoplastic norbornene polymers; polycarbonate polymers; polyethylene terephthalate, and , polyester polymers such as polyethylene naphthalate; styrene polymers such as polystyrene and acrylonitrile styrene copolymers; polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; vinyl chloride polymers; nylon, and amide polymers such as aromatic polyamide; imide polymers; sulfone polymers; polyether sulfone polymers; polyetheretherketone polymers; polyphenylene sulfide polymers; vinylidene chloride polymers; vinyl alcohol polymers; vinyl butyral polymers. Examples include polymers; arylate polymers; polyoxymethylene polymers; epoxy polymers; and polymers obtained by mixing these polymers.
Among these, triacetylcellulose, polyethylene terephthalate, or a polymer having an alicyclic structure is preferable as the material for the resin base material, and triacetylcellulose is more preferable.

The first base material contains various additives (for example, an optical anisotropy adjuster, a wavelength dispersion adjuster, fine particles, a plasticizer, an ultraviolet inhibitor, a deterioration inhibitor, a release agent, etc.). Good too.

The first base material may have a single layer structure or a multilayer structure.
When the first base material has a multilayer structure, it may have a structure including a support and an alignment film.
Examples of the support include the resin base materials described above.
The alignment film can be formed by rubbing an organic compound (preferably a polymer), obliquely depositing an inorganic compound, forming a layer with microgrooves, or applying an organic compound (e.g., ω-tricosane) by the Langmuir-Blodgett method (LB film). acids, dioctadecylmethylammonium chloride, methyl stearate).
Examples of the alignment film include a photo-alignment film.
The thickness of the alignment film is not particularly limited as long as it can exhibit the alignment function, but it is preferably 0.01 to 5.0 μm, more preferably 0.05 to 3.0 μm, and even more preferably 0.5 to 1.0 μm. preferable.
The alignment film may be peelable.

The thickness of the first base material is not particularly limited, and is preferably 5 to 200 μm, more preferably 10 to 100 μm, and even more preferably 20 to 90 μm.

[First retardation layer]
The first retardation layer is a layer provided adjacent to the first base material, and is a layer formed by fixing a horizontally aligned liquid crystal compound.
Here, "horizontal alignment" refers to an alignment in which the angle between the surface of the first base material and the director of the liquid crystal molecules is parallel (homogeneous alignment) when the liquid crystal compound is a rod-shaped liquid crystal compound; When is a discotic liquid crystal compound, it refers to an orientation in which the surface of the first base material and the disc surface are parallel to each other. It should be noted that it is not required to be strictly horizontal (parallel), but includes a range of error allowed in the technical field to which the present invention belongs. For example, it means that the angle is within a strict angle of ±10°, and the error from the exact angle is preferably 5° or less, more preferably 3° or less.
Further, the "fixed" state is a state in which the orientation (horizontal orientation) of the liquid crystal compound is maintained. Specifically, the layer usually has no fluidity in the temperature range of 0 to 50°C, or -30 to 70°C under more severe conditions, and the orientation form changes due to external fields or external forces. It is preferable to be in a state where the fixed orientation form can be stably maintained. Note that when the liquid crystal compound has a polymerizable group, the alignment state of the liquid crystal compound can be easily fixed by the curing treatment described below.

Liquid crystal compounds can generally be classified into rod-like types and disk-like types based on their shapes. Furthermore, there are low-molecular type and high-molecular type, respectively. Polymers generally refer to those with a degree of polymerization of 100 or more (Polymer Physics/Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992). In the present invention, any liquid crystal compound can be used, but a rod-like liquid crystal compound or a discotic liquid crystal compound is preferable. Further, a monomer or a relatively low molecular weight liquid crystal compound having a degree of polymerization of less than 100 is preferable.

It is preferable that the liquid crystal compound has a polymerizable group. That is, the liquid crystal compound is preferably a polymerizable liquid crystal compound. Examples of the polymerizable group that the liquid crystal compound has include an acryloyl group, a methacryloyl group, an epoxy group, and a vinyl group.
By polymerizing such a polymerizable liquid crystal compound, the orientation of the liquid crystal compound can be fixed. Note that after the liquid crystal compound is fixed by polymerization, it is no longer necessary to exhibit liquid crystallinity.

As the rod-shaped liquid crystal compound, for example, those described in claim 1 of Japanese Patent Application Publication No. 11-513019 or paragraphs [0026] to [0098] of JP-A-2005-289980 are preferable, and as the discotic liquid crystal compound, For example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 or paragraphs [0013] to [0108] of JP-A-2010-244038 are preferable.

As the liquid crystal compound, a reverse wavelength dispersion liquid crystal compound can be used.
Here, in this specification, a "reverse wavelength dispersion" liquid crystal compound refers to the in-plane retardation (Re) value measured at a specific wavelength (visible light range) of a retardation film produced using this compound. In other words, as the measurement wavelength becomes larger, the Re value becomes the same or becomes higher.

In the present invention, the first retardation layer is preferably a layer formed by fixing a horizontally aligned disk-shaped liquid crystal compound. Among these, it is more preferable that the first retardation layer is a layer formed by fixing a horizontally aligned discotic liquid crystal compound having a polymerizable group by polymerization.

<Specific polymer>
As described above, the first retardation layer is a layer in which a polymer (specific polymer) that does not have a photo-alignable group is unevenly distributed on the first base material side surface.
Here, the term "photoalignable group" refers to a group that has a photoalignment function that induces rearrangement or anisotropic chemical reaction when irradiated with anisotropic light (e.g., plane-polarized light). .

In the present invention, it is preferable that the specific polymer has a repeating unit represented by the following formula (1) because the releasability of the base material is further improved.

In the above formula (1), R ¹ represents a hydrogen atom or a methyl group.
L ¹ is a single bond, -O-, -CO-, -NR ^L -, a divalent aliphatic group that may have a substituent, or a divalent aliphatic group that may have a substituent. Represents a divalent linking group selected from the group consisting of aromatic groups and combinations thereof. R ^L represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
R ² represents an alkyl group having 1 to 20 carbon atoms. However, in the case of an alkyl group having 2 to 20 carbon atoms, one or more of -CH ₂ - constituting the alkyl group may be substituted with -COO- or -CO-.

The divalent aliphatic group represented by one embodiment of L ¹ includes an alkylene group. The number of carbon atoms in the divalent aliphatic group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
The divalent aromatic group represented by one embodiment of L ¹ includes an arylene group having 6 to 12 carbon atoms. Among them, a phenylene group is preferred.
The above combination represented by one embodiment of ^L1 includes -COO-, -CONR ^L -, a divalent aliphatic group which may have a -COO- substituent, and a -CONR ^L -substituent. Examples include divalent aliphatic groups that may be present.
Here, examples of substituents that the divalent aliphatic group and the divalent aromatic group may have (hereinafter abbreviated as "substituent X") include halogen atoms, alkyl groups, and alkoxy groups. , an aryl group, an aryloxy group, a cyano group, a carboxy group, an alkoxycarbonyl group, and a hydroxyl group.
Further, the number of carbon atoms in the alkyl group represented by one embodiment of R ^L is preferably 1 to 10, more preferably 1 to 5.

As the repeating unit represented by the above formula (1), a repeating unit represented by the following formula (1-1) is preferable. Note that R ¹ in the following formula (1-1) represents a hydrogen atom or a methyl group as in the above formula (1).

When the specific polymer has a repeating unit represented by the above formula (1), the content of the repeating unit represented by the above formula (1) is not particularly limited; On the other hand, it is preferably 40 to 100% by mass, more preferably 60 to 100% by mass.

In the present invention, it is preferable that the specific polymer has a repeating unit represented by the following formula (2) because the releasability of the base material is further improved.

In the above formula (2), R ³ represents a hydrogen atom or a methyl group.
L ³ represents a single bond or a divalent linking group.
X ¹ is -OH, -COOH, -PO ₃ H, {-OP(=O)(OH) ₂ }, -CO ₂ M ¹ , -SO ₃ M ¹ , -NT ¹ T ² , oxazoline group, - Represents NG ¹ G ² G ³ E ¹ or a group having a betaine structure.
M ¹ represents an alkali metal, an alkaline earth metal, Mg, Al, or Q ¹ Q ² Q ³ Q ⁴ N ⁺ . Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
T ¹ and T ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. However, T ¹ and T ² may be bonded to each other to form a ring structure containing a nitrogen atom.
G ¹ , G ² and G ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
E ¹ represents an anion.

The divalent linking group represented by one aspect of L ³ in the above formula (2) is not particularly limited, but includes, for example, -CO-, -O-, an alkylene group (preferably having 1 to 20 carbon atoms), and a cycloalkylene group. (preferably having 3 to 20 carbon atoms), an arylene group (preferably having 6 to 20 carbon atoms), -SO-, -SO ₂ -, -NH-, -NR-, and 2 formed by a combination of two or more of these. and a valent linking group. The above R represents an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms).
When L ³ represents a divalent linking group, it is preferably a divalent linking group consisting of at least one selected from the group consisting of -O-, -COO-, -CONH-, and an alkylene group. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 12 carbon atoms, and even more preferably an alkylene group having 1 to 6 carbon atoms.

As described above, X ¹ in the above formula (2) is -OH, -COOH, -PO ₃ H, {-OP(=O)(OH) ₂ }, -CO ₂ M ¹ , -SO ₃ M ¹ , -NT ¹ T ² , an oxazoline group, -NG ¹ G ² G ³ E ¹ , or a group having a betaine structure.
Among these, -COOH, -PO ₃ H, {-OP(=O)(OH) ₂ }, -CO ₂ M ¹ , -SO ₃ M ¹ , - because the peelability of the base material is further improved. It is preferable to represent NT ¹ T ² , an oxazoline group, -NG ¹ G ² G ³ E ¹ , or a group having a betaine structure.
Further, it is more preferable to represent -NG ¹ G ² G ³ E ¹ because the peelability of the base material is further improved.

When X ¹ in the above formula (2) represents -CO ₂ M ¹ , it is preferably -CO ₂ ^- .(M ¹ ) ⁺ in the form of a salt.
Here, (M ¹ ) ⁺ represents an alkali metal ion, an alkaline earth metal ion, Mg ²⁺ , Al ³⁺ , or Q ¹ Q ² Q ³ Q ⁴ N ⁺ . Note that when (M ¹ ) ⁺ is Mg ²⁺ , one Mg ²⁺ and two CO ₂ ⁻ preferably form a salt. When (M ¹ ) ⁺ is Al ³⁺ , one Al ³⁺ and three CO ₂ ⁻ preferably form a salt.

When X ¹ in the above formula (2) represents -SO ₃ M ¹ , it is preferably -SO ₃ ^- .(M ¹ ) ⁺ in a salt state.
Here, (M ¹ ) ⁺ represents an alkali metal ion, an alkaline earth metal ion, Mg ²⁺ , Al ³⁺ , or Q ¹ Q ² Q ³ Q ⁴ N ⁺ . Note that when (M ¹ ) ⁺ is Mg ²⁺ , one Mg ²⁺ and two SO ₃ ⁻ preferably form a salt. When (M ¹ ) ⁺ is Al ³⁺ , one Al ³⁺ and three SO ₃ ⁻ preferably form a salt.

Examples of the alkali metal represented by one embodiment of ^M1 include lithium (Li), sodium (Na), potassium (K), and cesium (Cs).
Examples of the alkaline earth metal represented by one embodiment of ^M1 include calcium (Ca), strontium (Sr), and barium (Ba).

As described above, Q ¹ , Q ² , Q ³ and Q ⁴ in Q ¹ Q ² Q ³ Q ⁴ N ⁺ (quaternary ammonium salt) represented by one embodiment of M ¹ are each independently a hydrogen atom or a carbon Represents an alkyl group of numbers 1 to 20. The alkyl group represented by one embodiment of Q ¹ , Q ² , Q ³ and Q ⁴ may be linear or branched, and is preferably an alkyl group having 1 to 10 carbon atoms, and preferably an alkyl group having 1 to 7 carbon atoms. More preferably, it is an alkyl group having 1 to 4 carbon atoms.
The alkyl groups represented by Q ¹ , Q ² , Q ³ and Q ⁴ may have a substituent. In addition, examples of the substituent include the above-mentioned substituent X.

When X ¹ in the above formula (2) represents -NT ¹ T 2 , T ¹ and ^{T 2 each} independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a carbon number Represents 1 to 20 alkoxy groups. However, T ¹ and T ² may be bonded to each other to form a ring structure containing a nitrogen atom.
The alkyl group represented by one embodiment of T ¹ and T ² may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 7 carbon atoms. , more preferably an alkyl group having 1 to 4 carbon atoms.
The alkyl group represented by one embodiment of T ¹ and T ² may have a substituent. In addition, examples of the substituent include the above-mentioned substituent X.
The alkoxy group represented by one embodiment of T ¹ and T ² may be linear or branched, preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 7 carbon atoms. , more preferably an alkoxy group having 1 to 4 carbon atoms.
The alkoxy group represented by one embodiment of T ¹ and T ² may have a substituent. In addition, examples of the substituent include the above-mentioned substituent X.
When T ¹ and T ² are bonded, -NT ¹ T ² becomes a cyclic group. Examples of such groups include morpholino groups.
Most preferably T ¹ and T ² represent hydrogen atoms.

When X ¹ in the above formula (2) represents -NG ¹ G ² G ³ E ¹ , it is preferably -N ⁺ G ¹ G ² G ³ ·E ¹ in a salt state.
The anion represented by E ¹ is not particularly limited, and includes, for example, halide ions such as fluoride ion (F ^- ), chloride ion (Cl ^- ), bromide ion (Br ^- ), and iodide ion (I ^- ); water; Oxide ion (OH ⁻ ); Cyanide ion (CN ⁻ ); Nitrate ion (NO ₃ ⁻ ); Carbonate ion (CO ₃ ²⁻ ); Sulfate ion (SO ₄ ²⁻ ); Methanesulfonate anion (CH ₃ SO ₃ ⁾ , sulfonate anions such as benzenesulfonate anion, p-toluenesulfonate anion, and trifluoromethanesulfonate anion; perchlorate anion; borate anions such as tetrafluoroborate anion and tetraphenylborate anion; hexafluorophosphate anion; acetate anion, etc. It will be done. In addition, when E ¹ is a divalent anion, it is preferable that one E ¹ and two NG ¹ G ² G ³ form a salt.

G ¹ , G ² and G ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group represented by G ¹ , G ² and G ³ may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms. , more preferably an alkyl group having 1 to 4 carbon atoms.
The alkyl groups represented by G ¹ , G ² and G ³ may have a substituent. In addition, examples of the substituent include the above-mentioned substituent X.

In the present invention, since the releasability of the base material is further improved, X ¹ in the above formula (2) represents a group having a betaine structure, and the group having a betaine structure is represented by the following formula (BT1), ( It is preferable to represent a group represented by any one of BT2), (BT3) and (BT4).

In the above formulas (BT1) to (BT4), G ⁴ to G ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
L ⁵ to L ⁸ each independently represent a divalent linking group.
* represents the bonding position.

The alkyl group having 1 to 20 carbon atoms represented by one embodiment of G ⁴ to G ¹² in the above formulas (BT1) to (BT4) includes 1 to 20 carbon atoms represented by one embodiment of G ¹ , G ² and G ³ described above. It is the same as that described for the alkyl group of ~20.

The divalent linking groups represented by L ⁵ to L ⁸ in the above formulas (BT1) to (BT4) preferably represent alkylene groups. The alkylene group is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms.
The alkylene group may have a substituent. In addition, examples of the substituent include the above-mentioned substituent X.

The repeating unit represented by the above formula (2) can be formed, for example, by polymerizing the compound shown below. Specific examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, and 2-hydroxyethyl acrylate. -Hydroxypropyl, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl methacrylate, polypropylene glycol acrylate , polypropylene glycol methacrylate, isopropenyloxazoline, styrene boronic acid, 2-(N,N-dimethylamino)ethyl (meth)acrylate, 2-(N-tert-butylamino)ethyl (meth)acrylate, etc. meth)acrylates; (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, Nn-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, Nn-butyl( meth)acrylamide, N-methylol(meth)acrylamide, N-(2-hydroxyethyl)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-(2-dimethylaminoethyl)( Acrylamides such as meth)acrylamide, N-(3-dimethylaminopropyl)(meth)acrylamide, diacetone(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N-(meth)acryloylmorpholine; N-(2 -(meth)acryloyloxyethyl)-N,N,N-trimethylammonium chloride, N-(2-(meth)acryloyloxyethyl)-N,N,N-trimethylammonium bromide, N-(2-( meth)acryloyloxyethyl)-N,N,N-trimethylammonium iodide, N-(2-(meth)acryloyloxyethyl)-N,N,N-trimethylammonium methanesulfonate, N-(2-(meth)acryloyloxyethyl)-N,N,N-trimethylammonium methanesulfonate ) Acryloyloxyethyl)-N,N-diethyl-N-methylammonium = methanesulfonate, N-(2-(meth)acryloyloxyethyl)-N-butyl-N,N-dimethylammonium = iodide, N-(2 (meth)acryloyl group-containing quaternary ammonium salts such as (meth)acryloyloxypropyl)-N,N-diethyl-N-methylammonium chloride; 2-((2-(meth)acryloyloxyethyl)dimethylammonium ) acetate (also called N-(2-(meth)acryloyloxyethyl)-N,N-dimethylglycine), 3-((2-(meth)acryloyloxyethyl)dimethylammonio)propanoate, 4-((2 - Carboxybetaines such as (meth)acryloyloxyethyl)dimethylammonio)butanoate, 5-((2-(meth)acryloyloxyethyl)dimethylammonio)pentanoate; ((2-(meth)acryloyloxyethyl)dimethyl ammonio)methanesulfonate, 2-((2-(meth)acryloyloxyethyl)dimethylammonio)ethanesulfonate, 3-((2-(meth)acryloyloxyethyl)dimethylammonio)propane-1-sulfonate, 4 - Sulfobetaines such as ((2-(meth)acryloyloxyethyl)dimethylammonio)butane-1-sulfonate; 2-(meth)acryloyloxyethyl dividrogen phosphate, 4-(meth)acryloyloxybutyl dividrogen = (Meth)acryloyl group-containing phosphoric acid esters such as phosphate; Examples include phosphorylcholines such as (2-(meth)acryloyloxyethyl)phosphorylcholine and (4-(meth)acryloyloxybutyl)phosphorylcholine; Not limited.

When the specific polymer has a repeating unit represented by the above formula (2), the content of the repeating unit represented by the above formula (2) is not particularly limited, but the content of all repeating units in the specific polymer is On the other hand, it is preferably 40 to 100% by mass, more preferably 60 to 100% by mass.

In the present invention, it is preferable that the specific polymer has a repeating unit containing an alicyclic structure in the side chain, and the repeating unit represented by the following formula (3) is preferred because the peelability of the base material is further improved. It is more preferable that it has a unit.

In the above formula (3), R ⁴ represents a hydrogen atom or a methyl group.
L ⁴ represents a divalent linking group.
Y ¹ represents a cycloalkane ring which may have a substituent.

The divalent linking group represented by L ⁴ includes -CO-, -O-, -S-, -C(=S)-, -CR ¹¹ R ¹² -, -CR ¹³ =CR ¹⁴ -, -NR ¹⁵ - or a divalent linking group consisting of a combination of two or more of these. R ¹¹ to R ¹⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms.
Among the divalent linking groups represented by L ⁴ , -CO-, -O-, -CO-O-, -C(=S)O-, -CR ¹¹ R ¹² -, -CR ¹¹ R ¹² -CR ¹¹ R ¹² -, -O-CR ¹¹ R ¹² -, -CR ¹¹ R ¹² -O-CR ¹¹ R ¹² -, -CO-O-CR 11 R ¹² -, -O-CO- ^{CR 11 R 12} -, - CR ¹¹ R ¹² -O-CO-CR ¹¹ R ¹² -, -CR ¹¹ R ¹² -CO-O-CR ¹¹ R ¹² -, -NR ¹⁵ -CR ¹¹ R ¹² -, and -CO-NR ¹⁵ -, etc. is preferred.

Examples of the cycloalkane ring represented by Y ¹ include a cyclohexane ring, a cyclopeptane ring, a cyclooctane ring, a cyclododecane ring, and a cyclodocosane ring. Among these, a cyclohexane ring is preferred.
Examples of the substituent that the cycloalkane ring may have include the above-mentioned substituent X.

When the specific polymer has a repeating unit containing an alicyclic structure in its side chain, its content is not particularly limited, but it is preferably 5 to 40% by mass, and 10 to 40% by mass based on all repeating units in the specific polymer. ~20% by mass is more preferred.

In the present invention, it is preferable that the specific polymer has a repeating unit containing a fluorine atom in its side chain, since the releasability of the base material is further improved, and the repeating unit is represented by the following formula (a). It is more preferable to have the following.

In the above formula (a), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
R ^a2 represents an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. Note that hereinafter, an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom is also simply referred to as a "fluoroalkyl group."

The number of carbon atoms in the alkyl group represented by one embodiment of R ^a1 in the above formula (a) is preferably 1 to 10, more preferably 1 to 5.

The fluoroalkyl group represented by R ^a2 in the above formula (a) is more preferably a fluoroalkyl group having 1 to 18 carbon atoms, and even more preferably a fluoroalkyl group having 2 to 15 carbon atoms.
Further, the number of fluorine atoms is preferably 1 to 25, more preferably 3 to 21, and most preferably 5 to 21.

Specifically, the monomer forming the repeating unit represented by the above formula (a) includes, for example, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3,3 -Pentafluoropropyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluorooctyl)ethyl (meth)acrylate, 2- (Perfluorodecyl)ethyl (meth)acrylate, 2-(perfluoro-3-methylbutyl)ethyl (meth)acrylate, 2-(perfluoro-5-methylhexyl)ethyl (meth)acrylate, 2-(perfluoro- 7-methyloctyl)ethyl (meth)acrylate, 1H,1H,3H-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, 1H,1H,7H-dodecafluoroheptyl (meth)acrylate ) acrylate, 1H,1H,9H-hexadecafluorononyl (meth)acrylate, 1H-1-(trifluoromethyl)trifluoroethyl (meth)acrylate, 1H,1H,3H-hexafluorobutyl (meth)acrylate, 3 -Perfluorobutyl-2-hydroxypropyl (meth)acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth)acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth)acrylate, 3-(perfluoro- 3-Methylbutyl)-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-5-methylhexyl)-2-hydroxypropyl (meth)acrylate, 3-(perfluoro-7-methyloctyl)-2-hydroxy Examples include propyl (meth)acrylate.

When the specific polymer has a repeating unit containing a fluorine atom in its side chain, its content is not particularly limited, but is preferably 5 to 20% by mass, and 5 to 20% by mass based on all repeating units in the specific polymer. 10% by mass is more preferred.

In the present invention, the weight average molecular weight (Mw) of the specific polymer is preferably 2,000 to 100,000, more preferably 3,000 to 50,000, and more preferably 4,000 to 20,000 because the peelability of the base material is further improved. It is more preferable that
Here, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) under the conditions shown below.
・Solvent (eluent): THF (tetrahydrofuran)
・Device name: TOSOH HLC-8320GPC
・Column: 3 TOSOH TSKgel Super HZM-H (4.6 mm x 15 cm) connected together ・Column temperature: 40°C
・Sample concentration: 0.1% by mass
・Flow rate: 1.0ml/min
・Calibration curve: Use the calibration curve of 7 samples of TOSOH TSK standard polystyrene Mw=2800000 to 1050 (Mw/Mn=1.03 to 1.06)

The content of the specific polymer in the first retardation layer is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total mass of the first retardation layer. .

<Photoalignment compound>
As described later, the laminate of the present invention includes an optically anisotropic layer B, which is different from the first retardation layer, on the opposite side of the first base material in the first retardation layer (optically anisotropic layer A). However, in this case, it is preferable that the optically anisotropic layer A, which is the first retardation layer, contains a photoalignment compound.

Here, the photo-alignment compound is not particularly limited as long as it is a compound having the above-mentioned photo-alignable group. , JP 2007-94071, JP 2007-121721, JP 2007-140465, JP 2007-156439, JP 2007-133184, JP 2009-109831, Patent No. 3883848, the azo compound described in Japanese Patent No. 4151746, the aromatic ester compound described in Japanese Patent Application Publication No. 2002-229039, the photoalignment property described in Japanese Patent Application Publication No. 2002-265541, and Japanese Patent Application Publication No. 2002-317013. maleimide and/or alkenyl-substituted nadimide compounds having units, photocrosslinkable silane derivatives described in Japanese Patent No. 4205195 and Japanese Patent No. 4205198, Japanese Patent Application Publication No. 2003-520878, Japanese Patent Application Publication No. 2004-529220, or Patent No. Preferable examples include the photocrosslinkable polyimide, polyamide or ester described in Japanese Patent No. 4,162,850. More preferred are azo compounds, photocrosslinkable polyimides, polyamides, or esters.

Among these, it is preferable to use a photosensitive compound having a photoalignable group that undergoes at least one of dimerization and isomerization due to the action of light as the photoalignment compound.
Examples of the photo-alignable group include a group having a cinnamic acid (cinnamoyl) structure (skeleton), a group having a coumarin structure (skeleton), a group having a chalcone structure (skeleton), and a group having a benzophenone structure (skeleton). , and a group having an anthracene structure (skeleton). Among these, a group having a cinnamoyl structure and a group having a coumarin structure are preferred, and a group having a cinnamoyl structure is more preferred.

When the first retardation layer is a rod-like liquid crystal compound, the in-plane retardation of the first retardation layer at a wavelength of 550 nm is not particularly limited, but is preferably 40 to 280 nm, more preferably 60 to 150 nm.
Further, the retardation in the thickness direction of the first retardation layer at a wavelength of 550 nm is not particularly limited, but is preferably 20 to 140 nm, more preferably 30 to 75 nm.
When the first retardation layer is a discotic liquid crystal compound, the in-plane retardation of the first retardation layer at a wavelength of 550 nm is not particularly limited, but is preferably 0 to 10 nm.
Furthermore, the retardation in the thickness direction of the first retardation layer at a wavelength of 550 nm is not particularly limited, but is preferably 10 to 120 nm, more preferably 15 to 60 nm.

The average thickness of the first retardation layer is not particularly limited, and is preferably 10 μm or less, more preferably 0.1 to 5.0 μm, and even more preferably 0.3 to 2.0 μm.
The average thickness is determined by measuring the thicknesses at five or more arbitrary points of the first retardation layer and arithmetic averaging them.

[Optically anisotropic layer B]
As shown in FIG. 2, the laminate of the present invention may have an optically anisotropic layer in addition to the first retardation layer. Specifically, when the first retardation layer containing the photoalignment compound described above is used as the optically anisotropic layer A, the first base material in the optically anisotropic layer A (first retardation layer) is opposite to the first base material. It may have an optically anisotropic layer B on the side.
In an embodiment having such an optically anisotropic layer B, since an alignment film is not required when forming the optically anisotropic layer B, the optically anisotropic layer is formed from the surface of the optically anisotropic layer A on the first base material side. The optical The area from the surface of the anisotropic layer A on the first substrate side to a depth position corresponding to 10% of the total thickness of the optically anisotropic layer A is defined as the substrate side surface layer area, and the area in the optically anisotropic layer A When the area from the surface of the optically anisotropic layer B side to a depth position corresponding to 10% of the total thickness of the optically anisotropic layer A is defined as the optically anisotropic layer B side surface layer area, the substrate side surface layer area It is preferable that the average value I _A2 of the secondary ion intensity derived from the photo-alignment compound in the optically anisotropic layer B side surface layer region is larger than the average value I _B2 of the secondary ion intensity derived from the photo-alignment compound in .
In the following description, the average value I _B2 of the secondary ion intensity derived from the photoalignment compound in the substrate side surface layer region of the optically anisotropic layer A is higher than the average value I B2 of the secondary ion intensity of the optically anisotropic layer A. The fact that the average value I _A2 of the secondary ion intensity derived from the photo-alignment compound in the side surface layer region is large is also simply referred to as "the photo-alignment compound is unevenly distributed on the side surface of the optically anisotropic layer B".

The optically anisotropic layer B is preferably a layer in which an oriented liquid crystal compound is fixed. When the liquid crystal compound has a polymerizable group, the alignment state of the liquid crystal compound can be easily fixed by the curing treatment described below.
The liquid crystal compound is as explained in the above-mentioned first retardation layer.
The state in which the liquid crystal compound is oriented (orientation state) is not particularly limited, and examples thereof include known orientation states. Examples of the orientation state include homogeneous orientation, homeotropic orientation, hybrid orientation, cholesteric orientation, twisted orientation, and tilted orientation. Note that the above-mentioned twisted orientation represents an alignment state in which the liquid crystal compound is twisted from one main surface to the other main surface of the optically anisotropic layer B with the thickness direction of the optically anisotropic layer B as the rotation axis. In the twisted orientation, the twist angle of the liquid crystal compound (the twist angle of the alignment direction of the liquid crystal compound) is usually more than 0° and less than 360° in many cases.

[Second base material/second retardation layer]
As shown in FIG. 3, the laminate of the present invention may include the first base material, the first retardation layer, the second retardation layer, and the second base material in this order.
In an embodiment having a second base material and a second retardation layer, the peeling force P1 between the first base material and the first retardation layer and the peeling force between the second base material and the second retardation layer are It is preferable that the force P2 satisfies the relationship expressed by the following formula (A).
Formula (A) P1<P2
Here, the peeling force P2 can also be calculated by the same procedure as the peeling force P1 described above. More specifically, an evaluation sample consisting of the second base material and the second retardation layer in the laminate is separately prepared, and the peeling force P2 can be calculated by the method described above.
In addition, although the above described a method of separately producing an evaluation sample, a peeling tape is pasted on the second base material in the laminate by the above procedure after peeling off the first base material from the laminate. Then, the peeling force P2 may be calculated by performing the above 180° test.

<Second base material>
The second base material is preferably a temporary support for transfer (releasable support) like the first base material described above.

<Second retardation layer>
The second retardation layer is preferably a layer in which an aligned liquid crystal compound is fixed. When the liquid crystal compound has a polymerizable group, the alignment state of the liquid crystal compound can be easily fixed by the curing treatment described below.
The liquid crystal compound is as explained in the above-mentioned first retardation layer.
The state in which the liquid crystal compound is oriented (orientation state) is not particularly limited, and examples thereof include the orientation state exemplified in the above-mentioned optically anisotropic layer B.

The second retardation layer is preferably a layer formed by fixing vertically aligned rod-shaped liquid crystal compounds. Among these, it is more preferable that the second retardation layer is a layer formed by fixing a vertically aligned rod-shaped liquid crystal compound having a polymerizable group by polymerization.
Note that the state in which the rod-shaped liquid crystal compound is vertically aligned means that the long axis of the rod-shaped liquid crystal compound is parallel to the thickness direction of the second retardation layer. Note that the angle between the long axis of the rod-like liquid crystal compound and the thickness direction of the second retardation layer is preferably in the range of 0 to 20 degrees, and the angle between the long axis of the rod-like liquid crystal compound and the thickness direction of the second retardation layer is not strictly required to be parallel. It is preferably within the range of .

The retardation in the thickness direction of the second retardation layer at a wavelength of 550 nm is not particularly limited, but is preferably -120 to -10 nm, more preferably -100 to -30 nm.

The average thickness of the second retardation layer is not particularly limited, and is preferably 10 μm or less, more preferably 0.1 to 5.0 μm, and even more preferably 0.3 to 2.0 μm.
The average thickness is determined by measuring the thicknesses of five or more arbitrary points of the second retardation layer and arithmetic averaging them.

[Optically anisotropic layer C]
The laminate of the present invention may have an optically anisotropic layer in addition to the second retardation layer. Specifically, when the second retardation layer described above is an optically anisotropic layer D, an optically anisotropic layer is formed on the side opposite to the second base material in the optically anisotropic layer D (second retardation layer). It may have layer C.
In an embodiment having such an optically anisotropic layer C, the optically anisotropic layer D contains the above-mentioned photoalignment compound because an alignment film is not required when forming the optically anisotropic layer C. It is preferable to measure the optical anisotropy by time-of-flight secondary ion mass spectrometry while irradiating an ion beam from the surface of the optically anisotropic layer D on the second base material side to the surface on the optically anisotropic layer C side. When measuring the secondary ion intensity of the photoalignment compound in the optically anisotropic layer D, it corresponds to 10% of the total thickness of the optically anisotropic layer D from the surface of the second base material side in the optically anisotropic layer D. The area up to the depth position is defined as the substrate side surface layer area, and from the surface of the optically anisotropic layer D on the optically anisotropic layer C side to a depth position corresponding to 10% of the total thickness of the optically anisotropic layer D. When the area is defined as the C-side surface layer region of the optically anisotropic layer, the average value I _B2 of the secondary ion intensity derived from the photo-alignment compound in the substrate-side surface layer region is higher than the light intensity in the optically anisotropic layer C-side surface layer region. It is more preferable that the average value I _A2 of the secondary ion intensity derived from the alignment compound is large.

[Adhesive layer/adhesive layer]
When the laminate of the present invention has the second base material and the second retardation layer described above, the laminate has an adhesive layer or a pressure-sensitive adhesive layer between the first retardation layer and the second retardation layer. Good too.
Examples of the adhesive layer include known adhesive layers. The adhesive layer is formed, for example, by applying an ultraviolet curable adhesive to form a coating film, and curing it by irradiating ultraviolet rays.
Examples of the adhesive layer include known adhesive layers.

〔Production method〕
The method for producing the above-mentioned laminate is not particularly limited as long as it can produce a laminate having the above-mentioned characteristics. Among these, a method for producing a laminate having the following steps 1 to 3 is preferred in terms of the productivity of the laminate. In addition, although the manufacturing method of the laminated body which has the 2nd base material and the 2nd retardation layer which were mentioned above is demonstrated below, the laminate which does not have the 2nd base material and the 2nd retardation layer which were mentioned above is explained. can be produced only by the following step 1.
Step 1: A first composition layer is formed by coating a first retardation layer forming composition containing a liquid crystal compound having a polymerizable group on a first base material, and the liquid crystal compound in the first composition layer is coated on a first base material. After horizontal orientation, the first composition layer is subjected to a curing treatment to obtain a laminate (hereinafter abbreviated as "first film") including a first base material and a first retardation layer. Step 2: A second retardation layer forming composition containing a liquid crystal compound having a polymerizable group and a polymer is applied onto a second base material to form a second composition layer, and the liquid crystal compound in the second composition layer is aligned. After that, the second composition layer is subjected to a curing treatment to obtain a second film including a second base material and a second retardation layer. Step 3: The first retardation layer and the second retardation layer in the first film are Step of laminating the first film and the second film so that the second retardation layer in the film faces each other to obtain a laminate.The steps of steps 1 to 3 will be described in detail below.

<Step 1>
Step 1 is to apply a first retardation layer forming composition onto a first base material to form a first composition layer, horizontally align a liquid crystal compound in the first composition layer, and then apply a first retardation layer forming composition onto a first substrate. This is a step of subjecting the composition layer to a curing treatment to obtain a first film including a first base material and a first retardation layer.

The first retardation layer forming composition contains a liquid crystal compound having a polymerizable group. The aspect of the liquid crystal compound is as described above.
The content of the liquid crystal compound having a polymerizable group in the first retardation layer forming composition is preferably 60 to 99% by mass, and 70 to 99% by mass based on the total solid content of the first retardation layer forming composition. 98% by mass is more preferred.
Note that the solid content refers to a component that can form the first retardation layer from which the solvent has been removed, and is defined as a solid content even if the component is liquid.

The first retardation layer forming composition contains a specific polymer. The aspect of the specific polymer is as explained in the above-mentioned first retardation layer.
The content of the specific polymer in the first retardation layer forming composition is preferably 0.1 to 10% by mass, and 0.2 to 5% by mass, based on the total solid content of the first retardation layer forming composition. Mass% is more preferred.

The first retardation layer forming composition may contain a polymerization initiator. The polymerization initiator used is selected depending on the type of polymerization reaction, and includes, for example, a thermal polymerization initiator and a photopolymerization initiator.
The content of the polymerization initiator in the composition for forming the first retardation layer is preferably 0.01 to 20% by mass, and preferably 0.5 to 20% by mass, based on the total solid content of the composition for forming the first retardation layer. 10% by mass is more preferable.

Other components that may be included in the composition for forming the first retardation layer include, in addition to the above, a polyfunctional monomer, a horizontal alignment agent, a surfactant, an adhesion improver, a plasticizer, and a solvent. Can be mentioned.

Methods for applying the composition for forming the first retardation layer include curtain coating method, dip coating method, spin coating method, print coating method, spray coating method, slot coating method, roll coating method, slide coating method, and blade coating method. , gravure coating method, and wire bar method.

After applying the first retardation layer forming composition, a drying treatment may be performed as necessary.

The treatment for horizontally aligning the liquid crystal compound in the formed first composition (orientation treatment) is not particularly limited, and a method of heating the first composition layer is preferred.
The conditions for heating the first composition layer are not particularly limited, but the heating temperature is preferably 50 to 250°C, more preferably 50 to 150°C, and the heating time is preferably 10 seconds to 10 minutes.
Moreover, after heating the first composition layer, the first composition layer may be cooled as necessary before the curing treatment (light irradiation treatment) described below.

The method of curing treatment performed on the first composition layer is not particularly limited, and examples include light irradiation treatment and heat treatment. Among these, from the viewpoint of manufacturing suitability, light irradiation treatment is preferred, and ultraviolet irradiation treatment is more preferred.
The irradiation conditions for the light irradiation treatment are not particularly limited, but an irradiation amount of 50 to 1000 mJ/cm ² is preferable.
The atmosphere during the light irradiation treatment is not particularly limited, but a nitrogen atmosphere is preferred.

<Step 2>
Step 2 is to apply the second retardation layer forming composition onto the second base material to form a second composition layer, align the liquid crystal compound in the second composition layer, and then apply the second composition. This is a step of subjecting the material layer to a curing treatment to obtain a second film including a second base material and a second retardation layer.

The second retardation layer forming composition contains a liquid crystal compound having a polymerizable group. The aspect of the liquid crystal compound is as described above.
The content of the liquid crystal compound having a polymerizable group in the composition for forming a second retardation layer is preferably from 60 to 99% by mass, and from 70 to 99% by mass, based on the total solid content of the composition for forming the second retardation layer. 98% by mass is more preferred.
Note that the solid content means a component that can form the second retardation layer from which the solvent has been removed, and is defined as a solid content even if the component is liquid.

The second retardation layer forming composition may contain other compounds than the liquid crystal compound having a polymerizable group.
Examples of other components include other components that may be included in the first retardation layer forming composition.

The solvent contained in the composition for forming the second retardation layer is preferably selected in consideration of compatibility with the second base material and the polymer.
For example, when the second base material is a cellulose acylate film, for example, methyl ethyl ketone has excellent compatibility with cellulose acylate, so the degree of uneven distribution can be increased by increasing the content of methyl ethyl ketone.

The steps of the method for forming the second retardation layer using the composition for forming the second retardation layer are the steps of the method for forming the first retardation layer using the composition for forming the first retardation layer in step 1. Since they are the same, their explanation will be omitted.

<Step 3>
Step 3 is a step of laminating the first film and the second film so that the first retardation layer in the first film and the second retardation layer in the second film face each other to obtain a laminate. It is.
When bonding the first film and the second film, it is preferable to bond them via the above-mentioned adhesive layer or pressure-sensitive adhesive layer.
When using an adhesive layer, for example, an adhesive is applied to the surface of the first film on the first retardation layer side, and the surface coated with the adhesive is connected to the second retardation layer of the second film. A desired laminate can be obtained by bonding the first film and the second film in contact with each other and performing a curing treatment. When the adhesive is an ultraviolet curable adhesive, the curing treatment includes ultraviolet irradiation treatment.
In addition, when using an adhesive layer as the adhesion layer, for example, the adhesive is applied to the surface of the first film on the first retardation layer side, and the adhesive is applied to the surface of the first film and the second layer of the second film is A desired laminate is obtained by laminating the first film and the second film with the retardation layer in contact with each other.

[Optical film]
The optical film of the present invention is obtained by peeling off the first base material (or the first base material and the second base material when the laminate of the present invention has a second base material) from the laminate of the present invention described above. It is an optical film and has a first retardation layer (a first retardation layer and a second retardation layer when the laminate of the present invention has a second retardation layer).
The optical film of the present invention may function as a so-called λ/4 plate.
A λ/4 plate is a plate that has the function of converting linearly polarized light of a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light), and the in-plane retardation Re (λ) at a specific wavelength λ nm is Re It refers to a plate (optically anisotropic layer) that satisfies (λ)=λ/4.
This formula only needs to be achieved at any wavelength in the visible light range (for example, 550 nm), but the in-plane retardation Re (550) at a wavelength of 550 nm satisfies the relationship 110 nm≦Re (550)≦180 nm. It is preferable.

[Polarizer]
The optical film of the present invention may be used as a polarizing plate in combination with a polarizer, and is preferably used as a circularly polarizing plate. Note that a circularly polarizing plate is an optical element that converts unpolarized light into circularly polarized light.
The polarizing plate of the present invention having the above configuration is used for antireflection of display devices such as liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescent displays (ELD), and cathode tube displays (CRT). It is suitably used for.

The polarizer may be any member that has the function of converting natural light into specific linearly polarized light, such as an absorption type polarizer.
The type of polarizer is not particularly limited, and commonly used polarizers can be used, such as iodine-based polarizers, dye-based polarizers using dichroic substances, and polyene-based polarizers. Iodine-based polarizers and dye-based polarizers are generally produced by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching the resulting material.
Note that a protective film may be disposed on one or both sides of the polarizer.

The arrangement relationship between the absorption axis of the polarizer and the optical film is not particularly limited, and the optimum arrangement is selected depending on the type of liquid crystal layer included in the optical film.
For example, when the first retardation layer in the optical film is a negative A plate, the angle between the absorption axis of the polarizer and the in-plane slow axis of the negative A plate is preferably in the range of 45 to 135°.

The polarizing plate may include other members than the optical film of the present invention and the polarizer.
The polarizing plate may have an adhesive layer or a pressure-sensitive adhesive layer between the optical film of the present invention and the polarizer.
Further, the polarizing plate may have a polymer film between the optical film of the present invention and the polarizer, but from the viewpoint of thinning, it is preferable not to have a polymer film. Examples of the polymer film include cellulose acylate film.

The method for manufacturing the polarizing plate is not particularly limited, and known methods may be used.
For example, a method of laminating a polarizer and an optical film via an adhesive layer or a pressure-sensitive adhesive layer can be mentioned.

[Image display device]
The optical film and polarizing plate of the present invention can be suitably applied to image display devices.
The image display device of the present invention includes a display element and the above-mentioned optical film or polarizing plate.
When applying the optical film of the present invention to an image display device, it is preferably applied as a circularly polarizing plate. In this case, the circularly polarizing plate is placed on the viewing side, and the polarizer in the circularly polarizing plate is placed on the viewing side.
The display element is not particularly limited, and examples include organic electroluminescence display elements and liquid crystal display elements.

The present invention will be explained in more detail below based on Examples. The materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the Examples shown below.

[Example 1]
[Preparation of first base material (cellulose acylate film)]
The following composition was put into a mixing tank, stirred, and further heated at 90° C. for 10 minutes. Thereafter, the resulting composition was filtered through a filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm to prepare a dope. The solid content concentration of the dope is 23.5% by mass, and the solvent of the dope is methylene chloride/methanol/butanol=81/18/1 (mass ratio).

――――――――――――――――――――――――――――――――
Cellulose acylate dope――――――――――――――――――――――――――――――
・Cellulose acylate (degree of acetyl substitution 2.86, viscosity average degree of polymerization 310) 100 parts by mass ・Sugar ester compound 1 (shown in the following formula (S4)) 6.0 parts by mass ・Sugar ester compound 2 (shown in the following formula (S5) ) 2.0 parts by mass ・Silica particle dispersion liquid (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 0.1 parts by mass ・Solvent (methylene chloride/methanol/butanol)
――――――――――――――――――――――――――――――――

The dope prepared above was cast using a drum film forming machine. The dope was cast from a die onto a metal support cooled to 0° C. and then the resulting web (film) was peeled off. Note that the drum was made of SUS (stainless steel).

After the web (film) obtained by casting is peeled off from the drum, it is dried for 20 minutes in a tenter device that clips both ends of the web with clips at 30 to 40°C during film transportation. did. Subsequently, the web was post-dried by zone heating while being rolled. After knurling the obtained web, it was wound up.
The thickness of the obtained cellulose acylate film was 40 μm.

[Formation of first retardation layer]
An optically anisotropic layer-forming composition (1-1) containing a discotic liquid crystal compound having the following composition was applied onto the first base material using a Giesser coating machine to form a composition layer. . The film on which the composition layer was formed was heated with hot air at 116°C for 1 minute, and a 365 nm UV-LED was heated at a UV temperature of 78°C while purging with nitrogen to create an atmosphere with an oxygen concentration of 100 volume ppm or less. Using this method, ultraviolet rays were irradiated with an irradiation amount of 150 mJ/cm ² . Thereafter, an optically anisotropic layer (1-1) corresponding to the first retardation layer was formed on the obtained coating film by annealing it with warm air at 115° C. for 25 seconds to produce a laminate. .
The thickness of the optically anisotropic layer (1-1) thus formed was 2 μm. The in-plane retardation Re at a wavelength of 550 nm was 0 nm, and the retardation Rth in the thickness direction at a wavelength of 550 nm was 60 nm. It was confirmed that the average inclination angle of the disk surface of the discotic liquid crystal compound with respect to the film surface was 0°, and that it was oriented horizontally with respect to the film surface.

――――――――――――――――――――――――――――――――
Composition for forming optically anisotropic layer (1-1)
――――――――――――――――――――――――――――――――
- 4 parts by mass of the following discotic liquid crystal compound 1 - 1 part by mass of the following discotic liquid crystal compound 2 - 95.0 parts by mass of the following discotic liquid crystal compound 3 - 12.0 parts by mass of the following polymerizable monomer 1 - Polymerization initiator S-1 (oxime type) 3.0 parts by mass ・Photoacid generator D-1 below 3.0 parts by mass ・Air side unevenly distributed polymer B-1 below 0.6 parts by mass ・Base material below Side unevenly distributed polymer P-1 (specific polymer) 0.6 parts by mass, diisopropylethylamine 0.2 parts by mass, methyl isobutyl ketone 360 parts by mass, ethyl propionate 90 parts by mass, methyl ethyl ketone 25 parts by mass --- ――――――――――――――――――――――――

Disc-shaped liquid crystal compound 1

Disc-shaped liquid crystal compound 2

Disc-shaped liquid crystal compound 2

Polymerizable monomer 1

Polymerization initiator S-1

Photoacid generator D-1

Air side unevenly distributed polymer B-1 (The numerical value in each repeating unit represents the content (mass%) of all repeating units. Also, the weight average molecular weight was 12,500.)

Base material side unevenly distributed polymer P-1 (weight average molecular weight: 7800)

[Comparative example 1]
A laminate was produced in the same manner as in Example 1, except that the base material side unevenly distributed polymer P-1 was not used.

[Comparative example 2]
A laminate was produced in the same manner as in Example 1, except that the substrate side unevenly distributed polymer P-9 shown below was used instead of the substrate side unevenly distributed polymer P-1 as the specific polymer.

Base material side unevenly distributed polymer P-9 (weight average molecular weight: 9000)

[Example 2]
A laminate was produced in the same manner as in Example 1, except that the substrate side unevenly distributed polymer P-2 shown below was used instead of the substrate side unevenly distributed polymer P-1 as the specific polymer.

Base material side unevenly distributed polymer P-2 (weight average molecular weight: 6300)

[Example 3]
A laminate was produced in the same manner as in Example 1, except that the substrate side unevenly distributed polymer P-3 shown below was used instead of the substrate side unevenly distributed polymer P-1 as the specific polymer.

Base material side unevenly distributed polymer P-3 (weight average molecular weight: 7200)

[Example 4]
A laminate was produced in the same manner as in Example 1, except that the substrate side unevenly distributed polymer P-4 shown below was used instead of the substrate side unevenly distributed polymer P-1 as the specific polymer.

Base material side unevenly distributed polymer P-4 (weight average molecular weight: 6800)

[Example 5]
A laminate was produced in the same manner as in Example 1, except that the substrate side unevenly distributed polymer P-5 shown below was used instead of the substrate side unevenly distributed polymer P-1 as the specific polymer.

Base material side unevenly distributed polymer P-5 (weight average molecular weight: 8400)

[Example 6]
A laminate was produced in the same manner as in Example 1, except that the substrate side unevenly distributed polymer P-6 shown below was used instead of the substrate side unevenly distributed polymer P-1 as the specific polymer.

Base material side unevenly distributed polymer P-6 (weight average molecular weight: 7700)

[Example 7]
A laminate was produced in the same manner as in Example 1, except that the substrate side unevenly distributed polymer P-7 shown below was used instead of the substrate side unevenly distributed polymer P-1 as the specific polymer.

Base material side unevenly distributed polymer P-7 (weight average molecular weight: 6700)

[Example 8]
A laminate was produced in the same manner as in Example 1, except that the substrate side unevenly distributed polymer P-8 shown below was used instead of the substrate side unevenly distributed polymer P-1 as the specific polymer.

Base material side unevenly distributed polymer P-8 (weight average molecular weight: 6500)

[Example 9]
A laminate was produced in the same manner as in Example 7, except that air side unevenly distributed polymer B-2 shown below was used instead of air side unevenly distributed polymer B-1.

Air side unevenly distributed polymer B-2 (The alphabet written in each repeating unit represents the content (mass%) of each repeating unit with respect to all repeating units, and it is 53% by mass and 47% by mass from the repeating unit on the left. In addition, the weight average molecular weight was 183,000.)

[Example 10]
The first retardation layer formed in the same manner as in Example 9 was used as an optically anisotropic layer A, and the optically anisotropic layer A thus obtained was exposed to UV light (ultra high pressure) passed through a wire grid polarizer at room temperature. A composition layer having orientation control ability was formed on the surface by irradiating with a mercury lamp; UL750 (manufactured by HOYA) at 7.9 mJ/cm ² (wavelength: 313 nm).
On the optically anisotropic layer A, a composition for forming an optically anisotropic layer (1-2) containing a rod-like liquid crystal compound having the following composition was coated using a Giesser coater, and heated to 120° C. with hot air at 95°C. heated for seconds. Subsequently, the obtained composition layer is subjected to UV irradiation (100 mJ/cm ² ) at 95° C. to fix the orientation of the liquid crystal compound, thereby forming an optically anisotropic layer corresponding to optically anisotropic layer B. (1-2) was formed to produce a laminate.
The thickness of the optically anisotropic layer (1-2) was 1.5 μm, and Δnd at a wavelength of 550 nm was 153 nm. It was confirmed that the average inclination angle of the disk surface of the discotic liquid crystal compound with respect to the film surface was 90°, and that it was oriented perpendicularly to the film surface.
If the width direction of the film is 0° (the longitudinal direction is 90° counterclockwise and -90° clockwise), when viewed from the optically anisotropic layer (1-2) side, the optically anisotropic layer ( The in-plane slow axis direction of 1-2) was -14°.

――――――――――――――――――――――――――――――――
Composition for forming optically anisotropic layer (1-2)
――――――――――――――――――――――――――――――――
- 80 parts by mass of the above discotic liquid crystal compound 1 - 20 parts by mass of the above discotic liquid crystal compound 2 - 1.8 parts by mass of the following alignment film interface alignment agent 1 - 10.0 parts by mass of the above polymerizable monomer 1 - 5.0 parts by mass of polymerization initiator S-1 (oxime type) 0.1 part by mass of the following fluorine-containing compound A 0.21 part by mass of the following fluorine-containing compound B 0.06 part by mass of the following fluorine-containing compound C Parts by mass・2.1 parts by mass of antifoaming agent 1 below・299 parts by mass of methyl ethyl ketone―――――――――――――――――――――――――――― ---

Alignment film interface alignment agent 1

Fluorine-containing compound A (in the following formula, a and b represent the content (mass%) of each repeating unit with respect to all repeating units, a represents 90% by mass, and b represents 10% by mass. Also, weight average molecular weight was 15,000.)

Fluorine-containing compound D (The numerical value in each repeating unit represents the content (mass%) of all repeating units. Also, the weight average molecular weight was 12,500.)

Fluorine-containing compound E (The content of the repeating unit on the left was 36% by mass, and the content of the repeating unit on the right was 64% by mass. Also, the weight average molecular weight was 12,500.)

Antifoaming agent 1

[Example 11]
[Formation of second retardation layer]
Using the cellulose acylate film described in Example 1 as the second base material, a composition for forming an optically anisotropic layer containing a rod-like liquid crystal compound having the following composition was coated on the cellulose acylate film using a Giesser coater. (1-4) was applied to form a composition layer. The film on which the composition layer was formed was heated with hot air at 60°C for 1 minute, and the irradiation amount was 100 mJ using a 365 nm UV-LED while purging with nitrogen so that the atmosphere had an oxygen concentration of 100 volume ppm or less. / ^cm2 of ultraviolet light was irradiated. Thereafter, an optically anisotropic layer (1-4) corresponding to the second retardation layer (optically anisotropic layer D) is formed on the obtained coating film by annealing with hot air at 120°C for 1 minute. did.
7. UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) passed through a wire grid polarizer was applied to the optically anisotropic layer (1-4) while the long film was continuously conveyed without being wound up. By irradiating with 9 mJ/cm ² (wavelength: 313 nm), a composition layer having orientation control ability was formed on the surface.
The thickness of the optically anisotropic layer (1-4) thus formed was 0.7 μm. The in-plane retardation Re at a wavelength of 550 nm was 0 nm, and the retardation Rth in the thickness direction at a wavelength of 550 nm was -85 nm. It was confirmed that the average inclination angle of the long axis direction of the rod-like liquid crystal compound with respect to the film plane was 90°, and that it was oriented perpendicularly to the film plane.

――――――――――――――――――――――――――――――――
Composition for forming optically anisotropic layer (1-4)
――――――――――――――――――――――――――――――――
- 100 parts by mass of the following rod-shaped liquid crystal compound (A) - 4.2 parts by mass of polymerizable monomer (A-400, manufactured by Shin Nakamura Chemical Co., Ltd.) - 5.1 parts by mass of the above polymerization initiator S-1 (oxime type)・3.0 parts by mass of the above photoacid generator D-1 ・5.1 parts by mass of the following polymer M-1 ・1.9 parts by mass of the following alignment film interface alignment agent 2 ・The following photoalignable polymer A-2 0.8 parts by mass・Diisopropylethylamine 0.2 parts by mass・Methyl ethyl ketone 93.8 parts by mass・Methyl isobutyl ketone 372.0 parts by mass―――――――――――――――― ――――――――――――――――

Rod-shaped liquid crystal compound (A) (mixture of the following liquid crystal compounds (RA) (RB) (RC) at a ratio of 84:14:2 (mass ratio))

Polymer M-1

Alignment film interface alignment agent 2

Photoalignable polymer A-2 (in the following formula: a to c are a:b:c=17:64:19, and indicate the content of each repeating unit with respect to all repeating units in the polymer.

While continuously conveying the above-mentioned long film without winding it up, use a Giesser coating machine to form an optically anisotropic layer containing a rod-like liquid crystal compound having the following composition on the optically anisotropic layer (1-4). Composition (1-3) was applied and heated with hot air at 80°C for 60 seconds. Subsequently, the obtained composition layer is subjected to UV irradiation (500 mJ/cm ² ) at 80° C. to fix the orientation of the liquid crystal compound, thereby forming an optically anisotropic layer corresponding to optically anisotropic layer C. (1-3) was formed.
The thickness of the optically anisotropic layer (1-3) was 1.25 μm, Δnd at a wavelength of 550 nm was 170 nm, and the twist angle of the liquid crystal compound was 85°. Assuming that the width direction of the film is 0° (longitudinal direction is 90°), the in-plane slow axis direction (orientation axis angle of the liquid crystal compound) when viewed from the optically anisotropic layer (1-3) side is The angle was 10° on the side and 95° on the side in contact with the optically anisotropic layer (1-4).
Note that the in-plane slow axis direction of the optically anisotropic layer is determined by observing the substrate from the surface side of the optically anisotropic layer with the width direction of the substrate as a reference of 0°, and when rotating clockwise (clockwise). Negative and counterclockwise (left rotation) times are shown as positive.

――――――――――――――――――――――――――――――――
Composition for forming optically anisotropic layer (1-3)
――――――――――――――――――――――――――――――――
- 100 parts by mass of the above rod-shaped liquid crystal compound (A) - 4 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V#360, manufactured by Osaka Organic Chemical Co., Ltd.) - Photopolymerization initiator (Irgacure 819, manufactured by BASF) 3 Parts by mass・0.60 parts by mass of the following left-handed chiral agent (L1)・0.08 parts by mass of the above fluorine-containing compound D・156 parts by mass of methyl ethyl ketone―――――――――――――――― ――――――――――――――――――

Left-handed chiral agent (L1)

By the above procedure, a roll-shaped laminated film (1B) in which an optically anisotropic layer (1-4) and an optically anisotropic layer (1-3) are directly laminated on a long cellulose acylate film is obtained. was created.

Fluorine-containing compound C (the numerical value in each repeating unit represents the content (mass%) with respect to all repeating units. Also, the weight average molecular weight was 12,800.)

[Preparation of optical laminate (1)]
The surface of the optically anisotropic layer B (optically anisotropic layer (1-2)) side of the laminate produced in Example 10 and the optically anisotropic layer C (optically anisotropic layer (1-3)) After corona treatment was applied to each side surface, the films were bonded together using a continuous machine using an ultraviolet curable adhesive composition (1) having the composition shown below so that the longitudinal direction of the films was parallel to each other.
The refractive index of the ultraviolet curable adhesive layer is 1.59, and the average refractive index in the axial direction of the adjacent optically anisotropic layer (1-2) and optically anisotropic layer (1-3) is 1.59, respectively. 59, 1.63, and the refractive index difference with the adhesive layer was 0.05 or less.
――――――――――――――――――――――――――――――
Ultraviolet curable adhesive composition (1)
――――――――――――――――――――――――――――――
Aronix UVX-6282 (Toagosei Chemical) 20 parts by mass Lumiplus LPK-2000 (Mitsubishi Gas Chemical) 80 parts by mass―――――――――――――――――――― ――――――

[Uneven distribution]
Regarding the laminates produced in Examples 1 to 11, the secondary ion strength of the specific polymer (the unevenly distributed polymer on the base material side) was measured using the method described above. It was confirmed that it was unevenly distributed on the base material side surface.
In addition, when the secondary ion intensity of the photoalignment compound (air side unevenly distributed polymer B-2) was measured using the method described above for the laminate produced in Example 10, it was found that the air side unevenly distributed polymer B-2 had optical anisotropy. It was confirmed that it was unevenly distributed on the layer B side surface.

[measurement]
[Measurement of peeling force P1 and P2]
For the laminates produced in Examples 1 to 11 and Comparative Examples 1 to 2, the surface side of the first retardation layer formed on the first base material was treated with a corona treatment device at an output of 0.3 kW and a treatment speed. It was processed once under the condition of 7.6 m/min.
Next, the following ultraviolet curable adhesive composition 1 was applied to the surface side of the first retardation layer and bonded to a polarizer. The resulting laminate was irradiated with ultraviolet rays at a dose of 600 mJ/cm ² (wavelength 365 nm) using a high-pressure mercury lamp to cure the adhesive layer.
Next, an adhesive layer was bonded to the opposite side of the polarizer to the surface bonded to the first retardation layer. A test piece with a width of 25 mm and a length of 150 mm was cut from the laminate on which the adhesive layer was formed, and the side of the adhesive layer of the test piece was bonded to a glass plate. A peeling tape (width 25 mm x length approximately 180 mm) was attached to one side of the test piece with a width of 25 mm on the surface of the test piece on the first base material side. Using a tensile testing machine, hold one end of the release tape and perform a peel test at a crosshead speed of 5 m/min at a temperature of 25°C and a relative humidity of 60%, with a peel angle of 180°, and the peel force P1 Measurements were made. The peeling force P1 was defined as the peeling force when the force reached a steady state after the first base material was lifted and until the first base material was peeled off from the first retardation layer.
In addition, regarding the laminate produced in Example 11, the above-mentioned except that the laminate having the second base material, the optically anisotropic layer (1-4), and the optically anisotropic layer (1-3) was used. According to the same procedure as above, a 180° peel test of the second base material was conducted, and the peel force P2 was measured.
These results are shown in Table 1 below. Note that in Comparative Example 1, the base material could not be peeled off.
――――――――――――――――――――――――――――――――
Ultraviolet curable adhesive composition 1
――――――――――――――――――――――――――――――――
・Celoxide 2021P (manufactured by Daicel Corporation) 67.0 parts by mass ・2-ethylhexyl glycidyl ether 9.6 parts by mass ・Recaresin DME-100 (manufactured by Shin Nippon Chemical Co., Ltd.) 19.1 parts by mass ・CPI-100P ( (Manufactured by Sun-Apro Co., Ltd.) 4.3 parts by mass -----------------------------------------------------

[evaluation]
[Releasability]
A laminate was prepared from the first retardation layer obtained in Example and the second retardation layer obtained in Example 11 by the method described in Example 11, and from the laminate on which the adhesive layer was formed, the width A test piece of 25 mm x length 150 mm was cut, and the adhesive layer side of the test piece was bonded to a glass plate.
A peeling tape (width 25 mm x length approximately 180 mm) was attached to one side of the test piece with a width of 25 mm on the surface of the test piece on the first base material side. Using a tensile tester, hold one end of the release tape and perform a peel test five times at a crosshead speed of 5 m/min at a temperature of 25°C and a relative humidity of 60% at a peel angle of 180°. Gender was evaluated. The results are shown in Table 1 below.
Note that when the first base material is peeled off, there may be peeling between the first base material and the layer adjacent to the first base material, or between the second base material and the layer adjacent to the second base material. occurs, and the greater the number of times the first base material can be peeled off from the adjacent layer, the better the peelability is.
In addition, since this evaluation of peelability is correlated with the peeling force P1 mentioned above, the peelability of the base material in the laminate itself produced in Examples 1 to 11 is determined when the peeling force P1 is 0.12 N/25 mm or less. Therefore, it can be evaluated as having excellent releasability.
A: The first base material peeled off all five times.
B: The first base material peeled off 4 out of 5 times.
C: The first base material peeled off 3 out of 5 times.
D: The first base material peeled off 2 out of 5 times.
E: The first base material peeled off once out of five times.
F: The first base material never peeled off.

[Liquid crystal orientation]
A square film with a side length of 40 mm was cut out from the laminates produced in Examples 1 to 11 and Comparative Examples 1 to 2. The obtained sample was observed with a polarizing microscope under crossed nicols (using a 10x objective lens), and the liquid crystal orientation was evaluated based on the following criteria. The results are shown in Table 1 below.
A: There was no light leakage within the observation field.
B: There was light leakage within the observation field.

From the results shown in Table 1, it was found that when the specific polymer was not used, the releasability of the base material was poor (Comparative Example 1).
Furthermore, it was found that when a polymer having a photoalignable group was used as the unevenly distributed polymer on the substrate side, the liquid crystal alignment was poor (Comparative Example 2).

On the other hand, it was found that when a specific polymer was used as the unevenly distributed polymer on the substrate side, both the peelability of the substrate and the liquid crystal orientation were good (Examples 1 to 11).
In particular, from a comparison between Example 1 and Example 2, it was found that when the specific polymer had a repeating unit represented by the above formula (1), the releasability of the base material was further improved.
Further, from a comparison between Example 1 and Example 3, it was found that when the specific polymer had a repeating unit represented by the above formula (2), the releasability of the base material was further improved.
Further, from a comparison between Example 3 and Example 4, it is found that X in the above formula (2) is -COOH, -PO ₃ H, {-OP(=O)(OH) ₂ }, -CO ₂ M ¹ , -SO ₃ M ¹ , -NT ¹ T ² , an oxazoline group, -NG ¹ G ² G ³ E ¹ , or a group having a betaine structure was found to further improve the releasability of the base material. .
Further, from a comparison between Example 3 and Example 5, it was found that when X in the above formula (2) is -NG ¹ G ² G ³ E ¹ , the releasability of the base material is further improved.
Further, from a comparison between Example 3 and Example 6, it was found that when X in the above formula (2) is a group having a predetermined betaine structure, the releasability of the base material is further improved.
Further, from a comparison between Example 2 and Example 7, it was found that when the specific polymer had a repeating unit containing an alicyclic structure in its side chain, the releasability of the base material was particularly improved.

10A, 10B, 10C Laminated body 12 First base material 14 First retardation layer (optically anisotropic layer A)
15 Optically anisotropic layer B
16 Second retardation layer 18 Second base material 20 Laminated object

Claims (18)

A laminate including a first base material and a first retardation layer provided adjacent to the first base material,
The first base material is a temporary support for transfer,
The first retardation layer is a layer formed by fixing a horizontally aligned liquid crystal compound containing a polymer having no photoalignable group,
While irradiating an ion beam from the surface of the first retardation layer on the first base material side toward the surface on the opposite side to the first base material, the first rank was determined by time-of-flight secondary ion mass spectrometry. When measuring the secondary ion strength of the polymer in the retardation layer,
A region of the first retardation layer from the surface on the first base material side to a depth position corresponding to 10% of the total thickness of the first retardation layer is defined as a base material side surface layer region,
When the area from the surface of the first retardation layer opposite to the first base material to a depth position corresponding to 10% of the total thickness of the first retardation layer is defined as an air-side surface layer area,
A laminate, wherein an average value I _B1 of the secondary ion strength derived from the polymer in the base material side surface layer region is larger than an average value I _A1 of the secondary ion strength derived from the polymer in the air side surface layer region. The laminate according to claim 1, wherein a peeling force P1 between the first base material and the first retardation layer is 0.12 N/25 mm or less. The laminate according to claim 1, wherein the polymer has a repeating unit represented by the following formula (1).

In the formula (1),
R ¹ represents a hydrogen atom or a methyl group.
L ¹ is a single bond, -O-, -CO-, -NR ^L -, a divalent aliphatic group that may have a substituent, or a divalent aliphatic group that may have a substituent. Represents a divalent linking group selected from the group consisting of aromatic groups and combinations thereof. R ^L represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
R ² represents an alkyl group having 1 to 20 carbon atoms. However, in the case of an alkyl group having 2 to 20 carbon atoms, one or more of -CH ₂ - constituting the alkyl group may be substituted with -COO- or -CO-. The laminate according to claim 1, wherein the polymer has a repeating unit represented by the following formula (2).

In the formula (2),
R ³ represents a hydrogen atom or a methyl group.
L ³ represents a single bond or a divalent linking group.
X ¹ is -OH, -COOH, -PO ₃ H, {-OP(=O)(OH) ₂ }, -CO ₂ M ¹ , -SO ₃ M ¹ , -NT ¹ T ² , oxazoline group, - Represents NG ¹ G ² G ³ E ¹ or a group having a betaine structure.
M ¹ represents an alkali metal, an alkaline earth metal, Mg, Al, or Q ¹ Q ² Q ³ Q ⁴ N ⁺ . Q ¹ , Q ² , Q ³ and Q ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
T ¹ and T ² each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. However, T ¹ and T ² may be bonded to each other to form a ring structure containing a nitrogen atom.
G ¹ , G ² and G ³ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
E ¹ represents an anion. X ¹ in the formula (2) is -COOH, -PO ₃ H, {-OP(=O)(OH) ₂ }, -CO ₂ M ¹ , -SO ₃ M ¹ , -NT ¹ T ² , The laminate according to claim 4, which represents an oxazoline group, -NG ¹ G ² G ³ E ¹ , or a group having a betaine structure. The laminate according to claim 4, wherein X ¹ in the formula (2) represents -NG ¹ G ² G ³ E ¹ . X ¹ in the formula (2) represents a group having a betaine structure,
The laminate according to claim 4, wherein the group having the betaine structure is a group represented by any one of the following formulas (BT1), (BT2), (BT3) and (BT4).




In the above formulas (BT1) to (BT4),
G ⁴ to G ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
L ⁵ to L ⁸ each independently represent a divalent linking group.
* represents the bonding position. The laminate according to claim 1, wherein the polymer has a repeating unit containing an alicyclic structure in a side chain. The laminate according to claim 1, wherein the polymer has a repeating unit containing a fluorine atom in a side chain. The laminate according to claim 9, wherein the repeating unit containing a fluorine atom in a side chain is a repeating unit represented by the following formula (a).

In the formula (a),
R ^a1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
R ^a2 represents an alkyl group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. The first retardation layer is an optically anisotropic layer A containing a photoalignment compound,
Furthermore, an optically anisotropic layer B is provided on the opposite side of the first base material in the optically anisotropic layer A,
While irradiating an ion beam from the surface of the optically anisotropic layer A on the first base material side to the surface on the optically anisotropic layer B side, the optical anisotropy is measured using time-of-flight secondary ion mass spectrometry. When measuring the secondary ion strength of the photoalignment compound in the oriented layer A,
A region from the surface of the optically anisotropic layer A on the first base material side to a depth position corresponding to 10% of the total thickness of the optically anisotropic layer A is defined as a base material side surface layer region;
The area from the surface of the optically anisotropic layer A on the optically anisotropic layer B side to a depth position corresponding to 10% of the total thickness of the optically anisotropic layer A is referred to as the optically anisotropic layer B side surface layer. When set as an area,
The average value I _B2 of the secondary ion intensity derived from the photo-alignment compound in the surface layer region on the optically anisotropic layer B side is higher than the average value I B2 of the secondary ion intensity derived from the photo-alignment compound in the surface layer region on the substrate side. The laminate according to claim 1, wherein _A2 is large. having the first base material, the first retardation layer, the second retardation layer, and the second base material in this order,
The relationship between the peeling force P1 between the first base material and the first retardation layer and the peeling force P2 between the second base material and the second retardation layer is expressed by the following formula (A). The laminate according to claim 1, which satisfies the following.
Formula (A) P1<P2 An optical film obtained by peeling the first base material from the laminate according to any one of claims 1 to 11. An optical film obtained by peeling the first base material and the second base material from the laminate according to claim 12. A polarizing plate comprising the optical film according to claim 13. A polarizing plate comprising the optical film according to claim 14. An image display device comprising the polarizing plate according to claim 15. An image display device comprising the polarizing plate according to claim 16.