JP2022096970A - Laminate - Google Patents

Abstract

To provide a laminate which comprises a cured resin layer, a film-like linearly polarizing plate, an adhesive layer, and a film-like retardation layer arranged in the described order, and which significantly reduces cracking of the cured resin layer and a cured liquid crystal layer when end faces of a plurality of the laminates are polished together while being stacked on top of each other.SOLUTION: A laminate is provided, comprising a cured resin layer, a film-like linearly polarizing plate, an adhesive layer, and a film-like retardation layer including a cured liquid crystal layer, arranged in the described order. The cured resin layer satisfies a condition expressed as HM≥2.4×102 (N/mm2), where HM (N/mm2) represents a Martens hardness of the cured resin layer at 23°C. The adhesive layer satisfies a condition expressed as E/T≥2.5×103 (Pa/μm), where E (Pa) represents a storage modulus of the adhesive layer at 25°C and T (μm) represents a thickness thereof.SELECTED DRAWING: None

Description

The present invention relates to a laminate.

Conventionally, a laminated body including a linear polarizing plate, a hard coat layer laminated on one surface thereof, and a liquid crystal layer laminated on the other surface via an adhesive layer is known (Patent Document 1). ..

Japanese Unexamined Patent Publication No. 2020-106602

In the above-mentioned laminated body, when the end face was polished in a state where a plurality of laminated bodies were overlapped with each other, cracks may occur in the hard coat layer and / or the liquid crystal layer.

The present invention is a laminated body including a cured resin layer, a film-shaped linear polarizing plate, an adhesive layer, and a film-shaped retardation layer in this order, and the end face is provided in a state where a plurality of laminated bodies are superposed on each other. It is an object of the present invention to provide a laminate capable of minimizing cracks generated in a cured resin layer and a liquid crystal cured layer when polished.

The present invention provides the following laminated body and image display device.
[1] A cured resin layer, a film-shaped linear polarizing plate, an adhesive layer, and a film-shaped retardation layer are provided in this order.
The film-like retardation layer includes a liquid crystal curing layer, and includes a liquid crystal curing layer.
When the Martens hardness of the cured resin layer at a temperature of 23 ° C. is HM (N / mm ² ), the following formula (1):
HM ≧ 2.4 × 10 ² (N / mm ² ) (1)
The filling,
When the storage elastic modulus at a temperature of 25 ° C. is E (Pa) and the thickness is T (μm), the pressure-sensitive adhesive layer has the following formula (2):
E / T ≧ 2.5 × 10 ³ (Pa / μm) (2)
A laminate that meets the requirements.
[2] The laminate according to [1], wherein the film-shaped linear polarizing plate includes a thermoplastic resin film.
[3] The laminate according to [1] or [2], wherein the storage elastic modulus E (Pa) at a temperature of 25 ° C. is 3.0 × ¹⁰⁴ or more.
[4] The laminate according to any one of [1] to [3], wherein the thickness T (μm) is 30 m or less.
[5] The laminate according to any one of [1] to [4], wherein the film-like retardation layer includes two or more liquid crystal cured layers.
[6] The laminate according to any one of [1] to [5], wherein the laminate is single-leaved.
[7] The laminate according to any one of [1] to [6], wherein the laminate has a polished end face.
[8] A laminate for a flexible image display device including the laminate according to any one of [1] to [7], a front plate, and a touch sensor.
[9] An image display device having the laminate according to any one of [1] to [7].
[10] A flexible image display device having the laminate for the flexible image display device according to [8].

According to the present invention, it is a laminated body including a cured resin layer, a film-shaped linear polarizing plate, an adhesive layer, and a film-shaped retardation layer in this order, in a state where a plurality of laminated bodies are superposed on each other. It is possible to provide a laminate capable of minimizing cracks generated in the cured resin layer and the liquid crystal cured layer when the end face is polished.

It is a schematic sectional drawing which shows an example of the layer structure of a laminated linear polarizing plate. It is a schematic sectional drawing which shows another example of the layer structure of a laminated linear polarizing plate. It is a schematic sectional drawing which shows still another example of the layer structure of a laminated linear polarizing plate. It is a schematic perspective view schematically showing an example of the manufacturing method of the laminated body of this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited to the following embodiments. In all the drawings below, the scales are appropriately adjusted and shown in order to make each component easier to understand, and the scale of each component shown in the drawings does not necessarily match the scale of the actual component.

<Laminated body>
FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the laminated body. The laminate 1 shown in FIG. 1 includes a cured resin layer 100, a film-shaped linear polarizing plate 110, an adhesive layer 120, and a film-shaped retardation layer 130 in this order. The film-like retardation layer 130 includes a liquid crystal curing layer (not shown). The laminated body 1 may further include a layer other than the above-mentioned layer. Examples of the other layer include a protective film that can be bonded to the cured resin layer 100 side, a bonding layer that can be bonded to the film-like retardation layer 130 side, and the like.

The laminated body 1 is preferably laminated with the cured resin layer 100 and the film-shaped linear polarizing plate 110, the film-shaped linear polarizing plate 110 and the pressure-sensitive adhesive layer 120, the pressure-sensitive adhesive layer 120 and the film-shaped retardation layer 130 in direct contact with each other. There is.

The laminated body 1 may have a long shape or a single leaf shape. The laminate 1 is preferably single-leaved. The single-wafer-shaped laminate can be obtained by cutting from the long laminate. When the laminated body 1 has a single-wafer shape, the plan view shape of the laminated body 1 may be, for example, a square shape, preferably a square shape having a long side and a short side, and more preferably a rectangular shape. When the plan view shape of the laminated body 1 is rectangular, the length of the long side may be, for example, 10 mm or more and 1400 mm or less, preferably 30 mm or more and 600 mm or less. The length of the short side is, for example, 5 mm or more and 800 mm or less, preferably 30 mm or more and 500 mm or less, and more preferably 30 mm or more and 300 mm or less.
In addition, in this specification, a plan view means a view from the thickness direction of a layer.

When the laminated body 1 has a single-wafer shape, the laminated body 1 preferably has a polished end face for the purpose of removing fluff and the like generated on the end face of the laminated body at the time of cutting, and from the viewpoint of dimensional accuracy. In the laminated body 1, a part or all of the end faces may be polished in a plan view of the laminated body, and preferably all of the end faces are polished.
Further, when the plan view shape of the laminated body 1 is a square shape, the lengths of the sides of each layer constituting the laminated body 1 may be the same as each other. When the lengths of the sides are the same, the laminated body 1 has a square shape in a plan view.
When the laminated body 1 has a square shape in a plan view, each layer constituting the laminated body 1 has a cutout portion in any corner portion, for example, all the corner portions are notched. good. When the corner portion has a notch portion, the corner portion may be R-processed and notched in a curved shape, or may be notched in a straight line. When the plan view shape of the laminated body 1 is a square shape, any one of the sides constituting the laminated body 1 may be notched in a concave shape. The laminated body 1 may be provided with a through hole by being perforated in the plane in a plan view.

The laminate 1 may be, for example, a laminate having antireflection performance. Examples of the laminated body having antireflection performance include a circular polarizing plate. In the image display device, by providing a laminated body having antireflection performance on the front side of the image display device, it is possible to suppress a decrease in visibility due to reflection of external light.

The laminated body 1 can be used for an image display device. The image display device may be any such as a liquid crystal display device and an organic EL display device. The laminated body 1 may be arranged on the front side (visual recognition side) of the image display device, or may be arranged on the back side. When the laminate 1 is arranged on the front surface side of the image display device, it can be arranged so that the cured resin layer 100 side is the outermost surface.

When the image display device is a liquid crystal display device, the laminated body 1 can be arranged as a laminated body including a polarizing plate arranged on the front side of the front side or the back side of the liquid crystal cell. When the image display device is an organic EL display device, the laminated body 1 can be arranged on the front side as a circular polarizing plate arranged on the front side for the purpose of preventing reflection of external light.

［式中、ＨＭは硬化樹脂層のマルテンス硬さ（Ｎ／ｍｍ^２）、Ｆは荷重（Ｎ）、Ａｓ（ｈ）は深さ（ｈ）における圧子の表面積（ｍｍ^２）を表す］
に従って算出することができる。上記式より、硬化樹脂層のマルテンス硬さが大きくなると、一定荷重の押し込みに対する硬化樹脂層の変形量は小さくなる関係にあることが分かる。このことから、積層体の端面を研磨するときに一定の応力が加わり、フィルム状直線偏光板にひずみが生じたとしても、硬化樹脂層のマルテンス硬さが大きい場合には、硬化樹脂層の変形量は小さくなるため、硬化樹脂層のクラックが軽微になることが推定される。マルテンス硬さは後述の実施例の欄において説明する方法に従って測定することができる。
本明細書において、クラックとは、積層体を平面視において光学顕微鏡の透過光により観察したときに、積層体の機能が正常に発揮される領域における硬化樹脂層及び液晶硬化層の端部領域に観察される亀裂をいう。クラックは、後述の実施例の欄において説明する方法に従って観察することができる。 [Equation (1)]
In the laminated body ¹ , the following formula (1):
HM ≧ 2.4 × 10 ² (N / mm ² ) (1)
Meet. When the cured resin layer 100 of the laminated body 1 has the Martens hardness in the above range, the cracks generated in the cured resin layer 100 during polishing of the laminated body 1 tend to be slight. Martens hardness is calculated by the following formula:

[In the formula, HM represents the Martens hardness (N / mm ² ) of the cured resin layer, F represents the load (N), and As (h) represents the surface area (mm ² ) of the indenter at the depth (h)].
It can be calculated according to. From the above formula, it can be seen that as the Martens hardness of the cured resin layer increases, the amount of deformation of the cured resin layer with respect to the pressing of a constant load decreases. From this, even if a certain stress is applied when polishing the end face of the laminated body and the film-like linear polarizing plate is distorted, if the maltens hardness of the cured resin layer is large, the cured resin layer is deformed. Since the amount is small, it is presumed that the cracks in the cured resin layer will be minor. Martens hardness can be measured according to the method described in the Examples section below.
In the present specification, the crack means the edge region of the cured resin layer and the liquid crystal cured layer in the region where the function of the laminated body is normally exhibited when the laminated body is observed by the transmitted light of an optical microscope in a plan view. An observed crack. Cracks can be observed according to the method described in the Examples section below.

In the above formula (1), the right side is preferably 2.45 × 10 ² (N / mm ² ), more preferably 2.5 × 10 ² (N / mm 2) from the viewpoint of facilitating the slight cracks generated in the cured resin layer 100. N / mm ² ). The Martens hardness of the cured resin layer 100 is usually 5.0 × 10 ² (N / mm ² ) or less, preferably 4.0 × 10 ² (N / mm ² ) or less, for example 3.0 ×. It may be 10 ² (N / mm ² ) or less.

As a means for satisfying the above formula (1), for example, a method for adjusting the composition of a composition for forming a cured resin layer used for forming a cured resin layer described later, a method for adjusting the thickness of the cured resin layer, and a commercially available method. Examples thereof include a method of selecting and using a product satisfying the above formula (1) from among the products. Examples of the method for adjusting the composition of the composition for forming the cured resin layer include a method for adjusting the type and / or content of the polymerizable monomer and the additive constituting the curable resin.

[Equation (2)]
When the storage elastic modulus of the pressure-sensitive adhesive layer 120 at 25 ° C. is E (Pa) and the thickness of the pressure-sensitive adhesive layer 120 is T (μm), the laminate 1 has the following formula (2):
E / T ≧ 2.5 × 10 ³ (Pa / μm) (2)
Meet. When the pressure-sensitive adhesive layer 120 of the laminated body 1 satisfies the formula (2), cracks generated in the liquid crystal cured layer included in the film-like retardation layer 130 during polishing of the laminated body 1 tend to be slight. The storage elastic modulus and thickness of the pressure-sensitive adhesive layer 120 at 25 ° C. can be measured according to the method described in the column of Examples described later.

According to the present inventor, the higher the elasticity of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer for joining the film-shaped linear polarizing plate and the film-shaped retardation layer, the more the liquid crystal curing contained in the film-shaped retardation layer during polishing of the laminated body. It has been found that the cracks that occur in the layer can be minimized. This is because the higher the elasticity of the adhesive constituting the pressure-sensitive adhesive layer, the higher the elasticity of the laminated body tends to be. Therefore, the strain of the laminated body with respect to the stress during polishing becomes smaller, and as a result, the film-like phase difference Even if the layer is distorted, it is presumed that the amount of deformation is small. It was also found that the smaller the thickness of the pressure-sensitive adhesive layer, the smaller the cracks generated in the liquid crystal cured layer contained in the film-like retardation layer during polishing of the laminated body. This is because the laminated body has higher elasticity between the laminated body and the pressure-sensitive adhesive layer. Therefore, when the thickness of the pressure-sensitive adhesive layer is reduced, the physical properties of the laminated body approach the high-elasticity physical properties of the laminated body itself. It is presumed that this is because the strain of the laminate with respect to the stress during polishing becomes small, and as a result, even if the film-like retardation layer becomes strained, the amount of deformation thereof becomes small.
Further, when the laminated body 1 satisfies the formula (2) and the formula (1), cracks generated in the liquid crystal cured layer are generated as compared with the case where the formula (1) is not satisfied and the formula (2) is satisfied. It has been found that it can be made more minor.

In the above formula (2), the right side is preferably 4.0 × 10 ³ (Pa / μm) from the viewpoint of facilitating the miniaturization of cracks generated in the liquid crystal cured layer. In the above formula (2), the E / T is usually 1.0 × 10 ⁷ (Pa / μm) or less, and may be, for example, 5.0 × 10 ⁵ (Pa / μm) or less. The preferable ranges of the storage elastic modulus E and the thickness T of the pressure-sensitive adhesive layer 120 at 25 ° C. will be described later.

[Curing resin layer]
The cured resin layer 100 can be a layer containing a cured product of the curable resin. Examples of the curable resin include thermosetting resins and active energy ray-curable resins. The cured resin layer 100 can be a layer having functions such as a hard coat layer, an antiglare layer, an antireflection layer, a light diffusion layer, an antistatic layer, an antifouling layer, and a conductive layer.

The cured product of the curable resin can be formed from a composition for forming a cured resin layer containing the curable resin. The composition for forming a curable resin layer may be, for example, a thermosetting composition, a cationic curable composition, a radical curable composition, or the like. The composition for forming a cured resin layer can contain, for example, a polymerizable monomer, a polymerization initiator, an additive, a solvent and the like. Additives include, for example, plasticizers, UV absorbers, infrared absorbers, colorants such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, antioxidants, antioxidants, etc. Examples include lubricants and surfactants.

The cured resin layer 100 may be arranged on the side opposite to the film-shaped retardation layer 130 of the film-shaped linear polarizing plate 110, and preferably the polarization on the side opposite to the film-shaped retardation layer 130 of the film-shaped linear polarizing plate 110. The outermost layer of the laminated body 1 is arranged directly on the child protective layer or the linear polarizing layer, and more preferably on the polarizing element protective layer or the linear polarizing layer on the opposite side of the film-shaped retardation layer 130 of the film-shaped linear polarizing plate 110. It is arranged so as to be. The polarizing element protective layer or the linear polarizing layer will be described later. When the cured resin layer 100 is directly arranged on the polarizing element protective layer, for example, the cured resin layer forming composition is applied and cured on the thermoplastic resin film forming the polarizing element protective layer to form the cured resin layer. By forming a cured product of the composition for use, a thermoplastic resin film provided with the cured resin layer 100 can be produced, and then bonded to the linear polarizing layer via the adhesive layer. Further, a thermoplastic resin provided with a commercially available cured resin layer can also be used.
When the cured resin layer 100 is directly arranged on the linear polarizing layer, for example, the cured resin layer forming composition is applied and cured on the linear polarizing layer to obtain a cured product of the cured resin layer forming composition. By forming it, a film-shaped linear polarizing plate 110 provided with the cured resin layer 100 can be manufactured.

The thickness of the cured resin layer 100 may be, for example, 0.1 μm or more and 10 μm or less, preferably 1 μm or more and 5 μm or less.

When the cured resin layer 100 is a hard coat layer, it is possible to easily improve the hardness and scratch property of the linear polarizing layer or the polarizing element protection layer. The hardcoat layer can be formed from a cured product of a composition for forming a hardcoat layer containing an active energy ray-curable resin. Examples of the active energy ray-curable resin include acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, epoxy resins and the like. The hardcourt layer may contain additives to improve its strength. Additives are not limited, and include inorganic fine particles, organic fine particles, or mixtures thereof.

[Film-shaped linear polarizing plate]
The film-shaped linear polarizing plate 110 has a linear polarizing layer and a polarizing element protective layer provided on at least one side of the linear polarizing layer. The linearly polarized light layer is a polarizing element having a property of absorbing linearly polarized light having a vibration plane parallel to its absorption axis and transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis (parallel to the transmission axis). Can be done. The polarizing element protective layer is a layer for protecting the surface of the linear polarizing layer, particularly the linear polarizing layer, and can be arranged on one side or both sides of the linear polarizing layer via only the adhesive layer or directly. .. The film-shaped linear polarizing plate 110 may further have a base material and an alignment film described later. The film-shaped linear polarizing plate 110 can be flexible. The film-shaped linear polarizing plate 110 may further include a protective film described later.

The thickness of the film-shaped linear polarizing plate 110 may be, for example, 5 μm or more and 100 μm or less, preferably 10 μm or more and 80 μm or less.

[Linear polarizing layer]
Examples of the linear polarizing layer include a stretched film or a stretched layer on which a dichroic dye is adsorbed, or a film on which a dichroic dye is applied and cured. Specifically, iodine or a dichroic organic dye is used as the dichroic dye. For dichroic organic dyes, C.I. I. Included are dichroic direct dyes made of disazo compounds such as DIRECT RED 39 and dichroic direct dyes made of compounds such as trisazo and tetrakisazo.

[Stretched film on which a dichroic dye is adsorbed or a linearly polarized layer which is a stretched layer]
A linear polarizing layer, which is a stretched film having a dichroic dye adsorbed (hereinafter, may be abbreviated as “stretched film”), will be described. The stretched film on which the bicolor dye is adsorbed is usually a step of uniaxially stretching the polyvinyl alcohol-based resin film, and a step of dyeing the polyvinyl alcohol-based resin film with the bicolor dye to adsorb the bicolor dye. , And the polyvinyl alcohol-based resin film on which the bicolor dye is adsorbed can be produced through a step of treating with a boric acid aqueous solution and a step of washing with water after the treatment with the boric acid aqueous solution. The thickness of the linear polarizing layer, which is a stretched film on which the dichroic dye is adsorbed, may be, for example, 2 μm or more and 40 μm or less.

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

The saponification degree of the polyvinyl alcohol-based resin is usually 85 mol% or more and 100 mol% or less, preferably 98 mol% or more. The polyvinyl alcohol-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes can also be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 or more and 10000 or less, preferably 1500 or more and 5000 or less.

A film formed from such a polyvinyl alcohol-based resin is used as a raw film for a stretched film. The method for forming the film of the polyvinyl alcohol-based resin is not particularly limited, and the film can be formed by a known method. The film thickness of the polyvinyl alcohol-based raw film may be, for example, 10 μm or more and 150 μm or less.

The uniaxial stretching of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing with a dichroic dye. If the uniaxial stretching is performed after staining, the uniaxial stretching may be performed before the boric acid treatment or during the boric acid treatment. It is also possible to perform uniaxial stretching at these multiple stages. In uniaxial stretching, rolls having different peripheral speeds may be uniaxially stretched, or thermal rolls may be used to uniaxially stretch the rolls. Further, the uniaxial stretching may be a dry stretching in which stretching is performed in the atmosphere, or a wet stretching in which the polyvinyl alcohol-based resin film is swollen using a solvent. The draw ratio is usually about 3 times or more and 8 times or less.

Dyeing of the polyvinyl alcohol-based resin film with a dichroic dye is performed, for example, by immersing the polyvinyl alcohol-based resin film in an aqueous solution containing the dichroic dye. Specifically, iodine or a dichroic organic dye is used as the dichroic dye. For dichroic organic dyes, C.I. I. Included are dichroic direct dyes made of disazo compounds such as DIRECT RED 39 and dichroic direct dyes made of compounds such as trisazo and tetrakisazo. The polyvinyl alcohol-based resin film is preferably immersed in water before the dyeing treatment.

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

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

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

The polyvinyl alcohol-based resin film after the boric acid treatment is usually washed with water. The water washing treatment can be performed, for example, by immersing the boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of water in the washing treatment is usually 5 ° C. or higher and 40 ° C. or lower. The immersion time is usually 1 second or more and 120 seconds or less.

After washing with water, a drying treatment is performed to obtain a stretched film on which a dichroic dye is adsorbed. The drying process can be performed using, for example, a hot air dryer or a far-infrared heater. The temperature of the drying treatment is usually 30 ° C. or higher and 100 ° C. or lower, preferably 50 ° C. or higher and 80 ° C. or lower. The drying treatment time is usually 60 seconds or more and 600 seconds or less, preferably 120 seconds or more and 600 seconds or less. By the drying treatment, the moisture content of the stretched film on which the dichroic dye is adsorbed is reduced to a practical level. The water content is usually 5% by mass or more and 20% by mass or less, preferably 8% by mass or more and 15% by mass or less. When the moisture content is less than 5% by mass, the flexibility of the stretched film on which the dichroic dye is adsorbed is lost, and the stretched film on which the dichroic dye is adsorbed is damaged or broken after drying. Sometimes. Further, if the water content exceeds 20% by mass, the thermal stability of the stretched film on which the dichroic dye is adsorbed may deteriorate.

Next, a linearly polarizing layer, which is a stretched layer on which a dichroic dye is adsorbed (hereinafter, may be abbreviated as “stretched layer”) will be described. The stretched layer on which the bicolor dye is adsorbed is usually a step of applying a coating liquid containing the above polyvinyl alcohol resin on a substrate to obtain a laminated film, a step of uniaxially stretching the obtained laminated film, and uniaxial stretching. The step of dyeing the polyvinyl alcohol-based resin layer of the laminated film with a bicolor dye and adsorbing it, the step of treating the film on which the bicolor dye is adsorbed with a boric acid aqueous solution, and washing with water after the treatment with a boric acid aqueous solution. It can be manufactured through a process.
As an example of the base material, those exemplified in the description of the polarizing element protective layer described later are applied. The base material may be peeled off from the stretched layer, or the base material may be used as a polarizing element protective layer. The thickness of the base material may be, for example, 5 μm or more and 200 μm or less. When the base material is incorporated into the laminate 1, the thickness of the base material film is preferably 30 μm or less.

[Linear polarizing layer, which is a film coated with a dichroic dye and cured]
As the film obtained by applying and curing the dichroic dye, for example, a composition containing a dichroic dye having a liquid crystal property or a composition containing a dichroic dye and a liquid crystal compound is applied to a substrate and cured. Examples include films containing objects.

As an example of the base material, those exemplified as the thermoplastic resin film in the description of the polarizing element protective layer described later are applied. The base material may be peeled off and removed from the film coated with the dichroic dye and cured, or the base material may be used as a polarizing element protective layer. The thickness of the base material may be, for example, 5 μm or more and 200 μm or less. When the base material is incorporated into the laminate 1, the thickness of the base material is preferably 30 μm or less. The substrate may have a hardcourt layer, an antireflection layer or an antistatic layer on at least one surface. The hardcoat layer, antireflection layer and antistatic layer are formed only on the surface of the base material on the side where the cured product is not formed, or only on the surface of the base material on the side where the cured product is formed. You may.

It is preferable that the film coated with the dichroic dye and cured is thin, but if it is too thin, the strength is lowered and the processability tends to be inferior. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less.

Specific examples of the film coated with the dichroic dye and cured include those described in JP2013-37353A, JP2013-33249, and the like.

[Alignment film]
The alignment film can be arranged between the base material and the composition containing the dichroic dye having liquid crystallinity, or the layer of the cured product of the composition containing the dichroic dye and the liquid crystal compound. The alignment film has an orientation regulating force that aligns the liquid crystal layer formed on the liquid crystal layer in a desired direction. Examples of the alignment film include an orientation polymer layer formed of an orientation polymer, a photo-alignment polymer layer formed of a photo-alignment polymer, and a grub alignment film having an uneven pattern or a plurality of grubs (grooves) on the surface of the layer. Can be done. The thickness of the alignment film may be, for example, 10 nm or more and 500 nm or less, and preferably 10 nm or more and 200 nm or less.

The oriented polymer layer can be formed by applying a composition in which the oriented polymer is dissolved in a solvent to a substrate to remove the solvent, and if necessary, performing a rubbing treatment. In this case, in the oriented polymer layer formed of the oriented polymer, the orientation restricting force can be arbitrarily adjusted depending on the surface condition of the oriented polymer and the rubbing conditions.

The photo-oriented polymer layer can be formed by applying a composition containing a polymer or monomer having a photoreactive group and a solvent to a substrate and irradiating the substrate with polarized light. In this case, the orientation restricting force can be arbitrarily adjusted in the photo-alignment polymer layer depending on the polarization irradiation conditions for the photo-alignment polymer.

The grub alignment film is, for example, a method of forming an uneven pattern by exposure and development through an exposure mask having a pattern-shaped slit on the surface of a photosensitive polyimide film, and is active on a plate-shaped master having a groove on the surface. A method of forming an uncured layer of an energy ray-curable resin and transferring this layer to a substrate for curing. An uncured layer of an active energy ray-curable resin is formed on the substrate, and the layer has irregularities. It can be formed by a method of forming irregularities and hardening by pressing a roll-shaped master having the above.

[Polar protector protection layer]
The polarizing element protective layer can be formed from, for example, a thermoplastic resin film or a coating layer. The film-shaped linear polarizing plate 110 may have a polarizing element protective layer on only one side of the linear polarizing layer, or may have a polarizing element protective layer on both sides. When the film-shaped linear polarizing plate 110 has polarizing element protective layers on both sides of the linear polarizing layer, the polarizing element protective layers may be of the same type or different types. When the polarizing element protective layer is a thermoplastic resin film, the polarizing element protective layer can be bonded to the linear polarizing layer via an adhesive layer described later. When the splitter protective layer is a thermoplastic resin film, the thermoplastic resin film provided with the cured resin layer is arranged on the opposite side of the film-shaped linear polarizing plate 110 from the film-shaped retardation layer 130. As a layer, it can be used by being bonded to a linear polarizing layer. The film-shaped linear polarizing plate 110 preferably contains a thermoplastic resin film.

[Thermoplastic resin film]
The thermoplastic resin film that can be used as the polarizing element protective layer can be incorporated into the film-shaped linear polarizing plate 110 in the form of being bonded to one side or both sides of the linear polarizing layer. The thermoplastic resin film may be, for example, a translucent, preferably optically transparent thermoplastic resin film, and examples thereof include a chain polyolefin resin (polyethylene resin, polypropylene resin, poly). Methylpentene resin, etc.), Cyclic polyolefin resin (Norbornen resin, etc.) and other polyolefin resins; Triacetyl cellulose and other cellulose resins; Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and other polyester resins; Polycarbonate resin Resins; ethylene-vinyl acetate resin; polystyrene resin; polyamide resin; polyetherimide resin; (meth) acrylic resin such as polymethyl (meth) acrylate resin; polyimide resin; polyether sulfone resin; polysulfone system Resins; polyvinyl chloride-based resins; polyvinylidene chloride-based resins; polyvinyl alcohol-based resins; polyvinyl acetal-based resins; polyether ketone-based resins; polyether ether ketone-based resins; polyether sulfone-based resins; polyamideimide-based resins, etc. Be done. The thermoplastic resin can be used alone or in combination of two or more. Among them, a triacetyl cellulose-based resin film, a cyclic polyolefin-based resin film, and a (meth) acrylic-based resin film are preferable from the viewpoint of strength and translucency.

The thickness of the thermoplastic resin film may be, for example, 30 μm or less, preferably 25 μm or less from the viewpoint of thinning, and usually 1 μm or more, preferably 5 μm or more, and further preferably 15 μm or more. .. The thermoplastic resin film may or may not have a phase difference.

As the adhesive used for bonding the linear polarizing layer and the thermoplastic resin film, an active energy ray-curable adhesive such as an ultraviolet curable adhesive, an aqueous solution of a polyvinyl alcohol-based resin, or a cross-linking agent is blended therein. Examples thereof include water-based adhesives such as aqueous solutions and urethane-based emulsion adhesives. When the thermoplastic resin films are bonded to both sides of the linear polarizing layer, the adhesives forming the two adhesive layers may be of the same type or different types. For example, when a thermoplastic resin film is bonded on both sides, one side may be bonded using a water-based adhesive and the other side may be bonded using an active energy ray-curable adhesive. The ultraviolet curable adhesive may be a mixture of a radically polymerizable (meth) acrylic compound and a photoradical polymerization initiator, a mixture of a cationically polymerizable epoxy compound and a photocationic polymerization initiator, and the like. Further, a cationically polymerizable epoxy compound and a radically polymerizable (meth) acrylic compound may be used in combination, and a photocationic polymerization initiator and a photoradical polymerization initiator may be used in combination as an initiator. The thickness of the adhesive may be, for example, 0.1 μm or more and 5 μm or less.

When an active energy ray-curable adhesive is used, the adhesive is cured by irradiating it with active energy rays after bonding. The light source of the active energy ray is not particularly limited, but an active energy ray (ultraviolet ray) having a emission distribution having a wavelength of 400 nm or less is preferable, and specifically, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, and the like. Black light lamps, microwave-excited mercury lamps, metal halide lamps and the like are preferably used.

In order to improve the adhesiveness between the linear polarizing layer and the thermoplastic resin film, a corona was placed on the bonded surface of the linear polarizing layer and / or the thermoplastic resin film prior to bonding the linear polarizing layer and the thermoplastic resin film. Surface treatments such as treatment, flame treatment, plasma treatment, ultraviolet irradiation treatment, primer coating treatment, and saponification treatment may be performed.

[Coating layer]
The polarizing element protective layer formed from the coating layer may be formed by applying a cationically curable composition such as an epoxy resin or a radical curable composition such as (meth) acrylate and curing the layer, and may be polyvinyl alcohol. It may be obtained by applying an aqueous solution of a based resin or the like and drying it, and if necessary, a plasticizer, an ultraviolet absorber, an infrared absorber, a colorant such as a pigment or a dye, a fluorescent whitening agent, a dispersant, or heat. It may contain a stabilizer, a light stabilizer, an antioxidant, an antioxidant, a lubricant and the like.

When the polarizing element protective layer is a coating layer, the thickness of the polarizing element protective layer may be, for example, 0.1 μm or more and 30 μm or less, preferably 0.5 μm or more and 20 μm or less, and more preferably 1 μm or more from the viewpoint of thinning. It is 10 μm or less.

[Film-like retardation layer]
The film-shaped retardation layer 130 is laminated on the opposite side of the film-shaped linear polarizing plate 110 from the cured resin layer 100 via the pressure-sensitive adhesive layer 120. The film-shaped linear polarizing plate 110 can be flexible.

The film-like retardation layer 130 may include one layer or two or more retardation layers. The retardation layer can be a positive A layer such as a λ / 4 layer or a λ / 2 layer, and a positive C layer. The retardation layer may be formed from the liquid crystal cured layer described later, or may be formed from the resin film exemplified as the material of the above-mentioned thermoplastic resin film. The film-like retardation layer 130 may further include an alignment layer and a base material described later.

The film-like retardation layer 130 preferably includes a λ / 4 layer, more preferably a λ / 4 layer, and at least one of a λ / 2 layer and a positive C layer. When the retardation layer includes the λ / 2 layer, the λ / 2 layer and the λ / 4 layer can be laminated in order from the film-shaped linear polarizing plate 110 side. When the retardation layer contains a positive C layer, the λ / 4 layer and the positive C layer may be laminated in order from the film-shaped linear polarizing plate 110 side, and the positive C layer and λ / may be laminated in order from the film-shaped linear polarizing plate 110 side. Four layers may be laminated.

The thickness of the film-shaped retardation layer 130 may be, for example, 0.1 μm or more and 50 μm or less, preferably 1 μm or more and 30 μm or less, and more preferably 0.5 μm or more and 15 μm or less.

The film-like retardation layer 130 includes a liquid crystal curing layer. The liquid crystal cured layer is a layer of a cured product cured by polymerizing a polymerizable liquid crystal compound. The liquid crystal cured layer may be one in which the polymerizable liquid crystal compounds are polymerized with each other in a liquid crystal oriented state. The polymerizable liquid crystal compound may be oriented in-plane or vertically. When the polymerizable liquid crystal compound is oriented in the plane, the liquid crystal cured layer becomes a positive A layer showing an in-plane phase difference. When the polymerizable liquid crystal compound is vertically oriented, it becomes a positive C layer showing a phase difference in the thickness direction.
The polymerizable liquid crystal compound is a compound having a polymerizable group and can be in a liquid crystal state. The polymerizable liquid crystal compound is cured by the reaction between the polymerizable groups of the polymerizable liquid crystal compound and the polymerization of the polymerizable liquid crystal compound.

The liquid crystal curing layer included in the film-shaped retardation layer 130 may be one layer, two layers, or three or more layers. When the film-like retardation layer 130 includes two or more liquid crystal curing layers, the liquid crystal curing layers are usually laminated with each other via an adhesive layer. The film-like retardation layer 130 includes an alignment layer for orienting a polymerizable liquid crystal compound when forming a base material and / or a liquid crystal curing layer, in addition to a liquid crystal curing layer and an adhesive layer for laminating them. May include. When the film-like retardation layer 130 has a substrate, the substrate is usually removed when the film-like retardation layer 130 is attached to the linear polarizing plate.

The adhesive used for the adhesive layer includes an active energy ray-curable adhesive such as an ultraviolet curable adhesive, an aqueous solution of a polyvinyl alcohol-based resin or an aqueous solution containing a cross-linking agent, a urethane-based emulsion adhesive, and the like. Water-based adhesives can be mentioned. When the film-like retardation layer 130 includes two or more adhesive layers, the adhesives may be of the same type or different types. The thickness of the adhesive layer may be, for example, 0.1 μm or more and 5 μm or less.

The type of the polymerizable liquid crystal compound is not particularly limited, but can be classified into a rod-shaped type (rod-shaped liquid crystal compound) and a disc-shaped type (disk-shaped liquid crystal compound, discotic liquid crystal compound) according to its shape. Further, there are a small molecule type and a high molecular type, respectively. The polymer generally means a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, 2 pages, Iwanami Shoten, 1992). Any polymerizable liquid crystal compound can be used in the present invention. Further, two or more kinds of rod-shaped liquid crystal compounds, two or more kinds of disk-shaped liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a disk-shaped liquid crystal compound may be used. As the rod-shaped liquid crystal compound, for example, the compound described in claim 1 of JP-A No. 11-513019 can be preferably used. As the disk-shaped liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 or paragraphs [0013]-[0108] of JP-A-2010-244033 are preferable. Can be used.

Two or more kinds of polymerizable liquid crystal compounds may be used in combination. In that case, at least one type has two or more polymerizable groups in the molecule. That is, the layer obtained by curing the polymerizable liquid crystal compound is preferably a layer formed by fixing a liquid crystal compound having a polymerizable group by polymerization. In this case, it is no longer necessary to exhibit liquid crystallinity after forming a layer.

The polymerizable liquid crystal compound has a polymerizable group capable of carrying out a polymerization reaction. As the polymerizable group, for example, a functional group capable of an addition polymerization reaction such as a polymerizable ethylenically unsaturated group or a ring-polymerizable group is preferable. More specifically, examples of the polymerizable group include (meth) acryloyl group, vinyl group, styryl group, allyl group and the like. Among them, the (meth) acryloyl group is preferable. The (meth) acryloyl group is a concept that includes both a meta-acryloyl group and an acryloyl group.

The liquid crystal property of the polymerizable liquid crystal compound may be a thermotropic liquid crystal or a lyotropic liquid crystal, and when the thermotropic liquid crystal is classified by order, it may be a nematic liquid crystal or a smectic liquid crystal.

The liquid crystal cured layer can be formed by applying a composition containing a polymerizable liquid crystal compound (hereinafter, also referred to as a composition for forming a retardation layer) onto, for example, an alignment layer and irradiating it with active energy rays. .. The composition for forming a retardation layer may contain components other than the above-mentioned polymerizable liquid crystal compound. For example, it is preferable that the composition for forming a retardation layer contains a polymerization initiator. As the polymerization initiator used, for example, a thermal polymerization initiator or a photopolymerization initiator is selected depending on the type of the polymerization reaction. For example, examples of the photopolymerization initiator include α-carbonyl compounds, acyloin ethers, α-hydrocarbon-substituted aromatic acyloin compounds, polynuclear quinone compounds, and combinations of triarylimidazole dimers and p-aminophenyl ketones. The amount of the polymerization initiator used is preferably 0.01% by mass or more and 20% by mass or less, and 0.5% by mass or more and 5% by mass or less, based on the total solid content in the coating liquid. Is more preferable. The cured product is a state in which the formed layer alone can exist independently without being deformed or flowed.

Further, the composition for forming a retardation layer may contain a polymerizable monomer from the viewpoint of the uniformity of the coating film and the strength of the film. Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Among them, a polyfunctional radically polymerizable monomer is preferable.

The polymerizable monomer is preferably one that can be copolymerized with the above-mentioned polymerizable liquid crystal compound. The amount of the polymerizable monomer used is preferably 1% by mass or more and 50% by mass or less, and more preferably 2% by mass or more and 30% by mass or less, based on the total mass of the polymerizable liquid crystal compound.

Further, the composition for forming a retardation layer may contain a surfactant from the viewpoint of the uniformity of the coating film and the strength of the film. Examples of the surfactant include conventionally known compounds. Among them, fluorine-based compounds are particularly preferable.

Further, the composition for forming a retardation layer may contain a solvent, and an organic solvent is preferably used. Examples of the organic solvent include amide (eg, N, N-dimethylformamide), sulfoxide (eg, dimethyl sulfoxide), heterocyclic compound (eg, pyridine), hydrocarbon (eg, benzene, hexane), alkyl halide (eg, eg). , Chloroform, dichloromethane), esters (eg, methyl acetate, ethyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Among them, alkyl halides and ketones are preferable. Further, two or more kinds of organic solvents may be used in combination.

Further, the composition for forming the retardation layer includes a vertical alignment agent such as a polarizing element interface side vertical alignment agent and an air interface side vertical alignment agent, and a polarizing element interface side horizontal alignment agent, an air interface side horizontal alignment agent and the like. Various alignment agents such as the horizontal alignment accelerator may be contained. Further, the composition for forming a retardation layer may contain an adhesion improver, a plasticizer, a polymer and the like in addition to the above components.

The active energy ray includes ultraviolet rays, visible light, electron beams, and X-rays, and is preferably ultraviolet rays. Examples of the light source of the active energy ray include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excima laser, and a wavelength range. Examples thereof include LED light sources that emit light of 380 to 440 nm, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, and the like.

The irradiation intensity of ultraviolet rays is usually 100 mW / cm ² or more and 3,000 mW / cm ² or less in the case of ultraviolet B waves (wavelength range 280 nm or more and 310 nm or less). The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activating the cationic polymerization initiator or the radical polymerization initiator. The time for irradiating with ultraviolet rays is usually 0.1 seconds or more and 10 minutes or less, preferably 0.1 seconds or more and 5 minutes or less, more preferably 0.1 seconds or more and 3 minutes or less, and further preferably 0. . 1 second or more and 1 minute or less.

The ultraviolet rays can be irradiated once or in a plurality of times. Although it depends on the polymerization initiator used, the integrated light amount at a wavelength of 365 nm is preferably 700 mJ / cm ² or more, more preferably 1,100 mJ / cm ² or more, and 1,300 mJ / cm ² or more. It is more preferable to do so. The integrated light amount is advantageous for increasing the polymerization rate of the polymerizable liquid crystal compound constituting the liquid crystal cured layer and improving the heat resistance. The integrated light amount at a wavelength of 365 nm is preferably 2,000 mJ / cm ² or less, and more preferably 1,800 mJ / cm ² or less. The integrated light intensity may lead to coloring of the liquid crystal cured layer.

The thickness of the liquid crystal cured layer is preferably 0.5 μm or more. The thickness of the liquid crystal cured layer is preferably 10 μm or less, and more preferably 5 μm or less. The above-mentioned upper limit value and lower limit value can be arbitrarily combined. When the thickness of the liquid crystal cured layer is at least the above lower limit value, sufficient durability can be obtained. When the thickness of the liquid crystal cured layer is not more than the upper limit value, it can contribute to the thinning of the laminated body 1. As the thickness of the liquid crystal cured layer, a desired in-plane retardation value of a layer giving a phase difference of λ / 4, a layer giving a phase difference of λ / 2, or a positive C layer, and a phase difference value in the thickness direction can be obtained. Can be adjusted.

The film-shaped retardation layer 130 may include a stack of a plurality of retardation layers having different retardation characteristics. Each retardation layer may be laminated using an adhesive, or a composition containing a polymerizable liquid crystal compound may be applied to the surface of the already formed retardation layer and cured.

[Base material]
The layer containing the cured product of the polymerizable liquid crystal compound can be formed, for example, on the alignment layer provided on the substrate. The base material has a function of supporting the alignment layer and may be a long base material. This base material functions as a releasable support and can support a liquid crystal curing layer or an alignment layer for transfer. Further, it is preferable that the surface has an adhesive force that can be peeled off. Examples of the base material include a translucent, preferably optically transparent thermoplastic resin film. Examples of the thermoplastic resin film include those exemplified in the above description of the stator protective layer.

The substrate may be subjected to various anti-blocking treatments. Examples of the blocking prevention treatment include an easy-adhesion treatment, a treatment of kneading a filler and the like, an embossing treatment (knurling treatment) and the like. By applying such a blocking prevention treatment to the base material, it is possible to effectively prevent the base materials from sticking to each other when the base material is wound, so-called blocking, and the productivity tends to be improved easily. be.

[Orientation layer]
The layer containing the cured product of the polymerizable liquid crystal compound is formed on the substrate via the alignment layer. That is, the base material and the alignment layer are laminated in this order, and the layer containing the cured product of the polymerizable liquid crystal compound is laminated on the alignment layer.

The alignment layer is not limited to the vertical alignment layer, and may be an alignment layer that horizontally aligns the molecular axis of the polymerizable liquid crystal compound, or may be an alignment layer that tiltly aligns the molecular axis of the polymerizable liquid crystal compound. .. The alignment layer has solvent resistance that does not dissolve due to coating of a composition containing a polymerizable liquid crystal compound, which will be described later, and heat resistance in heat treatment for removing the solvent and aligning the liquid crystal compound. preferable. Examples of the alignment layer include an alignment layer containing an orientation polymer, a photoalignment film, and a grub alignment layer in which an uneven pattern or a plurality of grooves are formed and oriented on the surface. The thickness of the oriented layer is usually in the range of 10 nm or more and 10,000 nm or less.

Further, the alignment layer has a function of supporting the liquid crystal curing layer and may function as a releasable support. A liquid crystal curing layer for transfer can be supported, and the surface thereof may have an adhesive strength to the extent that it can be peeled off.

As the resin used for the alignment layer, a resin obtained by polymerizing a polymerizable compound is used. The polymerizable compound is a compound having a polymerizable group, and is usually a non-liquid crystalline non-liquid crystal compound that does not become a liquid crystal state. The polymerizable groups of the polymerizable compound react with each other to polymerize the polymerizable compound, thereby forming a resin. Such a resin is used as an alignment layer for orienting a polymerizable liquid crystal compound at the stage of forming the liquid crystal cured layer, and if it is not contained in the liquid crystal cured layer, it is used as a material for a known oriented layer. The resin is not particularly limited, and a cured product obtained by curing a conventionally known monofunctional or polyfunctional (meth) acrylate-based monomer under a polymerization initiator can be used. Specifically, examples of the (meth) acrylate-based monomer include 2-ethylhexyl acrylate, cyclohexyl acrylate, diethylene glycol mono2-ethylhexyl ether acrylate, diethylene glycol monophenyl ether acrylate, tetraethylene glycol monophenyl ether acrylate, and trimethyl propanetriacrylate. , Lauryl acrylate, lauryl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-phenoxyethyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxypropyl acrylate, benzyl acrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate. , Cyclohexyl methacrylate, methacrylic acid, urethane acrylate and the like can be exemplified. The resin may be one of these or a mixture of two or more.
The alignment layer can be peeled off and removed together with the substrate before and after the step of forming the retardation layer 30 and then laminating it with the film-shaped linear polarizing plate 110 or the like.

Further, the alignment layer can be included in the liquid crystal curing layer for the purpose of improving the peelability from the substrate and imparting the film strength to the liquid crystal curing layer. When the liquid crystal cured layer contains an oriented layer, it is preferable to use a cured product obtained by curing a monofunctional or bifunctional (meth) acrylate-based monomer, an imide-based monomer, or a vinyl ether-based monomer as the resin used for the oriented layer.
Examples of the monofunctional (meth) acrylate-based monomer include alkyl (meth) acrylates having 4 to 16 carbon atoms, βcarboxyalkyl (meth) acrylates having 2 to 14 carbon atoms, and alkylated phenyl (meth) having 2 to 14 carbon atoms. Examples thereof include acrylates, methoxypolyethylene glycol (meth) acrylates, phenoxypolyethylene glycol (meth) acrylates and isobonyl (meth) acrylates.
Bifunctional (meth) acrylate-based monomers include 1,3-butanediol di (meth) acrylate; 1,3-butanediol (meth) acrylate; 1,6-hexanediol di (meth) acrylate; ethylene glycol di. (Meta) acrylate; Diethylene glycol di (meth) acrylate; Neopentyl glycol di (meth) acrylate; Triethylene glycol di (meth) acrylate; Tetraethylene glycol di (meth) acrylate; Polyethylene glycol diacrylate; Bisphenol A bis (acrylate) Loyloxyethyl) ether; ethoxylated bisphenol A di (meth) acrylate; propoxylated neopentyl glycol di (meth) acrylate; ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, etc. Can be mentioned.
Examples of the imide-based resin obtained by curing the imide-based monomer include polyamide and polyimide. The imide-based resin may be one of these or a mixture of two or more.
Further, the resin forming the alignment layer may contain a monomer other than the monofunctional or bifunctional (meth) acrylate-based monomer, the imide-based monomer and the vinyl ether-based monomer, but the monofunctional or bifunctional (meth) The content ratio of the acrylate-based monomer, the imide-based monomer, and the vinyl ether-based monomer may be 50% by mass or more, preferably 55% by mass or more, and more preferably 60% by mass or more in the total monomer. ..

When the alignment layer is included in the film-like retardation layer 130, the thickness of the alignment layer is usually in the range of 10 nm or more and 10,000 nm or less, and the orientation of the film-like retardation layer 130 is in-plane orientation with respect to the film surface. The thickness of the alignment layer is preferably 10 nm or more and 1000 nm or less, and when the orientation of the film-like retardation layer 130 is perpendicular to the film surface, it is preferably 100 nm or more and 10,000 nm or less. When the thickness of the oriented layer is within the above range, the peelability of the base material can be improved and appropriate film strength can be imparted.

[Adhesive layer]
The pressure-sensitive adhesive layer 120 for bonding the film-shaped linear polarizing plate 110 and the film-shaped retardation layer 130 is usually a pressure-sensitive adhesive layer formed of a pressure-sensitive pressure-sensitive adhesive (hereinafter, also referred to as a pressure-sensitive adhesive). Can be done.

The storage elastic modulus E (Pa) of the pressure-sensitive adhesive layer 120 at 25 ° C. is preferably 3.0 × 10 ⁴ Pa or more, more preferably 6.0 × 10 ⁴ Pa or more, and further preferably 9.0. × 10 ⁴ Pa or more. The storage elastic modulus of the pressure-sensitive adhesive layer 120 at 25 ° C. is usually 1.0 × 10 ⁷ Pa or less, more preferably 1.0 × 10 ⁶ Pa or less. The storage elastic modulus of the pressure-sensitive adhesive layer 120 at 25 ° C. can be measured according to the measuring method described in the column of Examples described later.

The thickness of the pressure-sensitive adhesive layer 120 may be, for example, 50 μm or less, preferably 45 μm or less, and more 30 μm or less. The thickness of the pressure-sensitive adhesive layer 120 may be, for example, 1 μm or more, preferably 2 μm or more, and more preferably 3 μm or more.

The pressure-sensitive adhesive layer 120 can be composed of a pressure-sensitive adhesive composition containing a resin such as (meth) acrylic, rubber, urethane, ester, silicone, and polyvinyl ether as a main component. Among them, a pressure-sensitive adhesive composition using a (meth) acrylic resin as a base polymer is preferable from the viewpoint of transparency, weather resistance, heat resistance and storage elastic modulus. The pressure-sensitive adhesive composition may be an active energy ray-curable type or a thermosetting type.

Examples of the (meth) acrylic resin (base polymer) used in the pressure-sensitive adhesive composition include butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, and 2- (meth) acrylate. A polymer or copolymer having one or more (meth) acrylic acid esters such as ethylhexyl as a monomer is preferably used. It is preferable that the base polymer is copolymerized with a polar monomer. Examples of the polar monomer include (meth) acrylic acid, 2-hydroxypropyl (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, and glycidyl ( Examples thereof include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group and the like, such as meth) acrylate.

The pressure-sensitive adhesive composition may contain only the above-mentioned base polymer, but usually further contains a cross-linking agent. The cross-linking agent is a divalent or higher metal ion that forms a carboxylic acid metal salt with a carboxyl group; a polyamine compound that forms an amide bond with a carboxyl group; poly. Epoxy compounds and polyols that form an ester bond with a carboxyl group; polyisocyanate compounds that form an amide bond with a carboxyl group are exemplified. Of these, polyisocyanate compounds are preferable.

To form the pressure-sensitive adhesive layer 120, for example, the pressure-sensitive adhesive composition is dissolved or dispersed in an organic solvent such as toluene or ethyl acetate to prepare a pressure-sensitive adhesive liquid, which is directly applied to the target surface of the laminate to adhere. A method of forming an agent layer or a sheet-like adhesive layer is formed on a separate film that has been subjected to a mold release treatment, and the adhesive layer is formed on the target surface of the film-like linear polarizing plate 110 or the film-like retardation layer 130. It can be performed by a transfer method or the like.

The separate film can be a film made of a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, a polyester resin such as polyethylene terephthalate, or the like. Of these, a stretched film of polyethylene terephthalate is preferable.

The pressure-sensitive adhesive layer 120 contains optional components such as glass fibers, glass beads, resin beads, fillers composed of metal powder and other inorganic powders, pigments, colorants, antioxidants, ultraviolet absorbers, antistatic agents and the like. be able to.

Examples of the antistatic agent include ionic compounds, conductive fine particles, conductive polymers and the like, and ionic compounds are preferably used.
The cation component constituting the ionic compound may be an inorganic cation or an organic cation.
Examples of the organic cation include pyridinium cation, imidazolium cation, ammonium cation, sulfonium cation, phosphonium cation, piperidinium cation, pyrrolidinium cation and the like, and examples of the inorganic cation include lithium ion and potassium ion.
On the other hand, the anion component constituting the ionic compound may be an inorganic anion or an organic anion, but an anion component containing a fluorine atom is preferable because it provides an ionic compound having excellent antistatic performance. As anion components containing a fluorine atom, hexafluorophosphate anion [(PF _6- ⁾ ], bis (trifluoromethanesulfonyl) imide anion [(CF ₃ SO ₂ ) ₂ N- ^] anion, bis (fluorosulfonyl) imide anion [ (FSO ₂ ) ₂ N- ^] Anions and the like can be mentioned.

[Other layers]
The laminate 1 may further include, for example, at least one of a laminated layer and a protective film.

[Lated layer]
In the laminated body 1, the laminated layer may be arranged on the outermost surface on the film-like retardation layer 130 side. The bonding layer can be a layer for bonding a touch sensor panel, an image display element, or the like to the laminated body 1. The laminating layer is usually composed of an adhesive. As the pressure-sensitive adhesive constituting the bonding layer, a conventionally known pressure-sensitive adhesive can be used without particular limitation, and a pressure-sensitive adhesive having a base polymer such as an acrylic polymer, a urethane-based polymer, a silicone-based polymer, or a polyvinyl ether-based polymer can be used. Can be used. Further, it may be an active energy ray-curable pressure-sensitive adhesive, a thermosetting pressure-sensitive adhesive, or the like.

[Protect film]
The protective film can be arranged on the cured resin layer 100 side of the laminated body 1. The laminate 1 can include a protective film for protecting the surface thereof, typically the surface of the cured resin layer. After the polarizing plate is attached to, for example, an image display element or another optical member, the protective film is peeled off and removed together with the pressure-sensitive adhesive layer contained therein.

The protective film is composed of, for example, a base film and an adhesive layer laminated on the base film. As for the pressure-sensitive adhesive layer, the above description of the bonded layer is applied. The resin constituting the base film is, for example, a polyethylene resin such as polyethylene, a polypropylene resin such as polypropylene, a polyester resin such as polyethylene terephthalate or polyethylene naphthalate, or a thermoplastic resin such as a polycarbonate resin. be able to. A polyester resin such as polyethylene terephthalate is preferable.

The thickness of the protective film is not particularly limited, but is preferably in the range of, for example, 20 μm or more and 200 μm or less. When the thickness of the base material is 20 μm or more, the strength tends to be easily imparted to the laminated body 1.

[Layer structure of laminated body]
FIG. 2 is a schematic cross-sectional view showing another example of the layer structure of the laminated body. The laminate 2 shown in FIG. 2 includes a cured resin layer 100, a film-shaped linear polarizing plate 110, an adhesive layer 120, and a film-shaped retardation layer 130 in this order. The film-shaped linear polarizing plate 110 includes a polarizing element protective layer 111, an adhesive layer 112, and a linear polarizing layer 113. The film-like retardation layer 130 includes a first liquid crystal curing layer 131, a first adhesive layer 132, and a second liquid crystal curing layer 133.

FIG. 3 is a schematic cross-sectional view showing still another example of the layer structure of the laminated body. The laminate 3 shown in FIG. 3 includes a protective film 140, a cured resin layer 100, a film-shaped linear polarizing plate 110, an adhesive layer 120, a film-shaped retardation layer 130, and a bonded layer 150. Prepare in order. The film-shaped linear polarizing plate 110 includes a polarizing element protective layer 111, an adhesive layer 112, and a linear polarizing layer 113. The film-like retardation layer 130 includes a first liquid crystal curing layer 131, a first adhesive layer 132, a second liquid crystal curing layer 133, a second adhesive layer 134, and a third liquid crystal curing layer 135.

[Manufacturing method of laminated body]
The laminate can be manufactured, for example, by a method including a bonding step of bonding a film-shaped linear polarizing plate 110 provided with a cured resin layer 100 and a film-shaped retardation layer 130 via the pressure-sensitive adhesive layer 120. .. In the bonding step, when the layers are bonded to each other via the bonding layer, one or both of the bonding surfaces are subjected to a surface activation treatment such as corona treatment in order to improve the adhesion. Is preferable.
The cured resin layer 100, the film-shaped linear polarizing plate 110, and the film-shaped retardation layer 130 can be manufactured as described above, respectively.

The pressure-sensitive adhesive layer 120 can be prepared as a pressure-sensitive adhesive sheet. For the pressure-sensitive adhesive sheet, for example, a pressure-sensitive adhesive composition is prepared by dissolving or dispersing the pressure-sensitive adhesive composition in an organic solvent such as toluene or ethyl acetate, and a layer made of the pressure-sensitive adhesive is formed on a release film which has been subjected to a mold release treatment. It can be produced by forming it into a sheet shape and laminating another release film on the pressure-sensitive adhesive layer. Each layer can be bonded by a method in which an adhesive sheet from which one release film has been peeled off is attached to one layer, then the other release film is peeled off, and the other layer is attached.

As a method of applying the adhesive liquid on the release film, a usual coating technique using a die coater, a comma coater, a reverse roll coater, a gravure coater, a rod coater, a wire bar coater, a doctor blade coater, an air doctor coater, etc. Should be adopted.

The release film is preferably composed of a plastic film and a release layer. Examples of the plastic film include polyester films such as polyethylene terephthalate film, polybutylene terephthalate film, and polyethylene naphthalate film, and polyolefin films such as polypropylene film. Further, the release layer can be formed from, for example, a composition for forming a release layer. The main component (resin) constituting the release layer forming composition is not particularly limited, and examples thereof include silicone resin, alkyd resin, acrylic resin, and long-chain alkyl resin.

The method for producing the laminate may further include a polishing step of polishing the end face of the laminate. Since the method for manufacturing the laminate includes a polishing step, a laminate having a polished end face can be obtained.

The polishing process will be described with reference to FIG. The polishing process is, for example, the following process:
[A] The first step of stacking a plurality of laminated bodies to obtain the laminated product W, and [b] the rotation axis R along a direction parallel to the end face of the laminated body W and orthogonal to the laminating direction. A second step of cutting the end face of the laminate W by rotating the rotary tool 60 centered and having a cutting blade relative to the laminate W can be included.

In the method for manufacturing the laminated body 1, for example, after performing the first step (the above [a]), first, the second step (the above [b]) is performed with respect to the four sides of the laminated body 1 having a rectangular shape in a plan view. ) Can be carried out. Next, polishing is performed on any of the corners and / or any of the four sides of the rectangular laminated body 1 by the second step ([b] above) to form a notch. Can be carried out.

The first step is a step of stacking a plurality of raw material laminates cut into a predetermined shape to obtain a laminate W. The number of raw material laminates contained in the laminate W is not particularly limited, but the laminate W may be, for example, a laminate of 100 to 500 laminates. The laminate constituting the laminate W may be obtained by cutting, for example, from a long laminate having a layered structure of the laminate.

The second step is a step of cutting the end face of the laminate W obtained in the first step with a rotary tool 60 to form a laminate having a polished end face.

The cutting process performed in the second step can be performed by a device provided with a support portion 50 and two rotary tools 60, for example, as shown in FIG. The support portion 50 is for pressing the laminate W from above and below to fix the laminate W itself so that it does not move during the cutting process and so that the stacked laminates do not shift. The rotary tool 60 is for cutting the end face of the laminate W, and can rotate about the rotation axis R.

The support portion 50 is a flat plate-shaped substrate (means for moving the laminate W) 51; a gate-shaped frame 52 arranged on the substrate 51; a rotary table arranged on the substrate 51 and rotatable about a central axis. 53; A cylinder 54 that is provided at a position facing the rotary table 53 in the frame 52 and can move up and down can be provided. The laminate W is sandwiched and fixed by the rotary table 53 and the cylinder 54 via the jig 55.

The rotary tool 60 has a disk-shaped rotating body that rotates about a rotation axis R. The rotation direction of the rotating body is the direction indicated by the arrow in FIG. On the board surface of the rotating body (the surface facing the end surface of the laminate W and parallel to the end surface), a plurality (for example, 2 to 10, preferably 3) are spaced apart in the rotation direction of the rotating body. ~ 7) cutting blades are arranged. The rotation axis R is preferably set so as to pass through the center of the board surface of the rotating body. The cutting blade is provided so as to project from the board surface of the rotating body toward the end surface side of the laminate W, and the rotating body rotates about the rotation axis R in a state where the cutting blade is in contact with the end surface of the laminate W. Thereby, the end face of the laminate W can be cut.

Two rotary tools 60 are provided on both sides of the substrate 51 so as to face each other. The rotary tool 60 is movable in the rotation axis R direction according to the size of the laminate W, and the substrate 51 is movable so as to pass between the two rotary tools 60. In the cutting process, the laminate W is fixed to the support portion 50, the position of the rotary tool 60 in the rotation axis R direction is appropriately adjusted, and then the rotary tool 60 is rotated around the rotary axis R while rotating the rotary tool 60. The substrate 51 is moved so that the laminate W passes between the rotating tools 60 facing each other. As a result, while the rotary tool 60 is relatively moved with respect to the laminate W along the direction parallel to the end surface of the laminate W and orthogonal to the laminate direction, the cutting blade of the rotary tool 60 is moved to the laminate. It is possible to perform a cutting process in which these end faces are scraped off by abutting against the exposed end faces facing each other of W.

The relative moving speed between the laminate W and the rotary tool 60 can be selected from, for example, a range of 200 mm / min or more and 5000 mm / min or less (more typically, a range of 500 mm / min or more and 3000 mm / min or less). can. The rotation speed of the rotary tool 60 can be selected from, for example, a range of 2000 rpm or more and 8000 rpm or less (more typically, a range of 2500 rpm or more and 6000 rpm or less).

As described above, the laminate of the present invention can minimize cracks generated in the cured resin layer and the liquid crystal cured layer in the polishing step.

<Image display device>
The laminate of the present invention can be used in an image display device. The image display device is a device having an image display panel, and includes a light emitting element or a light emitting device as a light emitting source. Examples of the image display device include a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, and the like. The laminate can be arranged on the visual side of the image display panel. The laminated body can be laminated on the image display device via the bonding layer.

The image display device may be a flexible image display device. The flexible image display device is a foldable image display device. The flexible image display device is composed of a laminate for a flexible image display device and an organic EL display panel. In the flexible image display device, the laminated body for the flexible image display device is arranged on the visual recognition side with respect to the organic EL display panel. The laminated body for a flexible image display device may include a front plate described later, a laminated body of the present invention, and a touch sensor. The stacking order of these front plates, laminated bodies and touch sensors is arbitrary. It is preferable that the front plate, the laminated body of the present invention, and the touch sensor are laminated in this order from the visual recognition side. It is also preferable that the front plate, the touch sensor, and the laminated body of the present invention are laminated in this order from the visual recognition side. The presence of the polarizing plate on the visual side of the touch sensor is preferable because the wiring pattern included in the touch sensor is difficult to visually recognize and the visibility of the displayed image is improved. Each member can be laminated using an adhesive, an adhesive, or the like. Further, a light-shielding pattern formed on at least one surface of any layer of the front plate, the polarizing plate, and the touch sensor can be provided.

[Front plate]
A front plate may be arranged on the visible side of the laminated body of this invention. The front plate can be laminated on the laminate via the adhesive layer. Examples of the adhesive layer include the above-mentioned adhesive layer and adhesive layer.

Examples of the front plate include those having a hard coat layer on at least one surface of glass or a resin film. As the glass, for example, highly transparent glass or tempered glass can be used. Particularly when a thin transparent surface material is used, chemically strengthened glass is preferable. The thickness of the glass can be, for example, 100 μm to 5 mm.

The front plate including the hard coat layer on at least one surface of the resin film can have flexible properties instead of being rigid like existing glass. The thickness of the hard coat layer is not particularly limited and may be, for example, 5 to 100 μm.

The resin film includes a cycloolefin derivative having a unit of a monomer containing a cycloolefin such as norbornene or a polycyclic norbornene-based monomer, and cellulose (diacetylcellulose, triacetylcellulose, acetylcellulosebutyrate, isobutyl ester cellulose). , Propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose) ethylene-vinyl acetate copolymer, polycycloolefin, polyester, polystyrene, polyamide, polyetherimide, polyacrylic, polyimide, polyamideimide, polyethersulfone, polysulfone, polyethylene, Polypropylene, Polymethylpentene, Polyvinyl Chloride, Polyvinylidene Chloride, Polyvinyl Alcohol, Polyvinylacetal, Polyetherketone, Polyetheretherketone, Polyethersulfone, Polymethylmethacrylate, Polyethyleneterephthalate, Polybutyleneterephthalate, Polyethylenenaphthalate, Polycarbonate , Polyurethane, epoxy and other polymers may be used. As the resin film, an unstretched uniaxial or biaxially stretched film can be used. Each of these polymers can be used alone or in combination of two or more. As the resin film, a polyamideimide film or a polyimide film having excellent transparency and heat resistance, a uniaxial or biaxially stretched polyester film, a cycloolefin derivative film having excellent transparency and heat resistance and being able to cope with an increase in the size of the film. , Polymethylmethacrylate films and triacetylcellulose and isobutylester cellulose films that are transparent and not optically anisotropic are preferred. The thickness of the resin film may be 5 to 200 μm, preferably 20 to 100 μm.

[Shading pattern]
The light-shielding pattern (bezel) can be formed on the display element side of the front plate. The shading pattern can hide each wiring of the display device so that it cannot be seen by the user. The color and / or material of the light-shielding pattern is not particularly limited, and can be formed of a resin substance having various colors such as black, white, and gold. In one embodiment, the thickness of the shading pattern may be 2 μm to 50 μm, preferably 4 μm to 30 μm, and more preferably 6 μm to 15 μm. Further, in order to suppress the mixing of air bubbles due to the step between the light-shielding pattern and the display unit and the visibility of the boundary portion, the light-shielding pattern can be given a shape.

[Touch sensor]
The touch sensor is used as an input means. As the touch sensor, various types such as a resistance film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, and a capacitance method have been proposed, and any method may be used. Of these, the capacitance method is preferable. The capacitance type touch sensor is divided into an active region and an inactive region located in the outer portion of the active region. The active area is an area corresponding to the area where the screen is displayed on the display panel (display unit), the area where the user's touch is sensed, and the inactive area is the area where the screen is not displayed on the display device (non-active area). This is the area corresponding to the display unit). The touch sensor has a substrate having flexible characteristics; a sensing pattern formed in an active region of the substrate; and a sensing pattern formed in an inactive region of the substrate, and is connected to an external drive circuit via the sensing pattern and a pad portion. Each sensing line for can be included. As the substrate having flexible characteristics, the same material as the transparent substrate of the window can be used. A touch sensor substrate having a toughness of 2,000 MPa% or more is preferable from the viewpoint of suppressing cracks that may occur in the touch sensor. More preferably, the toughness is 2,000 MPa% to 30,000 MPa%. Here, toughness is defined as the lower area of the curve to the fracture point in the stress-strain curve obtained through the tensile test of the polymer material.

Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise specified, "%" and "part" in the example are mass% and parts by mass.

[Martens hardness]
The cyclic olefin resin (COP) film on which the hard coat (HC) layer used in Examples and Comparative Examples was formed was cut into a size of 40 mm × 40 mm, and was placed on the cyclic olefin resin film side via an adhesive layer. Glass plates were pasted together to prepare a measurement sample. In an atmosphere with a temperature of 23 ° C. and a relative humidity of 55%, the surface of the measurement sample on the hard coat layer side is pressurized using an ultrafine hardness tester (FISCHERSCOPE HM2000: manufactured by Fisher Instruments Co., Ltd.). After applying the load at a speed of 1 mN / 5 seconds, the Martens hardness at 23 ° C. was measured with the creep time (time for maintaining the load of 1 mN) as 5 s.

[Storage modulus]
The storage elastic modulus of the pressure-sensitive adhesive layer was measured by the following method.
A plurality of adhesive layers were laminated so as to have a thickness of 0.2 mm. A cylinder having a diameter of 8 mm was punched out from the obtained pressure-sensitive adhesive layer, and this was used as a sample for measuring the storage elastic modulus E.
The storage elastic modulus (Pa) of the above sample was measured under the following conditions by a torsional shear method using a viscoelasticity measuring device (MCR300, manufactured by Physica) in accordance with JIS K7244-6.
〔Measurement condition〕
Normal force FN: 1N
Strain γ: 1%
Frequency: 1Hz
Temperature: 25 ° C

[Layer thickness]
The measurement was performed using a contact type film thickness measuring device (“MS-5C” manufactured by Nikon Corporation).

[Example 1]
(Preparation of laminated body)
A linear polarizing layer (thickness 8 μm) in which iodine was adsorbed and oriented on a polyvinyl alcohol-based resin film was prepared. Cyclic olefin resin (COP) film (thickness 25 μm) in which a hard coat (HC) layer having a Martens hardness of ^2.5 × 102 is formed on one surface of this linear polarizing layer via a water-based adhesive. (Hereinafter, it may be referred to as "HC (A) -COP film"), and the COP film side (the side opposite to the HC layer side) was bonded. An acrylic pressure-sensitive adhesive layer side of a protect film (thickness 53 μm) having an acrylic pressure-sensitive adhesive layer (thickness 15 μm) formed on a polyester-based resin film (thickness 38 μm) was bonded onto the HC layer of the polarizing element protective layer. .. A triacetyl cellulose (TAC) film (thickness 20 μm) as a polarizing element protective layer was bonded to the other surface of the linear polarizing layer via a water-based adhesive. As a result, a film-shaped linear polarizing plate (1) with a protective film was obtained. The film-like linear polarizing plate (1) with a protective film includes a protect film (polyester resin film, acrylic pressure-sensitive adhesive layer), an HC (A) -COP film (HC layer, COP film), a linear polarizing layer, and a TAC film. Was laminated in this order. The film-shaped linear polarizing plate (1) has a 380 nm transmittance of 0.01% or less, a 390 nm transmittance of 0.07% or less, and a 440 nm transmittance of 35% or more in a state where the protective film (thickness 53 μm) is removed. The transmittance was adjusted so that the 550 nm transmittance was 41% or more and the 610 nm transmittance was 41.5% or more.

Next, a λ / 4 plate (thickness 2 μm) which is a cured product layer of a polymerizable liquid crystal compound, an adhesive cured layer (thickness 2 μm) of an ultraviolet curable adhesive, and a positive which is a cured product layer of a polymerizable liquid crystal compound. A film-like retardation layer in which C plates (thickness 3 μm) were laminated in this order was prepared. Adhesion of the TAC film of the film-shaped linear polarizing plate (1) with a protective film and the λ / 4 plate of the film-shaped retardation layer with an adhesive having a storage elastic modulus of 1.2 × 105 Pa at ²⁵ ° C. They were bonded by an agent layer (thickness 15 μm). Subsequently, a bonding layer (1) with a release film was prepared in which a bonding layer (thickness 25 μm) formed by using an acrylic pressure-sensitive adhesive was formed on a release film (thickness 38 μm). The bonded layer of the bonded layer (1) with a release film is laminated on the positive C plate side of the film-shaped retardation layer bonded to the film-shaped linear polarizing plate (1) with a protective film, and the length of the long side is long. The laminate (1) was obtained by cutting into a rectangle having a length of 37 mm and a short side length of 35 mm. The laminate (1) is a film-like linear polarizing plate (1) with a protect film (protect film, HC (A) -COP film, linear polarizing layer, and TAC film), an adhesive layer, and a film-like retardation layer (λ). / 4 plate, bonding layer, positive C plate), and bonding layer (1) with release film (bonding layer, release film) were laminated in this order. From the film-shaped linear polarizing plate (HC (A) -COP film, linear polarizing layer, TAC film) in the laminated body (1) to the film-shaped retardation layer (λ / 4 plate, adhesive curing layer, positive C plate). The thickness of the laminated portion up to this point was 77 μm. Further, the direction of the short side of the laminated body (1) was parallel to the absorption axis of the linear polarizing layer.

(Making a laminate with a polished end face)
Using the apparatus shown in FIG. 4, a laminate W in which the raw material laminates are laminated according to the procedure of the first step described above is prepared, and the four sides of the raw material laminate are prepared according to the procedure of the second step described above. The end face corresponding to the above was polished. In each of the above polishings, the relative moving speed between the laminate W and the rotary tool 60 was set to 2100 mm / min, and the rotational speed of the rotary tool was set to 5400 rpm.

After polishing the end face, the crack length generated at the peripheral end of the laminated body was measured by observing the peripheral end of the laminated body with an optical microscope.

[Comparative Example 1]
Adhesion of the TAC film of the film-shaped linear polarizing plate (1) with a protective film and the λ / 4 plate of the film-shaped retardation layer with an adhesive having a storage elastic modulus of 2.5 × 10 ⁴ Pa at 25 ° C. A laminated body was obtained by the same procedure as in Example 1 except that the film was bonded by an agent layer (thickness 17 μm). With respect to the obtained laminated body, the crack length generated at the peripheral end portion of the laminated body was measured by observing the peripheral end portion of the laminated body with an optical microscope.

[Comparative Example 2]
A linear polarizing layer (thickness 8 μm) in which iodine was adsorbed and oriented on a polyvinyl alcohol-based resin film was prepared. A cyclic olefin resin (COP) film (thickness 25 μm) in which a hard coat (HC) layer having a Martens hardness of ^2.3 × 102 is formed on one surface of this linear polarizing layer via a water-based adhesive (thickness 25 μm). Hereinafter, the COP film side (the side opposite to the HC layer side) of "HC (B) -COP film") was bonded. An acrylic pressure-sensitive adhesive layer side of a protect film (thickness 53 μm) having an acrylic pressure-sensitive adhesive layer (thickness 15 μm) formed on a polyester-based resin film (thickness 38 μm) was bonded onto the HC layer of the polarizing element protective layer. .. A triacetyl cellulose (TAC) film (thickness 20 μm) as a polarizing element protective layer was bonded to the other surface of the linear polarizing layer via a water-based adhesive. As a result, a film-shaped linear polarizing plate (1) with a protective film was obtained. The film-like linear polarizing plate (1) with a protect film includes a protect film (polyester resin film, acrylic pressure-sensitive adhesive layer), HC (B) -COP film (HC layer, COP film), a linear polarizing layer, and a TAC film. Was laminated in this order. With the protective film (thickness 53 μm) removed, this polarizing plate has a 380 nm transmittance of 0.02% or less, a 390 nm transmittance of 12% or less, a 440 nm transmittance of 35% or more, and a 550 nm transmittance of 41.5. % Or more, and the transmittance was adjusted to have a transmittance of 41.5% or more at 610 nm. Except for this, a laminated body was obtained by the same procedure as in Example 1. With respect to the obtained laminated body, the crack length generated at the peripheral end portion of the laminated body was measured by observing the peripheral end portion of the laminated body with an optical microscope.

[Comparative Example 3]
Adhesion of the TAC film of the film-shaped linear polarizing plate (1) with a protective film and the λ / 4 plate of the film-shaped retardation layer with an adhesive having a storage elastic modulus of 2.5 × 10 ⁴ Pa at 25 ° C. A laminated body was obtained by the same procedure as in Comparative Example 1 except that the layers were bonded by an agent layer (thickness 17 μm). With respect to the obtained laminated body, the crack length generated at the peripheral end portion of the laminated body was measured by observing the peripheral end portion of the laminated body with an optical microscope.

1,2,3 Laminate, 50 Support, 51 Substrate, 52 Frame, 53 Rotating Table, 54 Cylinder, 55 Jig, 60 Rotating Tool, 100 Cured Resin Layer, 110 Film-shaped Straight Plate Plate, 111 Polarizer Protective Layer, 112 Adhesive layer, 113 Linear polarizing layer, 120 Adhesive layer, 130 Film-like retardation layer, 131 First liquid crystal curing layer, 132 First adhesive layer 132, 133 Second liquid crystal curing layer, 134 Second adhesive layer , 135 Third liquid crystal cured layer, 140 Protect film 140, 150 Laminated layer, R rotating shaft, W laminate

Claims (10)

A cured resin layer, a film-shaped linear polarizing plate, an adhesive layer, and a film-shaped retardation layer are provided in this order.
The film-like retardation layer includes a liquid crystal curing layer, and includes a liquid crystal curing layer.
When the Martens hardness of the cured resin layer at a temperature of 23 ° C. is HM (N / mm ² ), the following formula (1):
HM ≧ 2.4 × 10 ² (N / mm ² ) (1)
The filling,
When the storage elastic modulus at a temperature of 25 ° C. is E (Pa) and the thickness is T (μm), the pressure-sensitive adhesive layer has the following formula (2):
E / T ≧ 2.5 × 10 ³ (Pa / μm) (2)
A laminate that meets the requirements. The laminate according to claim 1, wherein the film-shaped linear polarizing plate includes a thermoplastic resin film. The laminate according to claim 1 or 2, wherein the storage elastic modulus E (Pa) at a temperature of 25 ° C. is 3.0 × ¹⁰⁴ or more. The laminate according to any one of claims 1 to 3, wherein the thickness T (μm) is 30 μm or less. The laminate according to any one of claims 1 to 4, wherein the film-like retardation layer includes two or more liquid crystal cured layers. The laminate according to any one of claims 1 to 5, wherein the laminate is single-leaved. The laminate according to any one of claims 1 to 6, wherein the laminate has a polished end face. A laminate for a flexible image display device including the laminate according to any one of claims 1 to 7, a front plate, and a touch sensor. An image display device having the laminate according to any one of claims 1 to 7. A flexible image display device having the laminate for the flexible image display device according to claim 8.

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