TW202231459A - Laminate - Google Patents

Abstract

The problem to be solved by the present invention is to provide a laminate including sequentially a cured resin layer, a film-shaped linear polarizing plate, an adhesive layer, and a film-shape phase difference layer. When an end face is polished in a state where a plurality of laminates are superposed on each other, cracks in the cured resin layer and in a liquid crystal cured layer can be minimized.

The solution proposed in the present application is a laminate including sequentially a cured resin layer, a film-shaped linear polarizing plate, an adhesive layer, and a film-shaped phase difference layer, wherein the film-shaped phase difference layer includes a liquid crystal cured layer; when the Martens Hardness of the cured resin layer at 23℃ is set as HM (N/mm²), HM≧2.4x10²(N/mm²) is satisfied; and when the storage modulus of elasticity of the adhesive layer at 25℃ is set as E(Pa), and the thickness thereof as T(μm), E/T≧2.5×10³(Pa/μm) is satisfied.

Description

Laminate

The present invention relates to a laminate.

Conventionally, a laminate including a linear polarizer, a hard coat layer (cured resin layer) laminated on one side, and a liquid crystal layer laminated on the other side via an adhesive is known (Patent Document 1).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2020-106602

The end surface of the above-mentioned laminated body is usually ground in a state in which a plurality of laminated bodies are overlapped with each other. When the end faces are polished in this way, cracks may occur in the hard coat layer or in the liquid crystal layer.

An object of the present invention is to provide a laminate including a cured resin layer, a film-like linear polarizing plate, an adhesive layer, and a film-like retardation layer in this order, and which are polished in a state where a plurality of laminates are overlapped with each other. In the case of the end face, the cracks generated by the hardened resin layer and the liquid crystal hardened layer can be reduced.

The present invention provides the following laminate and an image display device.

[1] A laminate comprising a cured resin layer, a film-like linear polarizing plate, an adhesive layer, and a film-like retardation layer in this order, wherein,

The film-like retardation layer includes a liquid crystal cured layer,

When the Martens Hardness of the cured resin layer at a temperature of 23° C. is set to HM (N/mm ² ), the following formula (1) is satisfied:

HM≧2.4×10 ² (N/mm ² ) (1)

When the storage elastic modulus of the aforementioned adhesive layer at a temperature of 25°C is set to E (Pa) and the thickness is set to T (μm), the following formula (2) is satisfied:

E/T≧2.5×10 ³ (Pa/μm) (2).

[2] The laminate according to [1], wherein the film-like linear polarizing plate contains 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 3.0×10 ⁴ or more.

[4] The laminate according to any one of [1] to [3], wherein the thickness T (μm) is 30 μm 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 layered body according to any one of [1] to [5], wherein the layered body has a blade shape.

[7] The layered body according to any one of [1] to [6], wherein the layered body has a polished end surface.

[8] A laminate for a flexible image display device, comprising the laminate according to any one of [1] to [7], a front panel, 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 a flexible image display device according to [8].

According to the present invention, it is possible to provide a laminate including a cured resin layer, a film-like linear polarizing plate, an adhesive layer, and a film-like retardation layer in this order, and which are polished in a state where a plurality of laminates are overlapped with each other. In the case of the end face, the cracks generated by the hardened resin layer and the liquid crystal hardened layer can be reduced.

1,2,3: Laminate

50: Support part

51: Substrate

52: Frame

53: Rotary machine

54: Cylinder

55: Aids

60: Rotation Tool

100: Hardened resin layer

110: film linear polarizer

111: polarizer protective layer

112: Adhesive layer

113: Linear polarizing layer

120: Adhesive layer

130: film retardation layer

131: 1st liquid crystal cured layer

132: The first adhesive layer

133: Second liquid crystal hardened layer

134: Second Adhesive Layer

135: 3rd liquid crystal hardened layer

140: Surface protection film

150: Lamination layer

R: Rotation axis

W: Laminate

FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of a laminated linear polarizing plate.

FIG. 2 is a schematic cross-sectional view showing another example of the layer structure of the laminated linear polarizing plate.

FIG. 3 is a schematic cross-sectional view showing another example of the layer structure of the laminated linear polarizing plate.

FIG. 4 is a schematic perspective view schematically showing an example of the method for producing the laminate of the present invention.

The embodiments of the present invention are described below with reference to the drawings, but the present invention is not limited to the following embodiments. In all the drawings below, the proportions of the components shown in the drawings are not necessarily the same as the proportions of the actual components, and the proportions of the components shown in the drawings are not necessarily the same as those of the actual components.

<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-like linear polarizer 110 , an adhesive layer 120 , and a film-like retardation layer 130 in this order. The film-like retardation layer 130 includes a liquid crystal hardening layer (not shown in the figure). The layered body 1 may further include other layers than the above-mentioned layers. Other layers include, for example, a surface protective film (pellicle film) that can be bonded on the side of the cured resin layer 100 , a bonding layer that can be bonded on the side of the film-like retardation layer 130 , and the like.

The laminated body 1 is preferably laminated by directly contacting the cured resin layer 100 and the film-like linear polarizing plate 110 , the film-like linear polarizing plate 110 and the adhesive layer 120 , the adhesive layer 120 and the film-like retardation layer 130 .

The layered body 1 may be elongated or leaf-shaped. The layered body 1 is preferably in the shape of a blade. The blade-shaped laminated body can be obtained by cutting out the elongated laminated body. When the layered body 1 is in the shape of a blade, the plan view shape of the layered body 1 can be, for example, a square shape, preferably a square shape with long sides and short sides, and particularly preferably a rectangle. When the planar view shape of the laminated body 1 is a rectangle, 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 particularly preferably 30 mm or more and 300 mm or less.

In the present specification, the term "planar view" refers to an observer from the thickness direction of the layer.

In the case where the laminated body 1 is in the shape of a blade, the laminated body 1 preferably has a ground surface for the purpose of removing chips and the like generated on the end face of the laminated body during cutting, and from the viewpoint of dimensional accuracy. end face. When the layered body 1 is viewed from above, a part or all of the end faces may be ground, and preferably all of the end faces are ground.

Moreover, when the planar view shape of the laminated body 1 is a square shape, the length of each side in each layer which comprises the laminated body 1 may be mutually the same. When the lengths of the respective sides are the same as each other, the plan view shape of the laminate 1 becomes a square.

When the layered body 1 has a square shape in plan view, any corner portion, for example, all the corner portions of the layers constituting the layered body 1 may be notch-processed to have a notch portion. When the corner portion has a notch portion, the corner portion can be R-processed and the notch can be notch-processed into a curved shape, or the notch can be notch-processed into a linear shape. When the shape of the layered body 1 in plan view is a square shape, any one of the sides constituting the layered body 1 may be notched into a concave shape. The layered body 1 may be provided with through holes by in-plane drilling in a plan view.

The laminate 1 may be, for example, a laminate having antireflection properties. As a laminated body which has antireflection property, a circular polarizing plate is mentioned, for example. In the image display device, by disposing the layered body having antireflection performance on the front side of the image display device, it is possible to suppress deterioration of visibility due to reflection of external light.

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

When the image display device is a liquid crystal display device, the layered body 1 can be arranged as a layered body of polarizing plates arranged on the front side on 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 polarizer arranged on the front side for the purpose of anti-reflection of external light.

[Formula 1)]

The layered body 1 satisfies the following formula (1) when the Martens hardness (hereinafter, simply referred to as Martens hardness for simplicity) of the cured resin layer 100 at a temperature of 23° C. is HM (N/mm ² ).

HM≧2.4×10 ² (N/mm ² ) (1)

When the cured resin layer 100 of the laminated body 1 has the Martens hardness in the above-mentioned range, the cracks generated in the cured resin layer 100 tend to be reduced when the laminated body 1 is ground. Martens hardness can be calculated according to the following formula.

In the formula, HM represents the Martens hardness (N/mm ² ) of the hardened resin layer, F represents the load (N), and As (h) represents the surface area (mm ² ) of the pressing piece at the depth (h).

As can be seen from the above formula, as the Martens hardness of the cured resin layer increases, the amount of deformation of the cured resin layer with respect to the press-fitting under a constant load is related to decrease. From this result, it is presumed that even when a certain stress is applied to the end face of the laminated body and a strain is generated in the film-like linear polarization, when the Martens hardness of the cured resin layer is large, the cured resin layer is deformed due to deformation. The amount becomes smaller and the cracking of the hardened resin layer is reduced. The Martens hardness can be measured according to the method described in the column of the following examples.

In this specification, the term "cracking" means the end of the hardened resin layer and the hardened liquid crystal layer in the region where the function of the laminate can be normally exhibited when the laminate is observed by the transmitted light of an optical microscope when viewed from above. Cracks observed in some areas. Cracks can be observed in accordance with the method described in the column of the examples described later.

The right side in the above formula (1) is preferably 2.45×10 ² (N/mm ² ), more preferably 2.5×10 ² (N/mm 2 ), from the viewpoint of easily reducing cracks generated in the cured resin layer 100 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, and may be, for example, 3.0×10 ² (N/mm ² ) the following.

Examples of means for satisfying the above formula (1) include: a method of adjusting the composition of a composition for forming a hardened resin layer for forming a hardened resin layer to be described later; a method of adjusting the thickness of the hardened resin layer; Among them, select and use a method that satisfies the above formula (1). The method of adjusting the composition of the composition for forming a curable resin layer includes, for example, a method of adjusting the type and/or content of the polymerizable monomer or additive constituting the curable resin.

[Formula (2)]

When the storage elastic modulus of the adhesive layer 120 at 25° C. is E (Pa) and the thickness of the adhesive layer 120 is T (μm), the laminate 1 satisfies the following formula (2).

E/T≧2.5×10 ³ (Pa/μm) (2)

By making the adhesive layer 120 of the laminated body 1 satisfy the formula (2), when the laminated body 1 is polished, the cracks generated by the liquid crystal cured layer included in the film-like retardation layer 130 tend to be slightly reduced. The storage elastic modulus and thickness of the adhesive layer 120 at 25° C. can be measured according to the methods described in the columns of the following examples.

The inventors have found that the more elastic the adhesive constituting the adhesive layer for bonding the film-like linear polarizing plate and the film-like retardation layer, the less hardening of the liquid crystal contained in the film-like retardation layer is during polishing of the laminate. cracks caused by the layer. The reason for this is presumed that the more elastic the adhesive constituting the adhesive layer is, the more the laminate tends to become highly elastic, and the strain of the laminate with respect to the stress at the time of polishing becomes smaller. As a result, strain occurs in the film-like retardation layer. , the deformation is also smaller. In addition, it has also been found that the smaller the thickness of the adhesive layer, the less the cracks generated in the liquid crystal hardening layer included in the film-like retardation layer during polishing of the laminate can be reduced. The reason for this is presumed to be that among the laminate and the adhesive layer, the laminate has higher elasticity, and when the thickness of the adhesive layer is reduced, the physical properties of the laminate are close to the physical properties of the high elasticity of the laminate itself, and the laminate is relatively The strain of the stress at the time of polishing becomes smaller, and as a result, even if strain occurs in the film-like retardation layer, the amount of deformation becomes smaller.

It was also found that when the laminated body 1 satisfies the formula (2) and satisfies the formula (1), compared with the case where the formula (1) is not satisfied and the formula (2) is satisfied, the generation of the liquid crystal hardening layer can be further reduced. cracked.

The right side in the above formula (2) is preferably 4.0×10 ³ (Pa/μm) from the viewpoint of easily reducing cracks generated in the liquid crystal cured layer. In the above formula (2), 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 preferred ranges of the storage elastic modulus E and the thickness T of the adhesive layer 120 at 25° C. will be described later.

[hardened resin layer]

The curable resin layer 100 may be a layer containing a cured product of a curable resin. As curable resin, a thermosetting resin, an active energy ray curable resin, etc. are mentioned, for example. The hardened resin layer 100 may be a functional layer 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 cured 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 may contain, for example, a polymerizable monomer, a polymerization initiator, an additive, a solvent, and the like. Examples of additives include plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments or dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, antistatic agents, antioxidants, lubricants agents, surfactants, etc.

The cured resin layer 100 may be disposed on the opposite side of the film-shaped linear polarizing plate 110 to the film-shaped retardation layer 130 , and is preferably directly disposed on the opposite side of the film-shaped linear polarizing plate 110 and the film-shaped retardation layer 130 . On the polarizer protective layer or the linear polarizer layer, it is particularly preferable to arrange the polarizer protective layer or straight line on the opposite side of the film-shaped linear polarizer 110 and the film-shaped retardation layer 130 so as to be the outermost layer of the laminated body 1 on the polarizing layer. The polarizer protective layer or the linear polarizing layer will be described later. When the hardened resin layer 100 is directly disposed on the polarizer protective layer, for example, the composition for forming a hardened resin layer may be coated on the thermoplastic resin film forming the polarizer protective layer and then hardened to form a hardened resin layer forming composition. The cured product of the composition is produced by producing a thermoplastic resin film including the cured resin layer 100, and is then bonded to the linear polarizing layer via the adhesive layer. Moreover, a commercially available thermoplastic resin provided with a hardening resin layer can also be used.

In addition, when the hardened resin layer 100 is directly disposed on the linear polarizing layer, for example, the hardening resin layer forming composition is coated on the linear polarizing layer and hardened to form a hardened product of the hardening resin layer forming composition, Thereby, the film-like linear polarizing plate 110 provided with the cured resin layer 100 is produced.

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 hardened resin layer 100 is a hard coat layer, the hardness and scratch resistance of the linear polarizer layer or the polarizer protective layer can be easily improved. The hard coat layer can be formed from a cured product of the composition for forming a hard coat layer containing an active energy ray-curable resin. Examples of active energy ray-curable resins include acrylic resins, polysiloxane-based resins, polyester-based resins, urethane-based resins, amide-based resins, epoxy-based resins, and the like. To increase strength, the hard coat layer may contain additives. The additive is not limited, and examples thereof include inorganic fine particles, organic fine particles, or a mixture thereof.

[Film Linear Polarizer]

The film-like linear polarizing plate 110 has a linear polarizing layer and a polarizer protective layer disposed on at least one side of the linear polarizing layer. The linear polarizing layer can be a polarizer with the following properties, that is, to absorb linearly polarized light with a vibration plane parallel to the absorption axis, and to transmit linearly polarized light with a vibration plane perpendicular to the absorption axis (parallel to the transmission axis) the nature of. The polarizer protective layer is used to protect the linear polarizing layer, especially the layer on the surface of the linear polarizing layer. The film-like linear polarizing plate 110 may further include a base material and an alignment film to be described later. The film-shaped linear polarizing plate 110 may have flexibility. The film-like linear polarizing plate 110 may further include a surface protective film (protective film) to be described later.

The thickness of the film-like 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 stretched layer to which a dichroic dye is adsorbed, or a film obtained by coating and curing the dichroic dye. Specifically, dichroic dyes use iodine or dichroic organic dye. Dichroic organic dyes include: dichroic direct dyes composed of disazo compounds such as C.I.DIRECT RED 39; dichroic direct dyes composed of trisazo, tetrazo and other compounds.

[Linear polarizing layer as a stretched film or stretched layer to which dichroic dyes are adsorbed]

Here, the linear polarizing layer which is a stretched film (hereinafter sometimes abbreviated as "stretched film") to which a dichroic dye is adsorbed will be described. A stretched film with a dichroic dye adsorbed can usually be produced through the following steps: a step of uniaxially stretching a polyvinyl alcohol-based resin film; dyeing the polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye The step of adsorbing the chromatic pigment; the step of treating the polyvinyl alcohol-based resin film adsorbed with the dichroic pigment with an aqueous solution of boric acid; and the step of washing with water after the treatment with an aqueous solution of boric acid. The thickness of the linear polarizing layer as the stretched film to which the dichroic dye is adsorbed may be, for example, 2 μm or more and 40 μm or less.

The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. As the polyvinyl acetate-based resin, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers that can be copolymerized with the vinyl acetate can also be used. Examples of other monomers that can be copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, (meth)acrylamides having an ammonium group, and the like.

The degree of saponification 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 denatured, and for example, aldehyde-denatured polyvinyl formaldehyde or polyvinyl acetal may be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 or more and 10,000 or less, preferably 1,500 or more and 5,000 or less.

To form such a polyvinyl alcohol-based resin into a film, a blank film as a stretched film can be used. The method for forming a film from a polyvinyl alcohol-based resin is not particularly limited, and it can be method to make films. The film thickness of the polyvinyl alcohol-based blank material 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 dyeing with a dichroic dye, simultaneously with dyeing, or after dyeing. In the case of performing uniaxial extension after dyeing, the uniaxial extension may be performed before the boric acid treatment, or may be performed during the boric acid treatment. In addition, it is also possible to perform uniaxial stretching in these plural stages. During the uniaxial stretching, the uniaxial stretching can be performed between rolls with different peripheral speeds, or the heating roller can be used for uniaxial stretching. In addition, the uniaxial stretching may be dry stretching in which the stretching is performed in the atmosphere, or wet stretching in which the polyvinyl alcohol-based resin film is stretched in a swollen state using a solvent. The stretching ratio is usually about 3 times or more and 8 times or less.

The dyeing with the dichroic dye of the polyvinyl alcohol-based resin film is performed by, for example, a method of immersing the polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic dye. Specifically, as the dichroic dye, iodine or a dichroic organic dye is used. Dichroic organic dyes include: dichroic direct dyes composed of disazo compounds such as C.I.DIRECT RED 39; dichroic direct dyes composed of trisazo, tetrazo and other compounds. The polyvinyl alcohol-based resin film is preferably dipped in water before dyeing.

In the case of using iodine as a dichroic dye, a method of dyeing a polyvinyl alcohol-based resin film by immersing it in an aqueous solution containing iodine and potassium iodide is usually employed.

The content of iodine in this aqueous solution is usually 0.01 part by mass or more and 1 part by mass or less per 100 parts by mass of water. In addition, 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. In addition, the immersion time (dyeing 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 a dichroic dye, a method of dyeing by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is usually employed. The content of the dichroic organic dye in the 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 mass part or less per 100 parts by mass of water. , more preferably 1×10 ^-3 parts by mass or more and 1×10 ^-2 parts by mass or less. The aqueous solution may also contain inorganic salts such as sodium sulfate as dyeing aids. The temperature of the dichroic dye aqueous solution used for dyeing is usually 20°C or higher and 80°C or lower. In addition, the immersion time (dyeing time) in this aqueous solution is usually 10 seconds or more and 1,800 seconds or less.

The boric acid treatment after dyeing by the dichroic dye is usually carried out by a method of immersing the dyed polyvinyl alcohol-based resin film in a boric acid aqueous solution. The content of boric acid in the boric acid aqueous 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 a dichroic dye, the boric acid aqueous solution preferably contains potassium iodide, and the content of potassium iodide in this case is usually 0.1 to 15 parts by mass per 100 parts by mass of water, preferably 0.1 to 15 parts by mass. 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, 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 subjected to water washing treatment. The water washing treatment can be performed by, for example, immersing the polyvinyl alcohol-based resin film treated with boric acid in water. The temperature of the water in the water washing treatment is usually 5°C or higher and 40°C or lower. In addition, the immersion time is usually 1 second or more and 120 seconds or less.

After washing with water, a drying treatment is applied to obtain a stretched film on which the 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 time is usually 60 seconds or more and 600 seconds or less, preferably 120 seconds or more and 600 seconds or less. By drying, the moisture content of the stretched film that adsorbs the dichroic dye is reduced to a practical level. The moisture content is usually 5 mass % or more and 20 mass % or less, preferably 8 mass % or more and 15 mass % or less. When the moisture content is less than 5% by mass, the stretched film to which the dichroic dye is adsorbed loses flexibility, and the stretched film to which the dichroic dye is adsorbed may be damaged or broken after drying. In addition, when the moisture content is higher than 20 mass %, the thermal stability of the stretched film to which the dichroic dye is adsorbed may be deteriorated.

Next, the linear polarizing layer which is a stretched layer (hereinafter sometimes abbreviated as "stretched layer") to which the dichroic dye is adsorbed will be described. The stretched layer to which the dichroic dye is adsorbed can usually be produced through the following steps: a step of applying a coating solution containing the above-mentioned polyvinyl alcohol-based resin on a substrate to obtain a laminated film; The step of axial stretching; the step of dyeing the polyvinyl alcohol-based resin layer of the uniaxially stretched laminate film with dichroic dyes to make them adsorb; the step of treating the film with the dichroic dyes adsorbed with boric acid aqueous solution; and the step of washing with boric acid solution after treatment.

As an example of a base material, what was illustrated in the description of the polarizer protective layer mentioned later can be applied. The base material may be peeled and removed from the extension layer, or the base material may be used as a polarizer 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 in the laminate 1, the thickness of the base film is preferably 30 μm or less.

[Linear polarizing layer as film after coating and curing of dichroic dye]

The film after applying the dichroic dye and curing may include, for example, a film comprising the following cured product, which is a composition containing a dichroic dye having liquid crystallinity, or a composition containing a dichroic dye and a liquid crystal compound. The composition is applied to a substrate and the latter is hardened.

As an example of a base material, what was illustrated by the thermoplastic resin film in the description of the polarizer protective layer mentioned later is applicable. The substrate can be peeled off from the film after the dichroic dye is coated and cured, or the substrate can be used as a polarizer 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 in the layered body 1, the thickness of the base material is preferably 30 μm or less. The substrate may have a hard coat layer, an anti-reflection layer or an anti-static layer on at least one surface. The hard coat layer, antireflection layer and antistatic layer may be formed only on the surface of the base material on the side where the hardened product is not formed, or only on the surface of the base material on the side where the hardened product is formed.

The film after coating with the dichroic pigment and hardening is preferably thin, but if it is too thin, the strength will decrease and the processability will tend to deteriorate. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and particularly preferably 0.5 μm or more and 3 μm or less.

Specifically, as the film after coating and curing the dichroic dye, those described in JP 2013-37353 A, JP 2013-33249 A, and the like are exemplified.

[Alignment Film]

The alignment film can be arranged between the above-mentioned base material and a layer containing a composition containing a dichroic dye having liquid crystallinity, or a cured product of a composition containing a dichroic dye and a liquid crystal compound. The alignment film system has an alignment restraint force to align the liquid crystal layer formed above it in a desired direction. Examples of the alignment film include: an alignment polymer layer formed of an alignment polymer, a photoalignment polymer layer formed of a photo-alignment polymer, a concave-convex pattern or a plurality of concavities on the surface of the layer The groove alignment film of the groove (groove). The thickness of the alignment film may be, for example, 10 nm or more and 500 nm or less, preferably 10 nm or more and 200 nm or less.

The alignment polymer layer can be formed by applying a composition obtained by dissolving the alignment polymer in a solvent to a substrate, removing the solvent, and performing rubbing treatment if necessary. In this case, in the alignment polymer layer formed of the alignment polymer, the alignment restraint force can be arbitrarily adjusted by the surface state of the alignment polymer or friction conditions.

The photoalignment 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 it with polarized light. In this case, in the photo-alignment polymer layer, the alignment restricting force can be arbitrarily adjusted by the polarized light irradiation conditions and the like for the photo-alignment polymer.

The groove alignment film can be formed by, for example, the following methods: a method of forming a concavo-convex pattern through exposure, development, etc. through an exposure mask having a pattern-shaped slit on the surface of the photosensitive polyimide film; A method of forming an uncured layer of active energy ray-curable resin on a plate-shaped original plate with grooves, transferring this layer to a substrate and curing; forming an uncured layer of active energy ray-curable resin on a substrate A method of forming unevenness by pushing a roll-shaped original plate having unevenness against this layer, etc., and then curing it.

[Polarizer protective layer]

The polarizer protective layer may be formed of, for example, a thermoplastic resin film or a coating layer. The film-like linear polarizing plate 110 may only have a polarizer protective layer on one side of the linear polarizing layer, or may have a polarizer protective layer on both sides. When the film-shaped linear polarizing plate 110 has polarizer protective layers on both sides of the linear polarizing layer, the polarizer protective layers may be of the same type or different types. When the polarizer protective layer is a thermoplastic resin film, the polarizer protective layer can be bonded to the linear polarizing layer via an adhesive layer described later. this In addition, when the polarizer protective layer is a thermoplastic resin film, the thermoplastic resin film with a hardened resin layer can be used as the polarizer protection disposed on the opposite side of the film-shaped linear polarizer 110 and the film-shaped retardation layer 130 The layer is used by being attached to the linear polarizing layer. The film-like linear polarizer 110 preferably includes a thermoplastic resin film.

[Thermoplastic resin film]

The thermoplastic resin film that can be used as the protective layer of the polarizer can be assembled to the film-like linear polarizing plate 110 in the form of being attached to one side or both sides of the linear polarizing layer. The thermoplastic resin film may be, for example, a light-transmitting thermoplastic resin film, preferably an optically transparent thermoplastic resin film, and examples thereof include chain polyolefin-based resins (polyethylene-based resins, polypropylene-based resins, polyamide resins) Polyolefin-based resins such as pentene-based resins, etc.), cyclic polyolefin-based resins (norbornene-based resins, etc.); cellulose-based resins such as cellulose triacetate; polyethylene terephthalate, polyethylene naphthalate Polyester resins such as ethylene formate and polybutylene terephthalate; polycarbonate resins; ethylene-vinyl acetate resins; polystyrene resins; polyamide resins; polyetherimide resin; (meth)acrylic resin such as poly(meth)acrylate resin; polyimide resin; polyether resin; polyvinyl resin; polyvinyl chloride resin; polyvinylidene chloride series resin; polyvinyl alcohol series resin; polyvinyl acetal series resin; polyether ketone series resin; polyether ether ketone series resin; Thermoplastic resins may be used alone or in combination of two or more. Among them, from the viewpoint of strength or light transmittance, a triacetate-based resin film, a cyclic polyolefin-based resin film, and a (meth)acrylic-based resin film are preferred.

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 generally 1 μm or more, preferably 5 μm or more, and more preferably 15 μm or more. The thermoplastic resin film may or may not have retardation.

The adhesive used for laminating the linear polarizing layer and the thermoplastic resin film includes active energy ray-curable adhesives such as ultraviolet curable adhesives; Water-based adhesives such as aqueous solutions and urethane-based emulsion adhesives. When bonding a thermoplastic resin film on both sides of the linearly polarizing layer, the adhesives for forming the two adhesive layers are the same or different. For example, when bonding a thermoplastic resin film 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 can be a mixture of a radically polymerizable (meth)acrylic compound and a photoradical polymerization initiator, or a mixture of a cationically polymerizable epoxy compound and a photocationic polymerization initiator. Furthermore, 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 together as an initiator. The thickness of the adhesive may be, for example, 0.1 μm or more and 5 μm or less.

In the case of using an active energy ray-curable adhesive, the adhesive is cured by irradiating an active energy ray after bonding. The light source of the active energy ray is not particularly limited, but it is preferably an active energy ray (ultraviolet) having a luminescence distribution at a wavelength of 400 nm or less, and specifically, it is suitable to use a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, and a chemical lamp. , black light lamp, microwave excited mercury lamp, metal halide lamp, etc.

In order to improve the adhesion between the linear polarizing layer and the thermoplastic resin film, corona treatment, flame treatment, Surface treatment such as plasma treatment, ultraviolet irradiation treatment, primer coating treatment, saponification treatment, etc.

[coating layer]

The polarizer protective layer formed by the coating layer may be, for example, one formed by coating and curing a cationic curable composition such as epoxy resin or a radical curable composition such as (meth)acrylate, or may be Aqueous solutions such as polyvinyl alcohol-based resins are coated and dried, and can also contain plasticizers, ultraviolet absorbers, infrared absorbers, colorants such as pigments or dyes, optical brighteners, dispersants, heat Stabilizers, light stabilizers, antistatic agents, antioxidants, lubricants, etc.

When the polarizer protective layer is a coating layer, the thickness of the polarizer protective layer may be, for example, 0.1 μm or more and 30 μm or less. From the viewpoint of thinning, it is preferably 0.5 μm or more and 20 μm or less, particularly preferably 1 μm or more. 10μm or less.

[Film-shaped retardation layer]

The film-like retardation layer 130 is laminated on the opposite side of the film-like linear polarizing plate 110 and the cured resin layer 100 via the adhesive layer 120 . The film-shaped linear polarizing plate 110 may have flexibility.

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

The film-like retardation layer 130 preferably includes a λ/4 layer, particularly preferably a λ/4 layer, and at least any one of a λ/2 layer and a positive-type C layer. When the retardation layer includes the λ/2 layer, the λ/2 layer and the λ/4 layer may be sequentially laminated from the film-like linear polarizing plate 110 side. When the retardation layer includes a positive-type C layer, the λ/4 layer and the positive-type C layer may be sequentially laminated from the film-shaped linear polarizer 110 side, or may be sequentially laminated from the film-shaped linear polarizer 110 side Positive type C layer and λ/4 layer.

The thickness of the film-like 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 particularly preferably 0.5 μm or more and 15 μm or less.

The film-like retardation layer 130 includes a liquid crystal cured layer. The liquid crystal cured layer is a layer of a cured product by polymerizing and curing a polymerizable liquid crystal compound. The liquid crystal hardening layer may be one in which the polymerizable liquid crystal compounds are polymerized with each other in the state of liquid crystal alignment. The polymerizable liquid crystal compound may be in in-plane alignment or vertical alignment. When the polymerizable liquid crystal compound exhibits in-plane alignment, the liquid crystal cured layer becomes a positive-type A layer that exhibits an in-plane retardation. When the polymerizable liquid crystal compound is vertically aligned, it becomes a positive-type C layer that exhibits retardation in the thickness direction.

A polymerizable liquid crystal compound is a compound which has a polymerizable group, and is a compound which can form a liquid crystal state. The polymerizable liquid crystal compound is cured by polymerizing the polymerizable liquid crystal compound by reacting the polymerizable groups of the polymerizable liquid crystal compound.

The liquid crystal cured layer with which the film-like retardation layer 130 is equipped may be one layer, or two layers or three or more layers. When the film-like retardation layer 130 includes two or more liquid crystal cured layers, the liquid crystal cured layers are usually laminated on each other through an adhesive layer. The film-like retardation layer 130 may include a base material and/or an alignment layer for aligning the polymerizable liquid crystal compound when forming the liquid crystal cured layer, in addition to the liquid crystal cured layer and the adhesive layer laminated with each other. When the film-shaped retardation layer 130 has a base material, the base material is usually removed when the film-shaped retardation layer 130 is attached to the linear polarizing plate.

Examples of the adhesive used in the adhesive layer include active energy ray-curable adhesives such as UV-curable adhesives, aqueous solutions of polyvinyl alcohol-based resins, aqueous solutions prepared with cross-linking agents, and urethanes. Water-based adhesives such as emulsion adhesives. When the film-like retardation layer 130 includes two or more adhesive layers, the adhesive may be the same or different. 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, and can be classified into a rod-shaped type (rod-shaped liquid crystal compound) and a discotic type (disc-shaped liquid crystal compound, discotic liquid crystal compound) in view of the shape. Furthermore, each has a low-molecular type and a high-molecular type. The term "polymer" generally means one with a degree of polymerization of 100 or more (Polymer Physics/Phase Transfer Kinetics, by Masao Doi, p. 2, Iwanami Shoten, 1992). In the present invention, any polymerizable liquid crystal compound can be used. Furthermore, two or more types of rod-like liquid crystal compounds, two or more types of discotic liquid crystal compounds, or a mixture of a rod-like liquid crystal compound and a discotic liquid crystal compound may be used. As the rod-like liquid crystal compound, for example, those described in claim 1 of JP-A No. 11-513019 can be suitably used. As the discotic liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP 2007-108732 A, or paragraphs [0013] to [0108] in JP 2010-244038 A can be suitably used.

The polymerizable liquid crystal compound may be used in combination of two or more. In this case, at least one type has two or more polymerizable groups in the molecule. That is, it is preferable that the layer which the said polymerizable liquid crystal compound hardens is a layer formed by fixing the liquid crystal compound which has a polymerizable group by polymerization. In this case, it is no longer necessary to develop liquid crystallinity after becoming a layer.

The polymerizable liquid crystal compound has a polymerizable group capable of a polymerization reaction. The polymerizable group is preferably, for example, a functional group that can undergo an addition polymerization reaction, such as a polymerizable ethylenically unsaturated group or a cyclic polymerizable group. More specifically, as a polymerizable group, a (meth)acryloyl group, a vinyl group, a styryl group, an allyl group, etc. are mentioned, for example. Among them, a (meth)acryloyl group is preferred. A (meth)acryloyl group is a concept including both a methacryloyl group and an acryl group.

The liquid crystallinity of the polymerizable liquid crystal compound can be thermotropic liquid crystal (thermotropic liquid crystal) or lyotropic liquid crystal (Lyotropic liquid crystal). Columnar liquid crystal.

The liquid crystal cured layer can be formed by applying, for example, a composition containing a polymerizable liquid crystal compound (hereinafter also referred to as a composition for forming a retardation layer) on an alignment layer and irradiating an active energy ray. Components other than the above-described polymerizable liquid crystal compound may be contained in the composition for forming a retardation layer. For example, the composition for forming a retardation layer preferably contains a polymerization initiator. The polymerization initiator used is selected according to the type of polymerization reaction, such as thermal polymerization initiator or photopolymerization initiator. Examples of photopolymerization initiators include α-carbonyl compounds, acyloin ethers, α-hydrocarbon-substituted aromatic acyloin compounds, polynucleoquinone compounds, triarylimidazole dimers, and p-aminophenone combination, etc. The amount of the polymerization initiator to be used is preferably 0.01 mass % or more and 20 mass % or less, particularly preferably 0.5 mass % or more and 5 mass % or less, based on the total solid content in the coating liquid. The so-called hardened material means a state in which the formed layer does not deform or flow and can exist independently even if it exists alone.

In addition, from the viewpoint of the uniformity of the coating film and the strength of the film, a polymerizable monomer may be contained in the composition for forming a retardation layer. The polymerizable monomer includes radically polymerizable or cationically polymerizable compounds. Among them, polyfunctional radically polymerizable monomers are preferred.

The polymerizable monomer is preferably copolymerizable with the above-mentioned polymerizable liquid crystal compound. The amount of the polymerizable monomer to be used is preferably 1 mass % or more and 50 mass % or less, particularly preferably 2 mass % or more and 30 mass % or less, with respect to the total mass of the polymerizable liquid crystal compound.

In addition, from the viewpoint of the uniformity of the coating film and the strength of the film, the composition for forming a retardation layer may contain a surfactant. As the surfactant, conventionally known compounds can be exemplified. Among them, fluorine-based compounds are particularly preferred.

Moreover, a solvent may be contained in the composition for retardation layer formation, and it is suitable to use an organic solvent. Examples of the organic solvent include amide (eg N,N-dimethylformamide), sulfene (eg such as dimethyl sulfoxide), heterocyclic compounds (such as pyridine), hydrocarbons (such as benzene, hexane), halogenated alkanes (such as chloroform, dichloromethane), esters (such as methyl acetate, ethyl acetate) esters, butyl acetate), ketones (eg acetone, butanone), ethers (eg tetrahydrofuran, 1,2-dimethoxyethane). Among them, halogenated alkanes and ketones are preferred. Moreover, 2 or more types of organic solvents can be used together.

In addition, the composition for forming a retardation layer may contain vertical alignment accelerators such as a polarizer interface side vertical alignment agent and an air interface side vertical alignment agent, as well as a polarizer interface side horizontal alignment agent and an air interface side horizontal alignment agent, etc. Various alignment agents for horizontal alignment accelerators. In addition, the composition for retardation layer formation may contain an adhesion improver, a plasticizer, a polymer, etc. in addition to the above-mentioned components.

The above-mentioned active energy rays include ultraviolet rays, visible light, electron beams, and X-rays, preferably ultraviolet rays. Examples of light sources for the active energy rays include: low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, emitting wavelengths ranging from 380 to 440 nm LED light source, chemical lamp, black light lamp, microwave excited mercury lamp, metal halide lamp, etc.

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

The ultraviolet rays may be irradiated once or divided into a plurality of times. Although it varies depending on the polymerization initiator used, the cumulative light intensity at a wavelength of 365 nm is preferably 700 mJ/cm ² or more, more preferably 1,100 mJ/cm ² or more, and more preferably 1,300 mJ/cm 2 ² or more. It is advantageous to increase the polymerization rate of the polymerizable liquid crystal compound constituting the liquid crystal cured layer and to improve the heat resistance by setting it as the above-mentioned integrated light quantity. The integrated light amount at a wavelength of 365 nm is preferably 2,000 mJ/cm ² or less, and particularly preferably 1,800 mJ/cm ² or less. If it does not fall within the range of the said integrated light quantity, there exists a possibility that the coloring of a liquid crystal hardening layer may be caused.

The thickness of the liquid crystal cured layer is preferably 0.5 μm or more. Moreover, 10 micrometers or less is preferable, and, as for the thickness of a liquid crystal cured layer, 5 micrometers or less is especially preferable. The above upper limit value and lower limit value can be arbitrarily combined. Sufficient durability can be obtained as the thickness of a liquid crystal cured layer is more than the said lower limit. When the thickness of a liquid crystal cured layer is below the said upper limit, it contributes to the reduction of the thickness of the laminated body 1. The thickness of the liquid crystal cured layer can be adjusted so that a layer imparting a retardation of λ/4, a layer imparting a retardation of λ/2, or a desired in-plane retardation value and a thickness direction retardation value of the positive type C layer can be obtained.

In the film-like retardation layer 130, a plurality of retardation layers having respective different retardation characteristics may be laminated. The retardation layer of each layer can be laminated using an adhesive, or a composition containing a polymerizable liquid crystal compound can be applied and cured on the surface of the formed retardation layer.

[Substrate]

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 the function of supporting the alignment layer, and can be a long base material. This base material functions as a releasable support, and can support a liquid crystal cured layer or an alignment layer for transfer. Furthermore, the surface preferably has a peelable adhesive force. The base material includes a light-transmitting thermoplastic resin film, preferably an optically transparent thermoplastic resin film. As a thermoplastic resin film, what was illustrated in the description of the said polarizer protective layer is mentioned.

The substrate can also be given various anti-caking treatments. Examples of the anti-caking treatment include easy bonding treatment, treatment such as kneading fillers, embossing (knurling treatment), and the like. By applying this anti-caking treatment to the base material, the adhesion of the base materials to each other when the base material is wound up, that is, so-called caking, can be effectively prevented, and the productivity tends to be easily improved.

[alignment layer]

The layer of the cured product containing the polymerizable liquid crystal compound is formed on the substrate via the alignment layer. That is, the base material and the alignment layer are sequentially laminated, and then the cured product containing 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 aligns the molecular axis of the polymerizable liquid crystal compound horizontally, or an alignment layer that aligns the molecular axis of the polymerizable liquid crystal compound obliquely. The alignment layer preferably has a solvent resistance that does not dissolve due to application of a composition containing a polymerizable liquid crystal compound, etc. described later, and is preferably used in a heat treatment for removing a solvent or aligning a liquid crystal compound. Those with heat resistance. Examples of the alignment layer include: an alignment layer containing an alignment polymer, a photo-alignment film, and a groove alignment layer in which a concave-convex pattern or a plurality of grooves are formed on the surface for alignment. The thickness of the alignment layer is usually in the range of 10 nm or more and 10000 nm or less.

In addition, the alignment layer may have a function of supporting the liquid crystal cured layer and function as a releasable support. The liquid crystal cured layer for transfer may be supported, and the surface may have adhesive force of such a degree that it can be peeled off.

The resin used in the alignment layer is a resin polymerized by a polymerizable compound. The polymerizable compound is a compound having a polymerizable group, and is usually a non-liquid crystalline polymerizable non-liquid crystalline compound that is not in a liquid crystal state. Polymerization is carried out by the reaction of the polymerizable groups of the polymerizable compound with each other The compound is polymerized to form a resin. This resin is used as an alignment layer for aligning the polymerizable liquid crystal compound in the formation stage of the liquid crystal hardened layer, as long as it is not included in the liquid crystal hardened layer and is used as a resin that is a material of a generally known alignment layer. It does not specifically limit, The hardened|cured material etc. which hardened the monofunctional or polyfunctional (meth)acrylate type monomer conventionally generally known in the presence of a polymerization initiator can be used. Specifically, the (meth)acrylate-based monomer may, for example, include 2-ethylhexyl acrylate, cyclohexyl acrylate, diethylene glycol mono-2-ethylhexyl ether acrylate, and diethylene glycol monophenyl Ether Acrylate, Tetraethylene Glycol Monophenyl Ether Acrylate, Trimethylolpropane Triacrylate, Lauryl Acrylate, Lauryl Methacrylate, Isobornyl Acrylate, Isobornyl Methacrylate, 2-Phenoxy Acrylate Ethyl ethyl ester, tetrahydrofuran methyl acrylate, 2-hydroxypropyl acrylate, benzyl acrylate, tetrahydrofuran methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, cyclohexyl methacrylate, methyl methacrylate base acrylic acid, urethane acrylate, etc. The resin may be one of these or a mixture of two or more.

After the retardation layer 30 is formed, the alignment layer can be peeled off together with the base material before and after the step of laminating with the film-like linear polarizer 110 .

Moreover, the liquid crystal cured layer may contain an alignment layer for the purpose of improving the peelability with the base material and imparting film strength to the liquid crystal cured layer. When the liquid crystal hardening layer includes an alignment layer, the resin used in the alignment layer is preferably a monofunctional or bifunctional (meth)acrylate-based monomer, imide-based monomer or vinyl ether-based monomer. Hardened product after hardening, etc.

Examples of monofunctional (meth)acrylate-based monomers include alkyl (meth)acrylates having 4 to 16 carbon atoms, β-carboxyalkyl (meth)acrylates having 2 to 14 carbon atoms, and β-carboxyalkyl esters having 2 to 14 carbon atoms. (meth) acrylic acid alkylated phenyl ester, methoxy polyethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate and (meth) acrylate, etc.;

Bifunctional (meth)acrylate-based monomers include: 1,3-butanediol di(meth)acrylate; 1,3-butanediol (meth)acrylate; 1,6-hexanedi alcohol di(meth)acrylate; ethylene glycol di(meth)acrylate; diethylene glycol di(meth)acrylate; neopentyl glycol di(meth)acrylate; triethylene glycol di(meth)acrylate meth)acrylate; tetraethylene glycol di(meth)acrylate; polyethylene glycol diacrylate; bis(acrylooxyethyl) ether of bisphenol A; ethoxylated bisphenol A bis(methyl) ) acrylate; propoxylated neopentyl glycol di(meth)acrylate; ethoxylated neopentyl glycol di(meth)acrylate and 3-methylpentanediol di(meth)acrylate and the like.

In addition, polyimide, polyimide, etc. are mentioned as an imide-type resin after hardening an imide-type monomer. The imide resin may be one of these or a mixture of two or more.

In addition, the resin forming the alignment layer may contain monomers other than monofunctional or bifunctional (meth)acrylate-based monomers, imide-based monomers and vinyl ether-based monomers, monofunctional or bifunctional (methyl) The content ratio of acrylate-based monomer, imide-based monomer, and vinyl ether-based monomer in the total monomers may be 50 mass % or more, preferably 55 mass % or more, particularly preferably 60 mass % or more .

When the alignment layer is included in the film retardation layer 130, the thickness of the alignment layer is usually in the range of 10 nm to 10000 nm. When the alignment of the film retardation layer 130 is in-plane alignment 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 alignment of the film-like retardation layer 130 is vertical alignment with respect to the film surface, it is preferably 100 nm or more and 10000 nm or less. When the thickness of an alignment layer exists in the said range, the peelability of a base material can be improved, and moderate film strength can be provided.

[Adhesive layer]

The adhesive layer 120 for laminating the film-like linear polarizing plate 110 and the film-like retardation layer 130 can usually be an adhesive formed by a pressure-sensitive adhesive (hereinafter also referred to as an adhesive). agent layer.

The storage elastic modulus E(Pa) of the 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 more preferably 9.0×10 ⁴ Pa or more. The storage elastic modulus of the 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 adhesive layer 120 at 25° C. can be measured according to the measurement method described in the column of the following examples.

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

The adhesive layer 120 may be composed of an adhesive composition mainly composed of resins such as (meth)acrylic, rubber, urethane, ester, polysiloxane, and polyvinyl ether. Among them, from the viewpoints of transparency, weather resistance, heat resistance, and storage elastic modulus, an adhesive composition having a (meth)acrylic resin as a base polymer is preferred. The adhesive composition may be of an active energy ray hardening type or a thermosetting type.

The (meth)acrylic resin (base polymer) used in the adhesive composition is suitable, for example, such as butyl (meth)acrylate, ethyl (meth)acrylate, and isooctyl (meth)acrylate. , (meth)acrylic acid 2-ethylhexyl (meth)acrylic acid ester of 1 or 2 or more as a polymer or copolymer of monomers. In the base polymer, it is preferable to copolymerize polar monomers. Examples of polar monomers include (meth)acrylic acid, 2-hydroxypropyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylamide, and N,N (meth)acrylate. - dimethylaminoethyl ester, A monomer having a carboxyl group, a hydroxyl group, an amide group, an amine group, an epoxy group, etc. of glycidyl (meth)acrylate.

The adhesive composition may contain only the above-mentioned base polymer, but usually further contains a cross-linking agent. Examples of the crosslinking agent include: those belonging to metal ions having a valence of two or more and forming a metal carboxylate salt with a carboxyl group; those belonging to a polyamine compound and forming an amide bond with a carboxyl group; those belonging to polyepoxy compounds or polyols Those that form an ester bond with a carboxyl group; those that belong to a polyisocyanate compound and those that form an amide bond with a carboxyl group. Among them, polyisocyanate compounds are preferred.

The formation of the adhesive layer 120 can be carried out, for example, by dissolving or dispersing the adhesive composition in an organic solvent such as toluene or ethyl acetate to prepare an adhesive liquid, and directly applying this to the layered body. The method of forming an adhesive layer on the object surface; or a sheet-shaped adhesive layer is pre-formed on the release film (separation film) after the release treatment is applied, and then this is moved to the film-shaped linear polarizer 110 or The mode of the target surface of the film-like retardation layer 130 .

The release film may be a film composed of polyethylene-based resins such as polyethylene, polypropylene-based resins such as polypropylene, polyester-based resins such as polyethylene terephthalate, and the like. Among them, a stretched film of polyethylene terephthalate is preferred.

The adhesive layer 120 may contain any components, such as glass fibers, glass beads, resin beads, fillers composed of metal powder or other inorganic powders, pigments, colorants, antioxidants, ultraviolet absorbers, antistatic agents, and the like.

Examples of the antistatic agent include ionic compounds, conductive fine particles, and conductive polymers, but ionic compounds are suitably used.

The cationic component constituting the ionic compound may be an inorganic cation or an organic cation.

Examples of organic cations include pyridinium cations, imidazolium cations, ammonium cations, sulfonium cations, phosphonium cations, piperidinium cations, pyrrolidinium cations, and the like. , and inorganic cations include lithium ions, potassium ions, and the like.

On the other hand, the anion component constituting the ionic compound may be an inorganic anion or an organic anion, and from the viewpoint of imparting an ionic compound excellent in antistatic performance, an anion component containing a fluorine atom is preferred. Examples of the anion component containing a fluorine atom include hexafluorophosphate anion [(PF ₆ ^- )], bis(trifluoromethanesulfonyl)imide anion [(CF ₃ SO ₂ ) ₂ N ^- ], bis(fluorosulfonyl) Acyl)imide anion [(FSO ₂ ) ₂ N ^- ] and the like.

[other layers]

The laminate 1 may further have, for example, at least one of a bonding layer and a surface protective film.

[lamination layer]

The laminated body 1 may have a bonding layer disposed on the outermost surface of the film-like retardation layer 130 side. The bonding layer may be a layer for bonding a touch sensor panel, an image display element, or the like to the laminate 1 . The adhesive layer is usually composed of an adhesive. The adhesives constituting the bonding layer can be used without particular limitations, and conventionally known adhesives can be used, including acrylic polymers, urethane polymers, polysiloxane polymers, and polyvinyl ether polymers Adhesives for basic polymers such as materials. Moreover, an active energy ray hardening type adhesive agent, a thermosetting type adhesive agent, etc. may be sufficient.

[Surface protection film]

The surface protection film may be arranged on the side of the cured resin layer 100 of the laminate 1 . The laminated body 1 may contain a surface protection film for protecting the surface (typically, the surface of the hardened resin layer). surface protection The film is peeled and removed together with the adhesive layer included in the film after bonding the polarizing plate to, for example, an image display element or other optical members.

The surface protective film is composed of, for example, a base film and an adhesive layer laminated thereon. About the adhesive layer, the description about the above-mentioned bonding layer is applied. The resin constituting the base film may be, for example, a polyethylene-based resin such as polyethylene, a polypropylene-based resin such as polypropylene, and a polyester-based resin such as polyethylene terephthalate or polyethylene naphthalate , Polycarbonate resins and other thermoplastic resins. Polyester resins, such as polyethylene terephthalate, are preferable.

The thickness of the surface 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, strength tends to be easily imparted to the layered body 1 .

[Layer Configuration of Laminated Body]

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

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

[Manufacturing method of laminated body]

The laminated body can be produced by, for example, a method including a bonding step of bonding the film-shaped linear polarizing plate 110 including the cured resin layer 100 and the film-shaped retardation layer 130 through the adhesive layer 120 . In the bonding step, when the layers are bonded via the bonding layer, in order to improve the adhesion, it is preferable to apply surface activation treatment such as corona treatment to one or both surfaces of the bonding surface.

The cured resin layer 100 , the film-like linear polarizing plate 110 , and the film-like retardation layer 130 can be manufactured in the above-described manner, respectively.

The adhesive layer 120 can be prepared as an adhesive sheet. The adhesive sheet can be produced by the following methods: for example, the adhesive composition is dissolved or dispersed in an organic solvent such as toluene or ethyl acetate to prepare an adhesive liquid, and the release film is applied to the release film after the mold release treatment. This is formed into a sheet-like layer composed of an adhesive, and then other release films are further attached to the adhesive layer. The layers can be bonded by a method of peeling off one of the peeling films and pasting the adhesive sheet on one of the layers, then peeling off the other peeling film and pasting the other layer.

As a method of applying the adhesive liquid to the release film, a die coater, a comma coater, a reverse roll coater, a gravure coater, a rod coater, and a wire bar coater can be used. Common coating techniques such as machine, knife coater, air knife coater, etc.

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

The manufacturing method of a laminated body may further comprise the grinding|polishing process of grinding|polishing the end surface of a laminated body. By making the manufacturing method of a laminated body contain a grinding|polishing process, the laminated body which has a grind|polished end surface can be obtained.

The grinding step will be described with reference to FIG. 4 . The grinding step may include, for example, the following steps:

[a] the first step of stacking a plurality of laminates to obtain the laminate W; and

[b] Cutting is performed by rotating the rotary tool 60 having a cutting edge relative to the layered product W in a direction parallel to the end face of the layered product W and orthogonal to the direction of the layered layering about the axis of rotation R The second step of processing the end face of the laminate W.

In the method for producing the layered body 1, for example, after the first step (the above-mentioned [a]), the four sides of the layered body 1 having a square shape in plan view can be processed by the second step ( Grinding is carried out in the above [b]). Next, with respect to any one of the corners and/or any of the four sides of the square-shaped laminated body 1 , a notch can be formed by polishing in the second step (the above-mentioned [b]), and notch processing can be performed.

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 sheets of the raw material layered product contained in the layered product W is not particularly limited, and the layered product W may be, for example, one in which 100 to 500 layers of the layered product are stacked. The layered product constituting the layered product W may be cut out from, for example, an elongated layered product having a layered structure of the layered product.

The second step is a step of forming a layered body having a polished end surface by cutting the end surface of the layered product W obtained in the first step by rotating the tool 60 .

For example, as shown in FIG. 4 , the cutting process performed in the second step can be performed by a device including a support portion 50 and two rotating tools 60 . The support portion 50 presses the laminate W from above and below, and is used to prevent the laminate W itself from moving during cutting. Moreover, it is fixed in such a way that the stacked laminated body does not deviate. The rotary tool 60 is for cutting the end face of the layered product W, and can be rotated around the rotation axis R. As shown in FIG.

The support part 50 may include: a flat substrate (moving means for the laminate W) 51; a door-shaped frame 52 arranged on the substrate 51; a rotary table arranged on the substrate 51 and rotatable about a central axis 53; and a pressure cylinder 54 which is arranged in the frame body 52 at a position opposite to the rotary table 53 and can move up and down. The laminate W is clamped and fixed by the rotary table 53 and the pressure cylinder 54 via an auxiliary tool (jig, also known as a jig) 55 .

The rotating tool 60 has a disk-shaped rotating body that rotates around the rotating axis R. The direction of rotation of the rotating body is the direction indicated by the arrow in FIG. 4 . On the disk surface of the rotating body (the surface opposite to the end surface of the laminate W and parallel to the end surface), a plurality of (for example, 2 to 10, preferably 3 to 10) are arranged at intervals along the rotation direction of the rotating body. 7) cutting edges. The rotation axis R is preferably set so as to pass through the center of the disk surface of the rotating body. The cutting edge is provided so as to protrude from the disk surface of the rotating body to the end surface side of the laminated object W, and the rotating body is rotated about the rotation axis R in a state where the cutting edge is in contact with the end surface of the laminated object W, whereby the rotating body can be rotated. The end face of the laminate W is cut.

On both sides of the base plate 51, the two rotary tools 60 are arranged to face each other. The rotary tool 60 can be moved in the direction of the rotation axis R according to the size of the laminate W, and the substrate 51 can be moved by the two rotary tools 60 between each other. During cutting, the laminate W is fixed to the support portion 50, and after the position of the rotary tool 60 in the direction of the rotation axis R is appropriately adjusted, the rotary tool 60 is rotated around the rotation axis R, and is passed through. The substrate 51 is moved so that the laminates W face the rotating tools 60 against each other. Thereby, the rotary tool 60 is made to face the laminated object W along the direction parallel to the end face of the laminated object W and orthogonal to the lamination direction. The cutting edge of the rotary tool 60 can be moved in such a way as to abut the exposed end faces of the laminate W, and the cutting process of removing these end faces can be performed.

The relative movement 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). The rotational speed of the rotary tool 60 can be selected from, for example, a range of 2,000 rpm or more and 8,000 rpm or less (more typically, 2,500 rpm or more and 6,000 rpm or less).

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

<Image Display Device>

The laminate of the present invention can be used in an image display device. An 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. As an image display apparatus, a liquid crystal display apparatus, an organic electroluminescence (EL: Electroluminescence) display apparatus, an inorganic electroluminescence (EL) display apparatus, a touch panel display apparatus etc. are mentioned, for example. The laminated body may be arranged on the viewing side of the image display panel. The layered product can be layered on the image display device through the bonding layer.

The image display device may be a flexible image display device. The flexible image display device is a bendable 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 a flexible image display apparatus, the laminated body for flexible image display apparatuses is arrange|positioned on the viewing side with respect to an organic electroluminescent display panel. The laminated body for flexible image display apparatuses can be equipped with the front panel mentioned later, the laminated body of this invention, and a touch sensor. The order of lamination of these front panels, laminates, and touch sensors is arbitrary. better The front panel, the laminate of the present invention, and the touch sensor are laminated in this order from the viewing side. It is also preferable that the front panel, the touch sensor, and the laminated body of the present invention are laminated in this order from the viewing side. When there is a polarizer on the viewing side of the touch sensor, the wiring pattern of the touch sensor becomes difficult to be seen, so that the visibility of the displayed image becomes good, which is preferable. Each member can be laminated using an adhesive, an adhesive, or the like. In addition, a light-shielding pattern formed on at least one side of any layer of the front panel, the polarizer, and the touch sensor may be provided.

[front panel]

A front panel may be arranged on the viewing side of the laminate of the present invention. The front panel may be laminated to the laminate via the subsequent lamination. For the next layer, for example, the above-mentioned adhesive layer or adhesive layer is exemplified.

As a front panel, what contains a hard-coat layer etc. on at least one surface of glass and a resin film is mentioned. As the glass, for example, high penetration glass or tempered glass can be used. Especially in the case of using a thin transparent surface material, the glass after chemical strengthening is preferably applied. The thickness of the glass can be set to, for example, 100 μm to 5 mm.

The front panel formed by including a hard coat layer on at least one side of the resin film may not be as rigid as the conventional glass, but has a flexible property. The thickness of the hard coat layer is not particularly limited, and may be, for example, 5 to 100 μm.

The resin film may be a film formed of the following polymers: cycloolefin-based derivatives having units of cycloolefin-containing monomers such as norbornene or polycyclic norbornene-based monomers, cellulose (cellulose diacetate) , cellulose triacetate, cellulose acetate butyrate, cellulose isobutyl ester, cellulose propionate, cellulose butyrate, cellulose acetate propionate), ethylene-vinyl acetate copolymer, polycyclic olefin, polyester , polystyrene, polyamide, polyetherimide, polyacrylic acid, polyimide, polyamideimide, polyetherimide, polyetherimide, polyethylene, polypropylene, polymethylpentene, poly Vinyl chloride, polydichloride Ethylene, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether dust, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, poly Polymers such as ethylene naphthalate, polycarbonate, polyurethane, epoxy, etc. As the resin film, an unstretched, uniaxially or biaxially stretched film can be used. These polymers can be used alone or in combination of two or more. The resin film is preferably: a polyimide film or a polyimide film, a uniaxially or biaxially stretched polyester film excellent in transparency and heat resistance; The large-scale cycloolefin derivative film, polymethyl methacrylate film; and cellulose triacetate and isobutyl cellulose film with transparency and no optical anisotropy. The thickness of the resin film is 5 to 200 μm, preferably 20 to 100 μm.

[shading pattern]

A light-shielding pattern (light-shielding portion) may be formed on the display element side of the front panel. The light-shielding pattern can hide each wiring of the display device from being viewed by the user. The color and/or material of the shading pattern is not particularly limited, and it can be formed of resin materials with various colors such as black, white, and gold. In one embodiment, the thickness of the light-shielding pattern may be in the range of 2 μm to 50 μm, preferably 4 μm to 30 μm, and particularly preferably 6 μm to 15 μm. In addition, in order to suppress the mixing of air bubbles and the visibility of the boundary portion due to the level difference between the light-shielding pattern and the display portion, the light-shielding pattern may be given a shape.

[touch sensor]

Touch sensors are used as input means. Various styles such as resistive film method, surface elastic wave method, infrared method, electromagnetic induction method, and electrostatic capacitance method have been proposed as touch sensors, but any method is acceptable. Among them, the electrostatic capacitance method is preferable. The electrostatic capacitive touch sensor is divided into an active area and an inactive area located on the outer contour of the active area. The active area is an area corresponding to the area (display portion) where the screen is displayed on the display panel, and is connected to the The inactive area is the area corresponding to the area (non-display portion) where the screen is not displayed in the display device. The touch sensor may include: a substrate with flexible properties; a sensing pattern formed on an active area of the substrate; and an inactive area formed on the substrate, and separated from the sensing pattern and the electrode pad for communicating with the outside The driving circuit is connected to each sensing line. The substrate with flexible properties can be made of the same material as the transparent substrate of the aforementioned window. From the viewpoint of suppressing possible cracking of the touch sensor, the substrate of the touch sensor preferably has a toughness of 2,000 MPa% or more. Particularly preferred are those with a toughness of 2,000 MPa% to 30,000 MPa%. Here, toughness is defined as the lower area of the curve up to the point of failure in the stress (MPa)-strain (%) curve (Stress-Strain Curve) obtained by the tensile test of the polymer material.

(Example)

The present invention will be described in more detail below by means of examples. "%" and "part" in the example are mass % and mass part unless otherwise specified.

[Martens hardness]

The cyclic olefin resin (COP: Cyclic Olefin Polymer) film having a hard coat (HC: Hard Coat) layer used in the Examples and Comparative Examples was cut into a size of 40 mm×40 mm, and the adhesive layer was interposed therebetween. The glass plate was bonded to the cyclic olefin-based resin film side to prepare a measurement sample. In an environment with a temperature of 23° C. and a relative humidity of 55%, using an ultra-micro hardness tester (FISCHERSCOPE HM2000: manufactured by Fischer Instruments Co., Ltd.), the hard coat side of the sample for measurement was tested at a pressing speed of 1 mN/5 sec. After applying a load to the surface of , the creep time (time to maintain a load of 1 mN) was set to 5 s and the Martens hardness at 23°C was measured.

[Stored elastic modulus]

The storage elastic modulus of the 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 adhesive layer, and this was used as a sample for measurement of the storage elastic modulus E.

For the above-mentioned sample, the storage elastic modulus (Pa) was measured by the torsional shear method under the following conditions using a viscoelasticity measuring apparatus (manufactured by Physica, MCR300) in accordance with JIS K7244-6.

[Measurement conditions]

Normal force FN: 1N

Strain γ: 1%

Frequency: 1Hz

Temperature: 25℃

[layer thickness]

The measurement was performed using a contact-type film thickness measuring apparatus (“MS-5C” manufactured by Nikon Co., Ltd.).

[Example 1]

(Fabrication of laminated body)

First, a linear polarizing layer (thickness 8 μm) in which iodine was adsorbed and aligned on a polyvinyl alcohol-based resin film was prepared. A cyclic olefin-based resin (COP) film (thickness 25 μm) (hereinafter sometimes referred to as "HC(A)-COP) having a hard coat (HC) layer with a Martens hardness of 2.5×10 ² is formed through a water-based adhesive. film") on the COP film side (the opposite side to the HC layer side), and attached to one side of the linear polarizing layer. The HC layer of the polarizer protective layer is attached to the acrylic adhesive layer side of the surface protection film (thickness 53 μm) with the acrylic adhesive layer (thickness 15 μm) formed on the polyester resin film (thickness 38 μm). superior. A triacetyl cellulose (TAC: Triacetyl Cellulose) film (thickness: 20 μm) as a polarizer protective layer was bonded to the other surface of the linear polarizing layer via an aqueous adhesive. Thereby, a film-like linear polarizing plate (1) with a surface protective film was obtained. The film-shaped linear polarizing plate (1) with a surface protective film is laminated in sequence with a surface protective film (polyester-based resin film, acrylic adhesive layer), HC(A)-COP film (HC layer, COP film), Linear polarizer and TAC film. The film-shaped linear polarizer (1) is adjusted to have a transmittance of 0.01% or less at 380nm, a transmittance of 0.07% or less at 390nm, and a transmittance of 35% at 440nm with the surface protective film (thickness 53μm) removed. Above, the transmittance of 550nm is more than 41%, and the transmittance of 610nm is more than 41.5%.

Next, a film-like retardation layer is prepared, in which a λ/4 plate (thickness: 2 μm) as a cured product layer of a polymerizable liquid crystal compound and an adhesive cured layer (thickness of an ultraviolet curable adhesive) are laminated in this order. 2 μm), and a positive C plate (thickness 3 μm) as a cured product layer of the polymerizable liquid crystal compound. The TAC of the film-like linear polarizing plate (1) with the surface protection film attached by an adhesive layer (thickness 15 μm) composed of an adhesive having a storage elastic modulus of 1.2×10 ⁵ Pa at 25°C λ/4 plate of film and film-like retardation layer. Next, the adhesive layer (1) with a release film was prepared, and the adhesive layer (1) with a release film was formed on the release film (thickness 38 μm) using an acrylic adhesive (thickness 25 μm) . The bonding layer of the bonding layer (1) with a release film is laminated on the positive C plate side of the film-shaped retardation layer bonded on the film-shaped linear polarizing plate (1) with a surface protection film, and cut out. The length of the long side was 37 mm, and the length of the short side was cut into a rectangle of 35 mm to obtain a layered body (1). The laminate (1) is a film-like linear polarizing plate (1) with a surface protective film (surface protective film, HC(A)-COP film, linear polarizing layer, and TAC film), an adhesive layer, a film-like Retardation layer (λ/4 plate, bonding layer, positive C plate) and bonding layer (1) with release film (bonding layer, release film). In the laminated body (1), from the film-shaped linear polarizing plate (HC(A)-COP film, linear polarizing layer, TAC film) to the film-shaped retardation layer (λ/4 plate, adhesive cured layer, positive type C The thickness of the laminated part up to the plate) was 77 μm. In addition, the direction of the short side of the layered body (1) is parallel to the absorption axis of the linear polarizing layer.

(Production of Laminates with Polished End Surfaces)

Using the apparatus shown in FIG. 4, following the steps of the first step described above to prepare a layered product W on which the raw material layered body is layered, and following the steps of the second step described above, for 4 corresponding to the raw material layered body. The end face of each edge is ground. In the above-mentioned polishing, the relative movement 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 the end surface grinding, the peripheral edge portion of the laminate was observed with an optical microscope to measure the length of cracks generated in the peripheral edge of the laminate.

[Comparative Example 1]

The TAC of the film-like linear polarizing plate (1) with the surface protection film attached by an adhesive layer (thickness 17 μm) composed of an adhesive with a storage elastic modulus of 2.5×10 ⁴ Pa at 25°C A laminated body was obtained by the same procedure as Example 1 except for the λ/4 plate of the film and the film-like retardation layer. About the obtained laminated body, the peripheral edge part of a laminated body was observed with an optical microscope, and the length of the crack which generate|occur|produced in the peripheral edge part of a laminated body was measured.

[Comparative Example 2]

A linear polarizing layer (thickness 8 μm) in which iodine was adsorbed and aligned on a polyvinyl alcohol-based resin film was prepared. A cyclic olefin resin (COP) film (thickness 25 μm) (hereinafter sometimes referred to as "HC(B)-COP) having a hard coat (HC) layer with a Martens hardness of 2.3×10 ² was formed through an aqueous adhesive. film") on the COP film side (the opposite side to the HC layer side), and attached to one side of the linear polarizing layer. The HC layer of the polarizer protective layer is attached to the acrylic adhesive layer side of the surface protection film (thickness 53 μm) with the acrylic adhesive layer (thickness 15 μm) formed on the polyester resin film (thickness 38 μm). superior. A triacetate cellulose (TAC) film (thickness 20 μm) as a polarizer protective layer was bonded to the other surface of the linear polarizing layer via an aqueous adhesive. Thereby, a film-like linear polarizing plate (1) with a surface protective film was obtained. The film-shaped linear polarizing plate (1) with a surface protective film is sequentially laminated with a surface protective film (polyester-based resin film, acrylic adhesive layer), HC(B)-COP film (HC layer, COP film), Linear polarizer and TAC film. This polarizer is adjusted to have a transmittance of 0.02% or less at 380nm, less than 12% at 390nm, more than 35% at 440nm, and more than 35% at 550nm with the surface protective film (thickness 53μm) removed. The penetration rate is more than 41.5%, and the 610nm transmission rate is more than 41.5%. Except for this, a layered body was obtained in the same procedure as in Example 1. About the obtained laminated body, the peripheral edge part of a laminated body was observed with an optical microscope, and the length of the crack which generate|occur|produced in the peripheral edge part of a laminated body was measured.

[Comparative Example 3]

The TAC of the film-like linear polarizing plate (1) with the surface protection film attached by an adhesive layer (thickness 17 μm) composed of an adhesive with a storage elastic modulus of 2.5×10 ⁴ Pa at 25°C A laminate was obtained in the same procedure as in Comparative Example 1 except for the λ/4 plate of the film and the film-like retardation layer. About the obtained laminated body, the peripheral edge part of a laminated body was observed with an optical microscope, and the length of the crack which generate|occur|produced in the peripheral edge part of a laminated body was measured.

[Table 1]

Claims (10)

A laminated body is provided with a hardened resin layer, a film-shaped linear polarizing plate, an adhesive layer and a film-shaped retardation layer in this order, wherein, The film-like retardation layer includes a liquid crystal cured layer, When the Martens hardness of the cured resin layer at a temperature of 23°C is set to HM (N/mm ² ), the laminate satisfies the following formula (1): HM≧2.4×10 ² (N/mm ² ) (1) When the storage elastic modulus of the aforementioned adhesive layer at a temperature of 25°C is set to E (Pa) and the thickness is set to T (μm), the laminate satisfies the following formula (2): E/T≧2.5×10 ³ (Pa/μm) (2). 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 3.0×10 ⁴ 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 layered body according to any one of claims 1 to 5, wherein the layered body is blade-shaped. The laminate according to any one of claims 1 to 6, wherein the laminate has a polished end surface. A laminate for a flexible image display device, comprising the laminate according to any one of claims 1 to 7, a front panel, 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 a flexible image display device according to claim 8.

Images