KR20200133668A - Long laminate and organic el display device - Google Patents

Abstract

An objective of the present invention is to provide a long lamination which can be manufactured more simply and with good productivity, has a high effect of suppressing light leakage in an oblique direction when long lamination is introduced as a member configuring an elliptical polarizing plate, and also can obtain a retardation plate having small changes in the color of the front surface thereof and the colors thereof in all directions. The long lamination comprises a first retardation layer, an optical alignment film, and a second retardation layer in sequence, and satisfies formula (1), 10° <= θa <= 30° or 60° <= θa <= 80° and formula (2), 2θa + 40° <= θb <= 2θa + 50°. One of the first retardation layer and the second retardation layer is a stretchable film, and the other retardation layer is a liquid crystal cured film. In formulas (1) and (2), θa is a smaller angle among angles formed by the longitudinal direction of the long lamination and a slow axis of the first retardation layer, and θb is a smaller angle among angles formed by the longitudinal direction of the first retardation layer and a slow axis of the second retardation layer.

Description

Long laminated body and organic EL display device TECHNICAL FIELD [LONG LAMINATE AND ORGANIC EL DISPLAY DEVICE}

The present invention relates to a long laminate and an organic EL display device.

The elliptically polarizing plate is an optical member in which a polarizing plate and a retardation plate are stacked, and in a device that displays an image in a planar state such as an organic EL image display device, in order to prevent light reflection from electrodes constituting the device. Is being used. In order to suppress light leakage in the oblique direction in this elliptically polarizing plate, Patent Literature 1 describes an optical film in which two retardation plates each composed of a horizontally aligned liquid crystal cured film are combined to provide optical compensation characteristics.

Japanese Patent Application Publication No. 2015-163938

However, the optical film produced using two horizontally aligned liquid crystal cured films as a retardation plate is generally produced by independently preparing each horizontally aligned liquid crystal cured film, and then further bonding them together in many cases. . In addition, even in the case of forming two horizontally aligned liquid crystal cured films in succession, it is necessary to repeat the application process of the composition for forming each horizontally aligned liquid crystal cured film, so that the manufacturing process is apt to become complicated and productivity is liable to decrease. There was.

In addition, in recent years, there is a continuous demand for thinning of displays such as image display panels, and additional thinning is also required for a retardation plate and an elliptically polarizing plate which are one of the constituent elements.

The present invention can be manufactured more simply and with good productivity, and when introduced as a member constituting an elliptically polarizing plate, a thin film can be formed by omitting the protective layer on one side of the polarizer, and further, light leakage It is an object of the present invention to provide a long stacked body capable of obtaining a retardation plate having a high suppression effect on the front surface and a small change in front color.

This invention provides the following preferable aspects.

[1] As a long laminate having a first retardation layer, a photoalignment film, and a second retardation layer in this order,

The long laminated body satisfies the following formulas (1) and (2), one of the first phase difference layer and the second phase difference layer is a stretched film, and the other is a liquid crystal cured film.

10° ≤ θa ≤ 30° or 60° ≤ θa ≤ 80° (1)

2θa + 40° ≤ θb ≤ 2θa + 50° (2)

[In the formula, θa is the smaller of the angles between the long direction of the long stacked body and the slow axis of the first retardation layer, and θb is the angle between the long direction of the first retardation layer and the slow axis of the second phase difference layer. It's a small angle.]

[2] The elongate laminate according to the above [1], wherein the first phase difference layer satisfies the following equation (3), and the second phase difference layer satisfies the following equation (4).

200 ㎚ <Re(550) ＜ 320 ㎚ (3)

100 ㎚ <Re(550) ＜ 160 ㎚ (4)

[In the formula, Re(550) represents an in-plane retardation value at a wavelength of 550 nm.]

[3] The long laminate according to [1] or [2], wherein the photoalignment film has a photoreactive group, and the photoreactive group is a dimerization reactive photoreactive group.

[4] The long laminate according to any one of [1] to [3], wherein the number average molecular weight of the photoalignment film is from 20000 to 100000.

[5] The elongate laminate according to any one of [1] to [4], wherein the thickness of the photoalignment film is 100 to 300 nm.

[6] The elongated laminate further has a transparent protective layer, an adhesive layer, and a polarizing layer,

Having a transparent protective layer, an adhesive layer, a polarizing layer, an adhesive layer, a first retardation layer, a photoalignment film, and a second retardation layer in this order,

The elongated laminate according to any one of [1] to [5], wherein the first retardation layer is a stretched film, and the second retardation layer is a liquid crystal cured film.

[7] The long laminate according to [6], wherein the total light transmittance in 380 nm of the transparent protective layer is 30% or less.

[8] The long laminate according to [6] or [7], wherein iodine is contained as the dichroic dye of the polarizing layer, and the absorption axis of the polarizing layer is in the long direction of the long laminate.

[9] An organic EL display device comprising a sheet body obtained from the elongate laminate according to any one of [1] to [8].

According to the present invention, it is possible to manufacture more easily and with good productivity, and when introduced as a member constituting an elliptically polarizing plate, it is possible to form a thin film by omitting the protective layer on one side of the polarizer. It is possible to provide a long stacked body capable of obtaining a retardation plate having a high leakage suppression effect and a small front color change.

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

Hereinafter, embodiments of the present invention will be described in detail. In addition, the scope of the present invention is not limited to the embodiments described herein, and various changes can be made without impairing the gist of the present invention.

The elongated laminate of the present invention has a first retardation layer and a second retardation layer in this order, and has a photoalignment film between the first retardation layer and the second retardation layer. Hereinafter, an example of the layer configuration of the elongated laminate of the present invention will be described based on Fig. 1, but the laminate of the present invention is not limited to these aspects.

1: is a figure which shows the cross section when the long laminated body of this invention was cut in the thickness direction. The elongate laminate 11 of the present invention is formed by laminating the first phase difference layer 1, the photoalignment film 3, and the second phase difference layer 2 in this order. In the layer configuration of the elongated laminate 11 shown in FIG. 1, the photoalignment film 3 is directly formed on the first retardation layer 1, and the first retardation layer 1 and the photoalignment film 3 are Exist adjacent to each other. Moreover, in the layer structure of the elongate laminated body 11 shown in FIG. 1, the 2nd phase difference layer 2 is formed directly on the photoalignment film 3, and the photoalignment film 3 and the 2nd phase difference layer 2 ) Exist adjacent to each other. Between the first retardation layer (1), the photoalignment film (3), and the second retardation layer (2), as long as the effect of the present invention is not affected, for example, an adhesive agent layer or a protective layer, etc. Although a layer may be included, the first retardation layer (1) and the optical alignment film (3) can be further improved by reducing the thickness of the laminate to further improve the effect of suppressing the change in front color and the flexibility when introduced into the elliptically polarizing plate. And the second phase difference layer 2 are preferably present adjacent to each other in this order.

In the elongate laminate of the present invention, one of the first phase difference layer and the second phase difference layer is a stretched film, the other is a liquid crystal cured film, and the following formulas (1) and (2) are satisfied.

10° ≤ θa ≤ 30° or 60° ≤ θa ≤ 80° (1)

2θa + 40° ≤ θb ≤ 2θa + 50° (2)

In equations (1) and (2), θa is the smaller of the angle between the long direction of the long stacked body and the slow axis of the first retardation layer, and θb is the long direction of the first retardation layer and the second retardation layer. It is the smaller of the angles formed by the slow axis.

The long laminate of the present invention may be formed by laminating a retardation layer that is a stretched film and a retardation layer that is a liquid crystal cured film. When the long laminate of the present invention further includes a polarizing layer, since the retardation layer made of a stretched film can also function as a protective layer of the polarizing layer, a protective layer is not formed on one side of the polarizing layer (polarizer). A retardation layer can be laminated. For this reason, in such a case, it is preferable that the retardation layer laminated to the polarizing layer via an adhesive layer is a stretched film, and the retardation layer laminated on the opposite side of the polarizing layer of the retardation layer is a liquid crystal cured film.

In the long laminate of the present invention, the smaller angle (θa) of the angles formed by the slow axis of the first retardation layer with respect to the long axis direction of the long laminate is 10° to 30° or 60° to 80°, The smaller angle (θb) of the angle formed by the long direction of the first phase difference layer and the slow axis of the second phase difference layer is in the range of 2θa + 40° to 2θa + 50°. When the first phase difference layer and the second phase difference layer are stacked to satisfy the above relationship, that is, equations (1) and (2), the elongated layered product of the present invention is introduced as a member constituting the elliptically polarizing plate It has a high suppression effect against light leakage, and can be a retardation plate having a small change in front color.

From the viewpoint of being easy to obtain a retardation plate that has a high suppression effect on light leakage or color change and exhibits excellent optical properties, the value of θa is preferably 13° to 27° or 63° to 77°, more preferably 15° to 25° or 65° to 75°. Further, the value of θb is preferably in the range of 2θa + 42° to 2θa + 48°, more preferably 2θa + 44° to 2θa + 46°.

In addition, in the long laminate of the present invention, the slow axis of the first retardation layer is at a specific angle that satisfies the equation (1) with respect to the long direction of the long laminate (that is, it is also the long direction of the first retardation layer) , On the first retardation layer that generates a slow axis in the above relationship with respect to the long stacked body, satisfying the equation (2) for the long direction of the first retardation layer (that is, it is also the long direction of the second retardation layer) A second phase difference layer that generates a slow axis at a specific angle is stacked. The elongate laminate of the present invention having such a configuration is, for example, polymerization containing a polymerizable liquid crystal compound for forming a second retardation layer on the stretched film while conveying the long stretched film as the first retardation layer. It is possible to continuously manufacture by applying a liquid crystal composition and curing in a state in which the polymerizable liquid crystal compound is aligned. In addition, for example, in the case of forming an elliptically polarizing plate by laminating a polarizing film including a polarizing layer, a long polarizing film wound in a roll shape is rolled by a so-called Roll to Roll method, and the first phase difference layer and the second phase difference of the present invention It can be laminated on an elongate laminate composed of layers. Thereby, for example, it is possible to continuously manufacture a final product such as an elliptically polarizing plate using a commercially available general polarizing film roll, and it is possible to manufacture an elliptically polarizing plate more simply and with good productivity.

In the elongated laminate of the present invention, it is preferable that the first phase difference layer satisfies the following equation (3), and that the second phase difference layer satisfies the following equation (4).

200 ㎚ <Re(550) ＜ 320 ㎚ (3)

100 ㎚ <Re(550) ＜ 160 ㎚ (4)

[In the formula, Re(550) represents an in-plane retardation value at a wavelength of 550 nm.]

If the first retardation layer has optical properties that satisfy Equation (3) and the second retardation layer has optical properties that satisfy Equation (4), the first retardation layer and the second retardation layer are stacked When introduced as an elliptically polarizing plate, the resulting long laminate has a higher suppression effect against light leakage and front color change, and becomes a retardation plate excellent in optical properties.

In the present invention, the first retardation plate more preferably has an optical property that satisfies the equation (5), and still more preferably the equation (6).

180 ㎚ <Re(550) ＜ 300 ㎚ (5)

200 nm <Re(550) <280 nm (6)

Further, the second retardation plate more preferably has an optical characteristic that satisfies the formula (7), and even more preferably the formula (8).

110 ㎚ <Re(550) ＜ 150 ㎚ (7)

130 ㎚ <Re(550) ＜ 145 ㎚ (8)

It is preferable that both the 1st phase difference layer and the 2nd phase difference layer have the optical characteristic represented by Formula (9), and it is more preferable to have the optical characteristic represented by Formula (9) and Formula (10).

Re(450)/Re(550) ≥ 1.00 (9)

1.00 ≥ Re(650)/Re(550) (10)

[In the formula, Re(λ) represents an in-plane retardation value at a wavelength of λ nm.]

The in-plane retardation value can be adjusted by the thickness d of the first retardation layer and the second retardation layer, respectively. Since the in-plane retardation value is determined by Re(λ) = (nx(λ)-ny(λ)) × d, the desired in-plane retardation value (Re(λ): each phase difference in the wavelength λ (nm) To obtain the in-plane retardation value of the layer), the three-dimensional refractive index and the film thickness d may be adjusted. In the above formula, d denotes the thickness of the target retardation layer, and nx denotes the main refractive index in the wavelength λ nm in a direction parallel to the plane of the retardation layer in the refractive index ellipsoid formed by the retardation layer. And ny represents a refractive index in a wavelength λ nm in a direction parallel to the plane of the retardation layer and perpendicular to the nx direction in the refractive index ellipsoid formed by the retardation layer.

A long laminate (phase difference plate) showing uniform polarization conversion performance in a wide wavelength range of visible light by combining the first and second retardation layers each having optical properties represented by equations (9) and/or equations (10) Can be obtained.

In the present invention, either one of the first retardation layer and the second retardation layer is a retardation layer formed of a stretched film. A stretched film is usually obtained by stretching a substrate. As the substrate, a transparent substrate having transparency capable of transmitting light, particularly visible light, is preferable, and it is preferable that the substrate has a transmittance of 80% or more with respect to a light having a wavelength of 380 to 780 nm. Examples of the transparent substrate include a substrate formed from a light-transmitting resin. Examples of the light-transmitting resin forming the substrate include polyolefins such as polyethylene and polypropylene; Cyclic olefin resins such as norbornene-based polymers; Polyvinyl alcohol; Polyethylene terephthalate; Polymethacrylic acid ester; Polyacrylic acid ester; Cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Polysulfone; Polyethersulfone; Polyether ketone; And polyphenylene sulfide and polyphenylene oxide. From the viewpoint of availability and transparency, polyethylene terephthalate, polymethacrylic acid ester, cellulose ester, cyclic olefin resin, or polycarbonate is preferable.

As for the cellulose ester, some or all of the hydroxyl groups contained in cellulose are esterified, and can be obtained from the market. Moreover, a cellulose ester base material can also be obtained from the market. As a commercially available cellulose ester base material, for example, "Fujitak (registered trademark) film" (Fuji Photographic Film Co., Ltd.); “KC8UX2M”, “KC8UY” and “KC4UY” (Konica Minoltaopt Co., Ltd.), and the like.

Polymethacrylic acid esters and polyacrylic acid esters (hereinafter, polymethacrylic acid esters and polyacrylic acid esters are collectively referred to as "(meth)acrylic acid resins") can be obtained from the market.

Examples of the (meth)acrylic resin include a homopolymer of an alkyl methacrylate or an alkyl acrylate, or a copolymer of an alkyl methacrylate and an alkyl acrylate. As an alkyl methacrylate ester, specifically, methyl methacrylate, ethyl methacrylate, propyl methacrylate, etc., and as an acrylic acid alkyl ester, specifically, methyl acrylate, ethyl acrylate, propyl acrylate, etc. Can be lifted. As such (meth)acrylic resin, a commercially available (meth)acrylic resin can be used. As the (meth)acrylic resin, you may use an impact-resistant grade (meth)acrylic resin.

In order to improve the mechanical strength of the stretched film, the (meth)acrylic resin may contain rubber particles. As the rubber particles, acrylic rubber particles are preferable. Here, the acrylic rubber particles are particles having rubber elasticity obtained by polymerizing an acrylic monomer mainly containing an acrylic acid alkyl ester such as butyl acrylate or 2-ethylhexyl acrylate in the presence of a polyfunctional monomer. The acrylic rubber particles may be those in which particles having such rubber elasticity are formed in a single layer, or may be a multilayer structure having at least one rubber elastic layer. In the multilayered acrylic rubber particles, particles having rubber elasticity as described above are used as the core, and the periphery is covered with a hard alkyl methacrylate ester polymer, and a hard alkyl methacrylate ester polymer is used as the core. And covering the periphery with an acrylic polymer having rubber elasticity as described above, and covering the periphery of the hard core with a rubber-elastic acrylic polymer, and further covering the periphery with a hard alkyl methacrylate-based polymer And the like. It is preferable that the rubber particles formed from the elastic layer have an average diameter of about 50 to 400 nm.

When the (meth)acrylic resin contains rubber particles, the content is usually about 5 to 50 parts by mass per 100 parts by mass of the (meth)acrylic resin. Since the (meth)acrylic resin and the acrylic rubber particles are commercially available in a state in which they are mixed, the commercial item may be used. As an example of a commercially available product of (meth)acrylic resin containing acrylic rubber particles, “HT55X” or “Technoroy S001” sold by Sumitomo Chemical Co., Ltd. can be mentioned. “Technoloy S001” is sold in the form of a film.

Cyclic olefin resin can be easily obtained from the market. Commercially available cyclic olefin resins include “Topas” (registered trademark) [Ticona (Germany)], “Aton” (registered trademark) [JSR Co., Ltd.], “ZEONOR” (registered trademark) [Nippon Xeon Co., Ltd.], “ZEONEX” (registered trademark) [Nippon Xeon Co., Ltd.] and “Apel” (registered trademark) [Mitsui Chemicals Co., Ltd.] are mentioned. Such a cyclic olefin-based resin can be formed into a film by known means such as a solvent casting method and a melt extrusion method to form a substrate. Moreover, a commercially available cyclic olefin resin base material can also be used. Commercially available cyclic olefin resin substrates include “Sushina” (registered trademark) [Sekisui Chemical Industry Co., Ltd.], “SCA40” (registered trademark) [Sekisui Chemical Industry Co., Ltd.], and “Zeonore Film. ”(Registered trademark) [Optes Co., Ltd.] and “Aton Film” (registered trademark) [JSR Co., Ltd.].

When the cyclic olefin resin is a copolymer of a cyclic olefin and an aromatic compound having a chain olefin or a vinyl group, the content ratio of the structural unit derived from the cyclic olefin is usually based on the total structural units of the copolymer. It is 50 mol% or less, Preferably it is a range of 15-50 mol%. Examples of the chain olefin include ethylene and propylene, and examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, and alkyl substituted styrene. When the cyclic olefin resin is a ternary copolymer of a cyclic olefin, a chain olefin, and an aromatic compound having a vinyl group, the content ratio of the structural unit derived from the chain olefin is based on the total structural units of the copolymer. , It is usually 5 to 80 mol%, and the content ratio of the structural unit derived from the aromatic compound having a vinyl group is usually 5 to 80 mol% with respect to all structural units of the copolymer. Such a ternary copolymer has an advantage of being able to relatively reduce the amount of expensive cyclic olefin used in its production.

By stretching the elongated substrate composed of the above resin in an oblique direction so that the smaller of the angle between the orientation axis and the elongate direction of the substrate is continuously inclined at 10° to 30° or 60° to 80°, A retardation layer made of a long stretched film that satisfies the formula (1) can be produced. As a method of stretching in the oblique direction, for example, a substrate roll in which a long substrate is wound in a roll shape is prepared, the substrate is continuously unwound from the substrate roll, and the unwound substrate is conveyed and heated in the long direction of the substrate. And a method of stretching in an oblique direction inclined at a desired angle. Specifically, as such a stretching method, for example, a method described in Japanese Unexamined Patent Publication No. 50-83482 or Japanese Unexamined Patent Publication No. Hei 2-113920 can be adopted.

The heating temperature of the substrate when the elongated substrate is stretched in the oblique direction is preferably a temperature in the vicinity of the glass transition temperature of the substrate (°C) to the glass transition temperature + 100°C, and the temperature in the vicinity of the glass transition temperature (°C) The range of-glass transition temperature + 50 degreeC is more preferable. In addition, in this specification, the "temperature (degreeC) near a glass transition temperature" means the glass transition temperature of a base material about ±5 degreeC.

In the elongate laminate of the present invention, the thickness of the retardation layer formed from the stretched film may be appropriately determined depending on the configuration of the elongate laminate, a display device to be applied, and the like, but is usually 300 μm or less. It is preferably 5 µm or more, more preferably 10 µm or more, and preferably 100 µm or less, and more preferably 50 µm or less. When the thickness of the retardation layer formed from the stretched film is within the above range, it is preferable from the viewpoint of thinning the laminate, and when introduced as a member constituting the elliptically polarizing plate, the effect of suppressing the color change and the flexibility are easily improved.

In the present invention, either one of the first phase difference layer and the second phase difference layer is a phase difference layer formed from a liquid crystal cured film. The liquid crystal cured film is usually obtained by applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound onto a photo-alignment film, and curing the polymerizable liquid crystal composition in a state in which the polymerizable liquid crystal compound is aligned. The polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition forming the phase difference layer is usually a liquid crystal compound having a polymerizable group, particularly a photopolymerizable group. The polymerizable liquid crystal compound is not particularly limited as long as it can form a liquid crystal cured film that satisfies the above formula (2), and for example, a rod-like or disk-shaped polymerizable liquid crystal compound conventionally known in the field of retardation films is used. Can be used. As a polymerizable liquid crystal compound for forming a retardation layer made of a liquid crystal cured film, only one type may be used, or two or more types may be used in combination.

When the rod-shaped polymerizable liquid crystal compound is horizontally aligned with respect to the substrate, the optical axis of the polymerizable liquid crystal compound coincides with the long axis direction of the polymerizable liquid crystal compound, and when the disk-shaped polymerizable liquid crystal compound is oriented, the polymerizable liquid crystal compound The optical axis of the compound exists in a direction orthogonal to the disk surface of the polymerizable liquid crystal compound. In order for the layer formed by polymerizing the polymerizable liquid crystal compound to exhibit an in-plane retardation, the polymerizable liquid crystal compound may be aligned in an appropriate direction. When the polymerizable liquid crystal compound is in the form of a rod, an in-plane retardation is expressed by horizontally aligning the optical axis of the polymerizable liquid crystal compound with respect to the substrate plane. In this case, the optical axis direction and the slow axis direction coincide. When the polymerizable liquid crystal compound is in the form of a disk, the in-plane retardation is expressed by horizontally aligning the optical axis of the polymerizable liquid crystal compound with respect to the substrate plane. In this case, the optical axis and the slow axis are orthogonal. The orientation state of the polymerizable liquid crystal compound can be adjusted by a combination of the photoalignment film and the polymerizable liquid crystal compound, and a retardation layer satisfying the formula (2) can be obtained by controlling the orientation state of the polymerizable liquid crystal compound.

As a rod-shaped polymerizable liquid crystal compound for forming a retardation layer made of a liquid crystal cured film, for example, a compound containing a group represented by formula (A) (hereinafter, also referred to as ``polymerizable liquid crystal compound (A)'') is mentioned. I can. In general, the polymerizable liquid crystal compound (A) tends to exhibit constant wavelength dispersibility in the polymer obtained by oriented the polymerizable liquid crystal compound alone in one direction, and the above-described polymerizable liquid crystal compound is used. A retardation layer having optical properties represented by formulas (9) and (10) can be obtained.

P11-B11-E11-B12-A11-B13- (A)

[In formula (A), P11 represents a polymerizable group.

A11 represents a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group. The hydrogen atom contained in the divalent alicyclic hydrocarbon group and the divalent aromatic hydrocarbon group may be substituted with a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a nitro group, and The hydrogen atom contained in the alkyl group of 6 and the alkoxy group having 1 to 6 carbon atoms may be substituted with a fluorine atom.

B11 is -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹ -, -NR ¹ -CO-, -CO-,- CS- or single bond. R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

B12 and B13 are each independently, -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O)-, -C(=O )-O-, -OC(=O)-, -OC(=O)-O-, -CH=N-, -N=CH-, -N=N-, -C(=O)-NR ¹ -, -NR ¹ -C(=O)-, -OCH ₂ -, -OCF ₂ -, -CH ₂ O-, -CF ₂ O-, -CH=CH-C(=O)-O-,- OC(=O)-CH=CH- or a single bond. R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

E11 represents an alkanediyl group having 1 to 12 carbon atoms, the hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms, and the hydrogen atom contained in the alkoxy group is substituted with a halogen atom You may have it. In addition, -CH ₂ -constituting the alkanediyl group may be substituted with -O- or -CO-.]

The number of carbon atoms of the aromatic hydrocarbon group and the alicyclic hydrocarbon group of A11 is preferably 3 to 18, more preferably 5 to 12, and particularly preferably 5 or 6. As A11, a cyclohexane-1,4-diyl group and a 1,4-phenylene group are preferable.

As E11, a linear C1-C12 alkanediyl group is preferable. -CH ₂ -constituting the alkanediyl group may be substituted with -O-.

Specifically, methylene group, ethylene group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1, 7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group and dodecane-1,12-di Linear alkanediyl groups having 1 to 12 carbon atoms such as diary; -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -and the like.

As B11, -O-, -S-, -CO-O-, and -O-CO- are preferable, and especially -CO-O- is more preferable.

As B12 and B13, each independently, -O-, -S-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O) -O- is preferable, and especially -O- or -OC(=O)-O- is more preferable.

The polymerizable group represented by P11 is preferably a radical polymerizable group or a cation polymerizable group in terms of high polymerization reactivity, particularly photopolymerization reactivity, and is easy to handle, and also because the production of a liquid crystal compound itself is easy. It is preferable that a genital group is a group represented by following formula (P-11)-formula (P-15).

[Formula 1]

[In formulas (P-11) to (P-15),

R ² to R ⁶ each independently represent a C 1 to C 6 alkyl group or a hydrogen atom.]

As a specific example of the group represented by Formula (P-11)-Formula (P-15), the group represented by following Formula (P-16)-Formula (P-20) is mentioned.

[Formula 2]

It is preferable that P11 is a group represented by formula (P-14)-formula (P-20), and a vinyl group, a p-stilbene group, an epoxy group, or an oxetanyl group is more preferable.

It is more preferable that the group represented by P11-B11- is an acryloyloxy group or a methacryloyloxy group.

Examples of the polymerizable liquid crystal compound (A) include compounds represented by formula (I), formula (II), formula (III), formula (IV), formula (V), or formula (VI).

P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-B16-E12-B17-P12 (I)

P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-A14-F11 (Ⅱ)

P11-B11-E11-B12-A11-B13-A12-B14-A13-B15-E12-B17-P12 (Ⅲ)

P11-B11-E11-B12-A11-B13-A12-B14-A13-F11 (Ⅳ)

P11-B11-E11-B12-A11-B13-A12-B14-E12-B17-P12 (Ⅴ)

P11-B11-E11-B12-A11-B13-A12-F11 (VI)

[In the formula,

A11, B11 to B13 and P11 have the same meaning as in the formula (A),

A12 to A14 are each independently the same as A11, B14 to B16 are each independently the same as B12, B17 is the same as B11, E12 is the same as E11, and P12 is the same as P11.

F11 is a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a cyano group, a nitro group, a trifluoromethyl group, a dimethylamino group, a hydroxy group, a methylol group, a formyl group, a sulfo group (-SO to ₃ -CH ₂ H), carboxyl group, alkoxy carbonyl group or a halogen atom having 1 to 10 carbon atoms, and the alkyl group constituting the alkoxy-is, or may be substituted with -O-].

As a specific example of a polymerizable liquid crystal compound (A), "3.8.6 network (completely crosslinked type)" and "6.5" of a liquid crystal manual (liquid crystal manual editing committee edition, Maruzen Co., Ltd. issued on October 30, 2000) .1 liquid crystal material b. Polymerizable nematic liquid crystal materials”, compounds having a polymerizable group, JP 2010-31223 A, JP 2010-270108 A, JP 2011-6360 A, and JP 2011- The polymerizable liquid crystal described in No. 207765, etc. are mentioned.

As a specific example of the polymerizable liquid crystal compound (A), the following formula (I-1)-formula (I-4), formula (II-1)-formula (II-4), formula (III-1)-formula Compounds represented by (III-26), formula (IV-1) to formula (IV-26), formula (V-1) to formula (V-2), and formula (VI-1) to formula (VI-6) Can be mentioned. In addition, in the following formula, k1 and k2 each independently represent the integer of 2-12. Such a polymerizable liquid crystal compound is preferred from the viewpoint of ease of synthesis or availability.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

As a disk-shaped polymerizable liquid crystal compound for forming a retardation layer made of a liquid crystal cured film, for example, a compound containing a group represented by formula (B) (hereinafter, also referred to as "polymerizable liquid crystal compound (B)") is mentioned. I can.

[Formula 12]

[In formula (B), R ¹¹ each independently represents any of the following formulas (B-1) to (B-5).]

[Formula 13]

X ¹¹ and Z ¹¹ in formulas (B-1) and (B-5) represent an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group is an alkoxy group having 1 to 5 carbon atoms. It may be substituted, and the hydrogen atom contained in the alkoxy group may be substituted with a halogen atom. Further, -CH ₂ -constituting the alkanediyl group may be substituted with -O- or -CO-. In formulas (B-1) to (B-4), m1 is 1 to 12.

As a specific example of a polymerizable liquid crystal compound (B), "6.5.1 liquid crystal material b. of liquid crystal manual (liquid crystal manual editing committee edition, Maruzen Co., Ltd. publication on October 30, 2000). Polymerizable nematic liquid crystal material The compound described in Fig. 6. 21", JP-A-7-258170, JP-A-7-30637, JP-A-7-309807, JP-A-H The polymerizable liquid crystal compound described in No. 8-231470, etc. are mentioned.

Since all of the above-described rod-shaped or disk-shaped polymerizable liquid crystal compounds are materials capable of producing a retardation layer satisfying formula (2) by controlling the orientation of the polymerizable liquid crystal compound, the liquid crystal in the present invention Any one can be used as the polymerizable liquid crystal compound for forming the retardation layer composed of a cured film, but from the viewpoint of birefringence expression, a rod-shaped polymerizable liquid crystal compound is preferable, and a polymerizable liquid crystal compound (A) is more preferable.

The content of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition for forming the retardation layer composed of the liquid crystal cured film is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 85 to 98 It is a mass part, More preferably, it is 90 to 95 mass parts. When the content of the polymerizable liquid crystal compound is within the above range, it is advantageous from the viewpoint of orientation of the obtained liquid crystal cured film.

The polymerizable liquid crystal composition for forming the retardation layer made of the liquid crystal cured film may further contain additives such as a solvent, a polymerization initiator, a leveling agent, an antioxidant, a photosensitizer, and a reactive additive in addition to the polymerizable liquid crystal compound. .

Since the polymerizable liquid crystal composition for forming the phase difference layer is usually applied on the photoalignment film in a state dissolved in a solvent, it is preferable to contain a solvent. The solvent is preferably a solvent capable of dissolving the polymerizable liquid crystal compound, and is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound. As a solvent, for example, water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol and propylene Alcohol solvents such as glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Alicyclic hydrocarbon solvents such as ethylcyclohexane; Aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-containing solvents such as chloroform and chlorobenzene; And amide solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone. These solvents can be used alone or in combination of two or more. Among these, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide solvents and aromatic hydrocarbon solvents are preferable.

The content of the solvent in the polymerizable liquid crystal composition is preferably 50 to 98 parts by mass, more preferably 70 to 95 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content occupied by 100 parts by mass of the polymerizable liquid crystal composition is preferably 2 to 50 parts by mass. When the solid content is 50 parts by mass or less, since the viscosity of the polymerizable liquid crystal composition is lowered, the thickness of the film becomes substantially uniform, and there is a tendency that nonuniformity is less likely to occur. The solid content may be appropriately determined in consideration of the thickness of the liquid crystal cured film to be produced.

The polymerization initiator is a compound capable of generating a reactive species by the contribution of heat or light and capable of initiating a polymerization reaction such as a polymerizable liquid crystal compound. Examples of the reactive active species include radicals or active species such as cation or anion. Among them, a photopolymerization initiator that generates radicals by irradiation with light is preferable from the viewpoint of easy reaction control.

Examples of the photoinitiator include benzoin compounds, benzophenone compounds, benzyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, oxime compounds, triazine compounds, iodonium salts and sulfonium salts. have. Specifically, Irgacure (registered trademark) 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 2959, Irgacure 754, Irgacure 379EG (above, manufactured by BASF Japan Co., Ltd.), Sakeall BZ, Sakeall Z, Sakeall BEE (above, manufactured by Seiko Chemical Co., Ltd.), Kayacure (kayacure) BP100 ( Nippon Explosives Co., Ltd.), Kayacure UVI-6992 (manufactured by Dow Corporation), Adeka Optoma SP-152, Adeka Optoma SP-170, Adeka Optoma N-1717, Adeka Optoma N-1919, Adeka Acruze NCI- 831, Adeka Cruise NCI-930 (above, manufactured by ADEKA Co., Ltd.), TAZ-A, TAZ-PP (above, manufactured by Nippon Sibel Hegner), and TAZ-104 (manufactured by Sanwa Chemical).

Since the photoinitiator can fully utilize the energy emitted from the light source and is excellent in productivity, the maximum absorption wavelength is preferably 300 nm to 400 nm, more preferably 300 nm to 380 nm, and among them α- Acetophenone-based polymerization initiators and oxime-based photopolymerization initiators are preferable.

As an α-acetophenone compound, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)- 2-benzylbutan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, and the like, and more preferably 2- Methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one and 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one. I can. As commercially available products of the α-acetophenone compound, Irgacure 369, 379EG, 907 (above, manufactured by BASF Japan Co., Ltd.) and Seiko BEE (manufactured by Seiko Chemical Corporation), etc. are mentioned.

The oxime photopolymerization initiator generates radicals such as a phenyl radical and a methyl radical by irradiation with light. The polymerization of the polymerizable liquid crystal compound preferably proceeds by this radical, but among them, an oxime photopolymerization initiator that generates a methyl radical is preferable from the viewpoint of high initiation efficiency of the polymerization reaction. Moreover, it is preferable to use a photoinitiator which can efficiently use ultraviolet rays of 350 nm or more in wavelength from a viewpoint of making a polymerization reaction progress more efficiently. As a photoinitiator capable of efficiently using ultraviolet rays having a wavelength of 350 nm or more, a triazine compound or carbazole compound containing an oxime structure is preferable, and a carbazole compound containing an oxime ester structure is more preferable from the viewpoint of sensitivity. Examples of the oxime photoinitiator include 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanol, 1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like. Commercially available products of oxime ester photopolymerization initiators include Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above, manufactured by BASF Japan Co., Ltd.), Adeka Optoma N-1919, and Adeka Cruise. NCI-831 (above, manufactured by ADEKA Co., Ltd.), etc. are mentioned.

The content of the photoinitiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass per 100 parts by mass of the polymerizable liquid crystal compound. Within the above range, the reaction of the polymerizable group proceeds sufficiently, and it is difficult to disturb the orientation of the polymerizable liquid crystal compound.

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

Moreover, by using a photosensitizer, a photoinitiator can be made highly sensitive. Examples of the photosensitizer include xanthones such as xanthone and thioxanthone; Anthracenes having substituents such as anthracene and alkyl ether; Phenothiazine; Rubrene is mentioned. Photosensitizers can be used alone or in combination of two or more. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass per 100 parts by mass of the polymerizable liquid crystal compound.

The polymerizable liquid crystal composition for forming a phase difference layer comprising a liquid crystal cured film may contain a reactive additive. As a reactive additive, it is preferable to have a carbon-carbon unsaturated bond and an active hydrogen reactive group in the molecule. In addition, the term "active hydrogen reactive group" herein refers to a group having reactivity with a group having an active hydrogen such as a carboxyl group (-COOH), a hydroxyl group (-OH), and an amino group (-NH ₂ ), and glycidyl group, oxa Representative examples thereof include a sleepy group, a carbodiimide group, an aziridine group, an imide group, an isocyanate group, a thioisocyanate group, and a maleic anhydride group. The number of carbon-carbon unsaturated bonds and active hydrogen reactive groups in the reactive additive is usually 1 to 20, and preferably 1 to 10, respectively.

In the reactive additive, it is preferable that at least two active hydrogen-reactive groups are present, and in this case, a plurality of active hydrogen-reactive groups may be the same or different.

The carbon-carbon unsaturated bond possessed by the reactive additive may be a carbon-carbon double bond, a carbon-carbon triple bond, or a combination thereof, but is preferably a carbon-carbon double bond. Especially, as a reactive additive, it is preferable if it contains a carbon-carbon unsaturated bond as a vinyl group and/or a (meth)acryl group. Further, the active hydrogen reactive group is preferably at least one selected from the group consisting of an epoxy group, a glycidyl group and an isocyanate group, and a reactive additive having an acrylic group and an isocyanate group is particularly preferable.

Specific examples of the reactive additive include compounds having a (meth)acrylic group and an epoxy group, such as methacryloxyglycidyl ether and acryloxyglycidyl ether; Compounds having a (meth)acryl group and an oxetane group, such as oxetane acrylate and oxetane methacrylate; Compounds having a (meth)acryl group and a lactone group, such as lactone acrylate and lactone methacrylate; Compounds having a vinyl group and an oxazoline group, such as vinyloxazoline and isopropenyloxazoline; Oligomers of compounds having a (meth)acryl group and an isocyanate group, such as isocyanatomethyl acrylate, isocyanatomethyl methacrylate, 2-isocyanatoethyl acrylate, and 2-isocyanatoethyl methacrylate. I can. Further, compounds having a vinyl group, a vinylene group and an acid anhydride, such as methacrylic anhydride, acrylic anhydride, maleic anhydride and vinyl maleic anhydride, may be mentioned. Among them, methacryloxy glycidyl ether, acryloxy glycidyl ether, isocyanatomethyl acrylate, isocyanatomethyl methacrylate, vinyloxazoline, 2-isocyanatoethyl acrylate, 2-isocya Natoethyl methacrylate and the above oligomers are preferred, and isocyanatomethylacrylate, 2-isocyanatoethylacrylate and the above oligomers are particularly preferred.

Specifically, a compound represented by the following formula (Y) is preferable.

[Formula 14]

[In formula (Y),

n represents an integer of 1 to 10, and R ¹ ′ represents a C 2 to C 20 divalent aliphatic or alicyclic hydrocarbon group or a C 5 to C 20 divalent aromatic hydrocarbon group. Two R ² ′ in each repeating unit is a group represented by one of -NH- and the other of >NC(=O)-R ³ ′. R ³ ′ represents a hydroxyl group or a group having a carbon-carbon unsaturated bond.

Formula R ³ 'wherein at least one R ^3' of the (Y) is a carbon-carbon unsaturated bond is a group having the.

Among the reactive additives represented by the above formula (Y), a compound represented by the following formula (YY) (hereinafter sometimes referred to as compound (YY)) is particularly preferred (in addition, n has the same meaning as above).

[Formula 15]

As the compound (YY), a commercial item can be used as it is or purified as necessary. As a commercial item, Laromer (registered trademark) LR-9000 (made by BASF) is mentioned, for example.

When the polymerizable liquid crystal composition contains a reactive additive, the content is usually 0.1 to 30 parts by mass, and preferably 0.1 to 5 parts by mass per 100 parts by mass of the polymerizable liquid crystal compound.

In the elongate laminate of the present invention, the thickness of the retardation layer formed from the liquid crystal cured film may be appropriately determined depending on the configuration of the elongate laminate, a display device to be applied, and the like, but is usually 10 μm or less. It is preferably 0.5 µm or more, preferably 5 µm or less, and more preferably 3 µm or less. When the thickness of the retardation layer formed from the liquid crystal cured film is within the above range, it is preferable from the viewpoint of thinning the laminate, and when introduced as a member constituting the elliptically polarizing plate, the effect of suppressing the color change and the flexibility are easily improved. .

The polymerizable liquid crystal composition for forming a retardation layer comprising a liquid crystal cured film can be obtained by stirring or the like at a predetermined temperature with a polymerizable liquid crystal compound and other components such as a solvent or a photopolymerization initiator, if necessary.

The retardation layer formed from the liquid crystal cured film is, for example,

A step of applying a polymerizable liquid crystal composition for forming a retardation layer on a photo-alignment film to obtain a coating film,

Drying the coating film to form a dry coating film, and

Process of forming a liquid crystal cured film by irradiating the dry coating film with active energy rays

It can be produced by a method containing.

In the present invention, the formation of the coating film of the polymerizable liquid crystal composition for forming a retardation layer can be usually carried out by applying a polymerizable liquid crystal composition for forming a retardation layer on a photoalignment film described later. As a coating method of the polymerizable liquid crystal composition, usually, a spin coating method, an extrusion method, a gravure coating method, a die coating method, a slit coating method, a bar coating method, a coating method such as an applicator method, or a printing method such as a flexo method A known method such as may be employed.

Subsequently, a dry coating film is formed by removing the solvent by drying or the like. Examples of the drying method include natural drying, ventilation drying, heat drying, and vacuum drying. By heating the coating film obtained from the polymerizable liquid crystal composition to a liquid crystal phase transition temperature or higher of the polymerizable liquid crystal compound contained in the polymerizable liquid crystal composition, while drying and removing the solvent from the coating film, the polymerizable liquid crystal compound is aligned in the horizontal direction. Since it can be made, heat drying is preferable from the viewpoint of productivity and the like. Further, in general, the liquid crystal phase transition temperature of the polymerizable liquid crystal compound in the polymerizable liquid crystal composition may be lower than the liquid crystal phase transition temperature as a polymerizable liquid crystal compound alone.

The heating temperature of the coating film can be appropriately determined in consideration of the polymerizable liquid crystal compound to be used, the material of the substrate for forming the retardation layer composed of a photoalignment film or a stretched film, etc., but usually, a phase transition of a polymerizable liquid crystal compound to a liquid crystal phase state In order to do so, it is necessary to have a temperature equal to or higher than the liquid crystal phase transition temperature. In order to bring the polymerizable liquid crystal compound into a horizontal alignment state while removing the solvent contained in the polymerizable liquid crystal composition, the heating temperature is preferably a liquid crystal phase (for example, a nematic phase or a smectic phase) of the polymerizable liquid crystal compound. It is a temperature higher than the transition temperature by 3°C or higher, more preferably 5°C or higher. The upper limit of the heating temperature is not particularly limited, but in order to avoid damage to the coating film or the retardation layer formed of a stretched film by heating, it is preferably 180°C or less, more preferably 150°C or less.

In addition, the liquid crystal phase transition temperature can be measured using, for example, a polarizing microscope equipped with a temperature control stage, a differential scanning calorimeter (DSC), a thermogravimetric differential thermal analyzer (TG-DTA), or the like. In addition, when two or more types are used in combination as a polymerizable liquid crystal compound, the phase transition temperature is a polymerization obtained by mixing all the polymerizable liquid crystal compounds constituting the polymerizable liquid crystal composition in the same ratio as the composition in the polymerizable liquid crystal composition. It means a temperature measured in the same manner as in the case of using a single type of polymerizable liquid crystal compound by using a mixture of sexual liquid crystal compounds.

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

The removal of the solvent from the coating film may be performed simultaneously with heating of the polymerizable liquid crystal compound to a liquid crystal phase transition temperature or higher, or may be performed separately, but is preferably performed simultaneously from the viewpoint of productivity improvement. Before heating the polymerizable liquid crystal compound to a liquid crystal phase transition temperature or higher, a predrying step for appropriately removing the solvent in the coating film under conditions in which the polymerizable liquid crystal compound contained in the coating film obtained from the polymerizable liquid crystal composition does not polymerize is performed. You may prepare. As a drying method in such a pre-drying process, a natural drying method, a ventilation drying method, a heat drying and a vacuum drying method, etc. are mentioned, and the drying temperature (heating temperature) in the drying process is the polymerizable liquid crystal compound to be used. It can be appropriately determined according to the type, the type of solvent, its boiling point, and its amount.

Next, in the obtained dry coating film, by polymerizing the polymerizable liquid crystal compound while maintaining the horizontal alignment state of the polymerizable liquid crystal compound, a liquid crystal cured film in which the polymerizable liquid crystal compound is aligned in the horizontal direction is formed. As the polymerization method, a thermal polymerization method or a photopolymerization method may be mentioned, but a photopolymerization method is preferable from the viewpoint of easy control of the polymerization reaction. In photopolymerization, as the light irradiated to the dry coating film, the type of polymerization initiator contained in the dried coating film, the type of the polymerizable liquid crystal compound (particularly, the type of the polymerizable group of the polymerizable liquid crystal compound) and the amount thereof It is appropriately selected according to. Specific examples thereof include at least one type of light or active electron beam selected from the group consisting of visible light, ultraviolet light, infrared light, X-ray, α-ray, β-ray, and γ-ray. Among them, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction, and because a photopolymerization device that is widely used in the art can be used, it is polymerizable so that photopolymerization is possible by ultraviolet light. It is preferable to select the kind of the polymerizable liquid crystal compound or polymerization initiator contained in the liquid crystal composition. Further, at the time of polymerization, the polymerization temperature can also be controlled by irradiating light while cooling the dry coating film by an appropriate cooling means. When the polymerization of the polymerizable liquid crystal compound is carried out at a lower temperature by employing such a cooling means, the material of the other layers constituting the elongated laminate of the present invention, such as the substrate forming the first retardation layer, has relatively low heat resistance. Even if used, the liquid crystal cured film of the second phase difference layer can be appropriately formed. Further, the polymerization reaction can also be promoted by increasing the polymerization temperature within a range in which a problem due to heat (transformation due to heat, etc.) does not occur during light irradiation. During photopolymerization, a patterned cured film can also be obtained by masking or developing.

As a light source of the active energy ray, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a halogen lamp, a carbon arc lamp, a tungsten lamp, a gallium lamp, an excimer laser, a wavelength range of 380 LED light sources emitting -440 nm, chemical lamps, black light lamps, microwave excitation mercury lamps, metal halide lamps, and the like.

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

In the present invention, the coating film of the composition for forming a retardation layer comprising a liquid crystal cured film is usually formed on the photoalignment film. The photoalignment film has an alignment regulating force that liquid crystal aligns a polymerizable liquid crystal compound in a desired direction. By using the photoalignment film as the alignment film, it is easy to control the alignment angle of the polymerizable liquid crystal compound with high precision, and it is easy to obtain a liquid crystal cured film having a longer shape and more excellent optical properties. In the present invention, as a photo-alignment film for aligning the polymerizable liquid crystal compound in a desired direction and obtaining a retardation layer that satisfies Formula (2), usually, an alignment regulating force for aligning the polymerizable liquid crystal compound in a horizontal direction with respect to the application plane is provided. A horizontally oriented photo-aligning film having is used.

The photo-alignment film is usually coated with a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter, also referred to as ``photo-alignment film-forming composition'') to a substrate, and after removing the solvent, polarized light (preferably, polarized UV ) Is obtained. The photoalignment film is also advantageous in that it can arbitrarily control the direction of the orientation regulating force by selecting the polarization direction of the polarized light to be irradiated.

The photoreactive group refers to a group that generates liquid crystal alignment ability by irradiation with light. Specifically, a group involved in the photoreaction which is the origin of the liquid crystal orientation ability, such as the orientation of molecules generated by light irradiation or isomerization reaction, dimerization reaction, photocrosslinking reaction or photodecomposition reaction, is mentioned. Among these, from the viewpoint of excellent orientation, a dimerization-reactive group or a group involved in a photocrosslinking reaction is preferable, and a dimerization-reactivity photoreactive group is more preferable. As the photoreactive group, a group having an unsaturated bond, particularly a double bond, is preferred, and a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), a nitrogen-nitrogen double bond (N=N Bond) and a group having at least one selected from the group consisting of a carbon-oxygen double bond (C=O bond).

Examples of the photoreactive group having a C=C bond include a vinyl group, a polyene group, a stilbene group, a stilbazole group, a stilbazolium group, a chalcone group, and a cinnamoyl group. Examples of the photoreactive group having a C=N bond include a group having a structure such as an aromatic sipe base and an aromatic hydrazone. Examples of the photoreactive group having an N=N bond include an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group, a formazane group, and a group having an azoxybenzene structure. As a photoreactive group which has a C=O bond, a benzophenone group, a coumarin group, an anthraquinone group, a maleimide group, etc. are mentioned. These groups may have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

Among them, a dimerization-reactive photoreactive group involved in the light dimerization reaction is preferable, and the amount of polarization irradiation required for photo-alignment is relatively small, and a photo-alignment film excellent in thermal stability and time-lapse stability is easy to obtain. In, a cinnamoyl group and a chalcone group are preferred. As a polymer having a photoreactive group, it is particularly preferable that the terminal portion of the side chain of the polymer has a cinnamoyl group to form a cinnamic acid structure.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment layer can be appropriately adjusted depending on the type of the polymer or monomer or the thickness of the target photoalignment layer, but at least 0.2 mass per mass of the composition for forming a photoalignment layer It is preferable to set it as %, and the range of 0.3-10 mass% is more preferable. The composition for forming a photoalignment film may contain a polymeric material such as polyvinyl alcohol or polyimide, or a photosensitizer within a range in which the characteristics of the photoalignment film are not significantly impaired.

The coating film of the composition for forming a photo-alignment film may be formed on the substrate, but by directly forming the film on the retardation layer formed of a stretched film, the manufacturing process of the long laminate can be reduced, and the long laminate can be improved with better productivity. Can be manufactured. Examples of the solvent contained in the composition for forming a photo-alignment film include the same solvents as those exemplified above as a solvent that can be used for the polymerizable liquid crystal composition for forming a retardation layer composed of a liquid crystal cured film. It can be appropriately selected depending on solubility.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photoalignment layer can be appropriately adjusted depending on the type of the polymer or monomer or the thickness of the target photoalignment layer, but at least 0.2 mass per mass of the composition for forming a photoalignment layer It is preferable to set it as %, and the range of 0.3-10 mass% is more preferable. The composition for forming a photoalignment film may contain a polymeric material such as polyvinyl alcohol or polyimide, or a photosensitizer within a range in which the characteristics of the photoalignment film are not significantly impaired.

As a method of applying the composition for forming a photoalignment film on the retardation layer formed from a stretched film, the same method as the method of applying the polymerizable liquid crystal composition for forming a retardation layer onto the photoalignment film may be mentioned. In the case of manufacturing the elongated laminate of the present invention by a continuous manufacturing method of a Roll to Roll format, a printing method such as a gravure coating method, a die coating method, or a flexo method is usually employed as the coating method.

As a method of removing the solvent from the applied composition for forming a photoalignment film, for example, a natural drying method, a ventilation drying method, a heat drying method, and a reduced pressure drying method may be mentioned.

In order to irradiate polarized light, a form of directly irradiating polarized UV light to the removal of the solvent from the applied composition for forming a photo-alignment film may be used, or a form of irradiating polarized light from the side of the retardation layer formed from the stretched film and transmitting the polarized light to irradiate . Moreover, the said polarized light is especially preferable if it is substantially parallel light. The wavelength of polarized light to be irradiated is preferably in a wavelength range in which the photoreactive group of a polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) in the wavelength range of 250 to 400 nm is particularly preferred. Examples of light sources used for polarized light irradiation include xenon lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and the like, high pressure mercury lamps, ultra high pressure mercury lamps, and metal halide lamps. Is more preferable. Among these, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferable because of their high luminous intensity of ultraviolet rays having a wavelength of 313 nm. Polarized UV can be irradiated by irradiating the light from the light source through a suitable polarizer. As such a polarizer, a polarizing filter, a polarizing prism such as a Glen Thompson, and a Glen Taylor, or a wire grid type polarizer can be used.

The number average molecular weight of the photoalignment film is preferably 20000 to 100000, more preferably 25000 or more, still more preferably 30000 or more, and more preferably 90000 or less, still more preferably 80000 or less. When the number average molecular weight of the photo-alignment film is within the above range, the adhesion with the layer adjacent to the photo-alignment film is increased, and a long laminate in which the first retardation layer and the second retardation layer are laminated with good adhesion through the photo-alignment film can be obtained. . The number average molecular weight of the photoalignment film can be controlled by the amount of the monomer used in the composition for photoalignment film formation, the kind or amount of the polymerization initiator, and the like.

In addition, the "number average molecular weight of the photoalignment film" as referred to herein is substantially equivalent to the number average molecular weight of the polymer constituting the cured photoalignment film, and the photoalignment film cured using a measuring device such as gel permeation chromatography. It is a molecular weight calculated by measuring itself. Detailed measurement and calculation methods are described in Examples to be described later.

The thickness of the photoalignment film is preferably 100 to 300 nm, more preferably 120 nm or more, still more preferably 130 nm or more, and more preferably 280 nm or less, and still more preferably 270 nm or less. . When a retardation layer made of a liquid crystal cured film is formed on a retardation layer made of a stretched film through a photo-alignment film, the liquid crystal orientation of the polymerizable liquid crystal compound constituting the retardation layer made of the liquid crystal cured film affects the orientation of the stretched film. There is a case to receive. When the thickness of the photoalignment film is within the above range, the influence of the orientation of the stretched film on the orientation of the polymerizable liquid crystal compound constituting the retardation layer of the liquid crystal cured film is suppressed, and the polymerizable liquid crystal compound is oriented with good precision in the desired direction. A retardation layer made of a cured film can be obtained.

The elongate laminate of the present invention obtained by laminating the first retardation layer, the light alignment layer, and the second retardation layer in this order has a function as a retardation plate. In addition to this configuration, a long laminate having a function as an elliptically polarizing plate is obtained by laminating a polarizing layer further.

An example of the layer structure of the elongate laminate of the present invention that functions as an elliptically polarizing plate is described based on FIG. 2. Fig. 2 is a diagram showing a cross section when the elongated laminate of the present invention is cut in the thickness direction. In the elongated laminate 11 of the present invention shown in FIG. 2, the retardation plate 12 formed by laminating the first retardation layer 1, the photoalignment film 3, and the second retardation layer 2 in this order. The polarizing layer 4 is present on the side opposite to the photoalignment layer 3 of the first retardation layer 1 through the adhesive layer 5, and further, the first retardation layer 1 of the polarizing layer 4 The protective layer 6 is present on the side opposite to the side through the adhesive layer 5. Other layers such as a protective layer may be present between the first retardation layer 1 and the polarizing layer 4 through the adhesive layer 5, but including the first retardation layer 1 and the polarizing layer 4 From the viewpoint of enhancing the adhesiveness with the polarizing plate 13, it is preferable that the first retardation layer 1 and the polarizing layer 4 are adjacent to each other via the adhesive layer 5. One of the first retardation layer (1) and the second retardation layer (2) is a stretched film, and the other is a liquid crystal cured film, from the viewpoint of the antireflection function, the first retardation layer (1) is a stretched film, and a polarizing plate ( 13) It is preferable that the first phase difference layer (1) is laminated on the side opposite to the photoalignment film via an adhesive layer.

The polarizing layer is a layer having a polarizing function. Examples of such a layer include a stretched film in which a dye having absorption anisotropy is adsorbed, or a film including a film to which a dye having absorption anisotropy is applied as a polarizer. As a dye having absorption anisotropy, a dichroic dye can be mentioned, for example.

A film comprising a stretched film adsorbing a dye having absorption anisotropy as a polarizer is usually a step of uniaxially stretching a polyvinyl alcohol-based resin film, and the dichroic property of the polyvinyl alcohol-based resin film is dyed with a dichroic dye. It is produced through a step of adsorbing a dye, a step of treating a polyvinyl alcohol-based resin film to which a dichroic dye is adsorbed with an aqueous boric acid solution, and a step of washing with water after treatment with an aqueous boric acid solution.

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

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

What formed such a polyvinyl alcohol-based resin into a film is used as a raw film of the polarizing layer 4. The method of forming a film of a polyvinyl alcohol-based resin is not particularly limited, and a known method can be used to form a film. The film thickness of the polyvinyl alcohol-based raw film can be, for example, about 10 to 150 µm.

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

Dyeing of a polyvinyl alcohol-based resin film with a dichroic dye is performed, for example, by a method of immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic dye.

Specifically, as a dichroic dye, iodine or a dichroic organic dye is used. As a dichroic organic dye, C.I. A dichroic direct dye composed of a disazo compound such as DIRECT RED 39, and a dichroic direct dye composed of a compound such as tris azo or tetrakis azo, and the like. In the present invention, it is preferable that iodine is contained as a dichroic dye in the polarizing layer. It is preferable that the polyvinyl alcohol-based resin film is subjected to an immersion treatment in water before the dyeing treatment.

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

On the other hand, when a dichroic organic dye is used as the 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 this aqueous solution is, per 100 parts by mass of water, usually about 1 × 10 ^-4 to 10 parts by mass, preferably 1 × 10 ^-3 to 1 part by mass, more preferably It is 1 × 10 ^-3 to 1 × 10 ^-2 parts by mass. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80°C. Moreover, the immersion time (dyeing time) for this aqueous solution is usually about 10 to 1,800 seconds.

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

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

Drying treatment is performed after washing with water, and a polarizer is obtained. Drying treatment can be performed using a hot air dryer or a far-infrared heater, for example. The temperature of the drying treatment is usually about 30 to 100°C, preferably 50 to 80°C. The drying treatment time is usually about 60 to 600 seconds, and preferably 120 to 600 seconds. By drying treatment, the moisture content of the polarizer is reduced to a practical level. The water content is usually about 5 to 20% by mass, preferably 8 to 15% by mass. When the moisture content is within the above range, a polarizer having appropriate flexibility and excellent thermal stability can be obtained.

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

Examples of the film to which the dye having absorption anisotropy is applied include a composition containing a dichroic dye having liquid crystal properties or a film obtained by applying a composition containing a dichroic dye and a polymerizable liquid crystal.

It is preferable that the film to which the dye having absorption anisotropy is applied is thinner, but if it is too thin, the strength decreases and the workability tends to be inferior. The thickness of the film is usually 20 µm or less, preferably 5 µm or less, and more preferably 0.5 to 3 µm.

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

A transparent protective layer may be laminated on one or both surfaces of the polarizing layer thus obtained through, for example, an adhesive layer. The transparent protective layer can contribute to preventing contraction and expansion of the polarizer, preventing deterioration of the polarizing layer due to temperature, humidity, ultraviolet rays, or the like, and preventing the occurrence of scratches in the polarizing layer.

In the present invention, the transparent protective layer refers to a protective layer having transparency that can transmit visible light, and the transparency refers to a property in which the luminous sensitivity corrected transmittance for light over a wavelength of 380 nm to 780 nm is 80% or more. . On the other hand, from the viewpoint of improving the effect of inhibiting deterioration of the polarizing layer due to ultraviolet rays, the total light transmittance at 380 nm of the transparent protective layer is preferably 30% or less, more preferably 25% or less, and still more preferably 20 % Or less. The lower the total light transmittance at 380 nm of the transparent protective layer is, the more preferable it is, but it is usually 0.1% or more.

As the transparent protective layer, in addition to transparency, those excellent in mechanical strength, thermal stability and/or isotropy are preferable. Specifically, for example, a film composed of a light-transmitting resin can be used, and examples of the substrate for forming the first phase difference layer include those exemplified above.

The thickness of the transparent protective layer is not particularly limited, but from the viewpoint of thinning the elongated layered product, it is generally 300 μm or less, preferably 20 to 200 μm, more preferably 30 to 150 μm, and 40 It is more preferable that it is -100 micrometers.

In the elongated laminate of the present invention, the retardation layer formed from the stretched film can also function as a transparent protective layer. Therefore, by forming a transparent protective layer only on one surface of the polarizing layer, and attaching a retardation layer formed from a stretched film on the surface of the protective layer opposite to the transparent protective layer, a thinner long laminate (long Elliptically polarizing plate) can be obtained. Accordingly, the present invention provides a long laminate (long elliptically polarizing plate) in which a transparent protective layer, an adhesive layer, a polarizing layer, an adhesive layer, a retardation layer formed from a stretched film, a light alignment film, and a retardation layer formed from a liquid crystal cured film are stacked in this order. ). The elongate laminate of such a structure can realize thinning compared with the elongate laminated body (elliptically polarizing plate) in which both the two retardation layers consist of a stretched film. In addition, in a long laminate in which both of the two phase difference layers are formed of a liquid crystal cured film, in order to secure a sufficient protective function for the polarizing layer, it is necessary to form transparent protective layers on both sides of the polarizing layer. In contrast, in the long laminate of the present invention in which the retardation layer made of a stretched film can also function as a protective layer for the polarizing layer, the transparent protective layer on one side of the polarizing layer can be made a retardation layer made of a stretched film. , It is advantageous in that it can be a thinner laminate while securing a sufficient protective function for the polarizing layer.

The pressure-sensitive adhesive/adhesive for forming the adhesive layer is not particularly limited, and examples thereof include a pressure-sensitive adhesive, a water-based adhesive, and an active energy ray-curable adhesive. Among them, active energy ray-curable adhesives and water-based adhesives are preferable from the viewpoint of thinning the formed adhesive layer.

The thickness of the adhesive layer may be appropriately determined depending on the type of adhesive to be used, the layer structure of the elongated laminate, and the like. The thickness of the adhesive layer is usually 0.001 to 5 µm, and from the viewpoint of achieving a thin layer of the laminate while securing sufficient interlayer adhesion, it is preferably 0.01 to 2 µm, more preferably 0.01 to 0.5 µm.

The elongated laminate of the present invention obtained by laminating the first retardation layer, the photoalignment film, and the second retardation layer in this order can be continuously produced by a Roll to Roll format, and thus can be produced with good productivity. When the first retardation layer is a stretched film and the second retardation layer is a liquid crystal cured film, for example,

(a) a step of preparing a substrate roll in which the substrate forming the first retardation layer is wound around a core,

(b) the step of continuously delivering the substrate from the substrate roll,

(c) a step of forming a long first phase difference layer by stretching the substrate to be conveyed at a desired angle intersecting with the long direction of the substrate,

(d) a step of continuously forming a photoalignment film on the first phase difference layer obtained in (c), and,

(e) Step of continuously forming a liquid crystal cured film as a second phase difference layer on the photoalignment film obtained in (d)

It can be produced by a method containing.

In the above method, the steps (a) to (c) of forming the first phase difference layer, the step (d) of forming the photo-alignment layer, and the step (e) of forming the second phase difference layer may be performed continuously, After the step (c) and/or step (d), the formed long first retardation layer or the long laminate in which the photoalignment film is laminated on the first retardation layer is wound around the core, and the subsequent steps are not continued. You may do it. In addition, instead of the steps (a) to (c), a commercially available elongated stretched film roll that satisfies the formula (1) may be used, and layers other than the first retardation layer, the photoalignment film, and the second retardation layer are included. In the case of doing so, a step of forming another layer may be included.

The method for producing the first retardation layer made of a stretched film by a method including the steps (a) to (c) is as described above as a method for producing a retardation layer formed from a stretched film. Further, by forming a second retardation layer made of a liquid crystal cured film on the retardation layer made of a long stretched film so that the slow axis of the obtained retardation layer becomes a specific angle with respect to the long direction, the equations (1) and (2) A long laminate of the present invention that satisfies the is obtained. The formation method of the retardation layer comprising a liquid crystal cured film is as described above.

In addition, the long laminate of the present invention comprising a polarizing layer and a transparent protective layer, in addition to the steps (a) to (e),

(f) A process of continuously laminating a polarizing layer through an adhesive layer on the side opposite to the photoalignment layer of the first or second retardation layer

(g) Process of continuously laminating a transparent protective layer through an adhesive layer on the side opposite to the retardation layer of the polarizing layer

It can be produced by a method containing. Steps (f) and (g) may be performed continuously with steps (a) to (e), and separately from steps (a) to (e), a transparent protective layer via an adhesive layer on one or both sides of the polarizing layer You may first manufacture a long laminated body in which is formed, and the laminated body may be laminated on a long laminate composed of a first retardation layer, a photoalignment film, and a second retardation layer via an adhesive layer.

In the long laminate of the present invention, when the first retardation layer, the second retardation layer, and the polarizing layer are laminated, the angle formed by the slow axis of the first retardation layer and the absorption axis of the polarizing layer is 12 to 25° or 65 to It is preferable to laminate such that the angle is 78°, and the angle formed by the slow axis of the second phase difference layer and the absorption axis of the polarizing layer is 2θa + 42° ≤ θb ≤ 2θa + 48°. The first phase difference layer constituting the elongated laminate of the present invention satisfies the equation (1), and the slow axis intersects at a specific angle with respect to the elongate direction. By using a retardation layer having such a slow axis, a general polarizing film manufactured by uniaxially stretching a polyvinyl alcohol-based resin film in the traveling direction (long direction) can be bonded to the retardation layer by a long roll to roll method. have. Thereby, it becomes possible to manufacture a long laminated body functioning as an elliptically polarizing plate continuously and with good productivity without requiring any special operation or apparatus, using a general polarizing film roll that can be easily obtained commercially.

The long laminate of the present invention may have a configuration provided by a conventional general elliptically polarizing plate or a polarizing film and a retardation plate. Examples of such a configuration include a pressure-sensitive adhesive layer (sheet) for bonding the elongated laminate of the present invention functioning as an elliptically polarizing plate to a display element such as an organic EL.

In the present invention, the width or length of the elongated laminate is not particularly limited, and can be appropriately determined depending on the layer structure and use of the elongated laminate, and manufacturing facilities. Usually, the length of the elongated laminate is 10 to 10,000 m, preferably 50 to 5000 m.

The long laminate of the present invention has a high suppression effect against light leakage when introduced as a member constituting an elliptically polarizing plate, and also has a small change in front color, so it can be preferably used as a constituent member of a display device. have. Accordingly, the present invention also includes a display device including a sheet body obtained from the elongated laminate of the present invention.

The elongate laminate of the present invention can be used for various display devices.

A display device is a device having a display element, and includes a light-emitting element or a light-emitting device as a light-emitting source. As a display device, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (e.g., a full-length emission display device (FED) ), surface field emission display (SED)), electronic paper (display using electronic ink or electrophoretic element, plasma display, projection type display (e.g. grating light valve (GLV) display, digital micromirror device) (Display device having (DMD)) and a piezoelectric ceramic display, etc. The liquid crystal display device includes a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, and a projection liquid crystal display device. Etc. These display devices may be a display device that displays a two-dimensional image or a three-dimensional display device that displays a three-dimensional image, In particular, the elongated laminate of the present invention is an organic electroluminescence (EL). It can be suitably used for a display device and an inorganic electroluminescent (EL) display device The elongated laminate of the present invention can be used as a sheet of various sizes and shapes, and can be introduced into various display devices. , By providing the elliptically polarizing plate of the present invention excellent in optical properties, good image display properties can be expressed.

Example

Hereinafter, the present invention will be described in more detail by examples. In addition, "%" and "part" in the examples mean mass% and mass parts, respectively, unless otherwise specified.

1. Example 1

(1) Preparation of the composition for forming a photoalignment film

The composition for photoalignment film formation was obtained by mixing the following components and stirring the obtained mixture at 80 degreeC for 1 hour.

Photoalignable material (5 parts):

Solvent (95 parts): Cyclopentanone

(2) Preparation of polymerizable liquid crystal composition

The composition of the polymerizable liquid crystal composition is shown below. After mixing each component and stirring the obtained solution at 80 degreeC for 1 hour, it cooled to room temperature and obtained the polymerizable liquid crystal composition.

<Composition>

Polymerizable liquid crystal : LC242 (manufactured by BASF) 19.2 part

Polymerization initiator: Irg907 (manufactured by BASF Japan) 0.5 copies

Leveling agent: BYK-361N (manufactured by Big Chemie Japan) 0.1 part

Reaction additive: LR-9000 1.1 part

(Laromer (registered trademark) manufactured by BASF Japan)

Solvent: PGMEA 79.1 copies

(Propylene glycol 1-monomethyl ether 2-acetate)

(3) Preparation of the first retardation layer consisting of a stretched film

Referring to the first retardation image of Japanese Patent Laid-Open No. 2013-235272, a long-sized cycloolefin polymer (COP) film (product name: ZEONOR (Zeonor)) manufactured by Nippon Xeon Co., Ltd. is placed in a direction perpendicular to the progress direction (width direction). ) Was obliquely stretched to form a first retardation layer. When performing oblique stretching, one peripheral edge portion of the COP film was stretched as it is in the width direction, and the other peripheral edge portion was stretched in the oblique direction with respect to the width direction. As a result of measuring the retardation value of the obtained retardation film using KOBRA-WR manufactured by Oji Measuring Equipment Co., Ltd., Re(550) = 271 nm, and the smaller of the angles formed by the long direction and the slow axis of the first retardation layer is 15 It was °. Moreover, as a result of measuring the film thickness of the 1st phase difference layer with an ellipsometer, it was 1.9 micrometers.

(4) Preparation of a long laminate (phase difference plate)

(I) Preparation of photoalignment film

The first phase difference layer was treated once under conditions of an output of 0.3 kW and a treatment speed of 3 m/min using a corona treatment apparatus (AGF-B10, manufactured by Kasuga Electric Corporation). On the surface subjected to the corona treatment, the composition for forming a photo-alignment film was applied with a bar coater, dried at 80° C. for 1 minute, and 100 mJ/ by using a polarizing UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Electric Corporation). Polarized UV exposure was performed at an angle of 75° with respect to the length direction of the COP with the accumulated light amount of cm 2. It was 150 nm as a result of measuring the film thickness of the obtained photoalignment film with an ellipsometer.

(Ii) the number average molecular weight of the photoalignment layer

After diluting the number average molecular weight of the obtained photoalignment film 10 times with tetrahydrofuran, it was measured according to the following method.

Device ; HLC-8220GPC (manufactured by Tosoh Corporation)

column ; TOSOH TSKgel MultiporeHXL-M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 ml/min

Detector; RI

Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-5000, A-500

(Iii) formation of a second phase difference layer made of a liquid crystal cured film

On the obtained photoalignment film, the polymerizable liquid crystal composition prepared in the above (2) was applied with a bar coater, dried at 100° C. for 1 minute, and then irradiated with ultraviolet rays using a high-pressure mercury lamp (in a nitrogen atmosphere, at a wavelength of 365 nm). In accumulated light quantity: 1200 mJ/cm<2>), the 2nd phase difference layer was formed, and the elongate laminated body (1) was obtained. As a result of measuring the film thickness of the obtained second phase difference layer with a laser microscope, the film thickness was 970 nm.

As a result of measuring the obtained phase difference value of the second phase difference layer using KOBRA-WR manufactured by Oji Measuring Equipment Co., Ltd., Re(550) = 135 nm, and the long direction of the first phase difference layer and the slow axis of the second phase difference layer are The smallest of the angles formed was 75°.

(5) Preparation of a long layered product (elliptically polarizing plate)

(I) Preparation of water-based adhesive

To 100 parts of water, 3 parts of carboxyl group-modified polyvinyl alcohol (Kurarepo Val KL318; manufactured by Kuraray Co., Ltd.) and a water-soluble polyamide epoxy resin (Sumireze Resin 650; manufactured by Sumika Chemtex Corporation, an aqueous solution having a solid content concentration of 30%) 1.5 Part was added and a water-based adhesive was prepared.

(Ii) Preparation of polarizing layer

A polyvinyl alcohol film (average polymerization degree of about 2400, saponification degree of 99.9 mol% or more) having a thickness of 30 µm was uniaxially stretched by about 5 times by dry stretching, and further maintained in a state of tension, in pure water at 40°C. It was immersed for a second. Thereafter, a dyeing treatment was performed by immersing in a dyeing aqueous solution having a mass ratio of iodine/potassium iodide/water of 0.044/5.7/100 at 28°C for 30 seconds. Next, it was immersed in an aqueous boric acid solution having a mass ratio of potassium iodide/boric acid/water of 11.0/6.2/100 at 70° C. for 120 seconds. Subsequently, after washing with pure water at 8° C. for 15 seconds, it was dried at 60° C. for 50 seconds and then at 75° C. for 20 seconds in a state maintained at a tension of 300 N, and iodine is adsorbed and oriented to the polyvinyl alcohol film. A 12 µm-thick polarizing layer (polarizer) was obtained.

With respect to the obtained polarizing layer, a film obtained by saponifying a triacetyl cellulose film (TAC; KC2UA; manufactured by Konica Minolta Co., Ltd., total light transmittance at 380 nm: 18%, thickness: 25 μm) on one surface as a front transparent protective layer The elongate laminate (1) was laminated on the other side so that the side opposite to the TAC film of the polarizing layer became the first phase difference layer side, and a water-based adhesive prepared so that the thickness of the adhesive layer obtained therebetween was 50 nm was injected. , And bonded with a nip roll. It dried at 60 degreeC for 2 minutes, maintaining the tension of the obtained bonding material at 430 N/m, and obtained the triacetyl cellulose film as a transparent protective film on one side, and the elliptically polarizing plate which has a long laminated body (1) on one side. The layer configuration of the elliptically polarizing plate was a second phase difference layer composed of a first phase difference layer composed of a front transparent protective layer/adhesive layer/polarization layer/adhesive layer/stretched film/light alignment film/liquid crystal cured film.

(6) Confirmation of adhesion

A sample for an adhesion test (10 cm long x 10 cm wide) was cut out from the produced long elliptically polarizing plate, and a 5 cm cello tape (registered trademark) was applied to one end of the sample, and the adhesive portion with the sample 2 cm After bonding as much as possible, the cello tape was peeled in the direction of 90° with respect to the bonding surface, and the adhesion was evaluated according to the following evaluation criteria. Table 1 shows the results.

<Evaluation criteria>

(I) Adhesion between the photo-alignment layer and the first retardation layer

○: No peeling occurred between the photoalignment film and the first retardation layer and/or the second retardation layer.

△: Partial peeling occurred between the photoalignment layer and the first retardation layer and/or the second retardation layer

X: The photoalignment film and the first retardation layer and/or the second retardation layer were almost or completely peeled off.

In addition, about peeling in a photoalignment film, it shows in the column of "alignment film" in Table 1.

(Ii) Adhesion between the polarizing layer and the retardation layer

○: No peeling occurred between the polarizing layer and the retardation layer

△: Partial peeling occurred between the polarizing layer and the retardation layer

X: The polarizing layer and the retardation layer were almost or completely peeled off

In addition, about peeling between a polarizing plate and a retardation layer, it shows in the column of "polarizing plate" in Table 1.

(7) SCI reflectance measurement

The surface of the elliptically polarizing plate on the side of the second retardation layer was bonded to the mirror using an adhesive. About the elliptically polarizing plate attached to the mirror, the SCI reflectance and reflection hue a*, b* were measured using the CM2600d manufactured by Konica Minolta. Table 1 shows the results.

2. Example 2

Except having changed the 1st retardation layer and the 2nd retardation layer as shown in Table 1, it carried out similarly to Example 1, and produced the elongate laminated body, and various physical properties were evaluated. Table 1 shows the results.

3. Example 3

Except having changed the 1st retardation layer and the 2nd retardation layer as shown in Table 1, it carried out similarly to Example 1, and produced the elongate laminated body, and various physical properties were evaluated. Table 1 shows the results.

4. Example 4

Except having changed the 1st retardation layer and the 2nd retardation layer as shown in Table 1, it carried out similarly to Example 1, and produced the elongate laminated body, and various physical properties were evaluated. Table 1 shows the results.

5. Example 5

Instead of triacetyl cellulose as the front surface protective layer, a norbornene resin film containing an ultraviolet absorber (product name Zeonore, manufactured by Nippon Xeon, total light transmittance at 380 nm: 8%) was used, and a first retardation layer, Except having changed the 2nd phase difference layer as shown in Table 1, it carried out similarly to Example 1, and produced the elongate laminated body, and various physical properties were evaluated. Table 1 shows the results.

6. Example 6

Except having used the photoalignment film which has the number average molecular weight shown in Table 1, it carried out similarly to Example 1, and produced the elongate laminated body, and various physical properties were evaluated. Table 1 shows the results.

7. Example 7

Except having used the photoalignment film which has the number average molecular weight shown in Table 1, it carried out similarly to Example 1, and produced the elongate laminated body, and various physical properties were evaluated. Table 1 shows the results.

8. Example 8

A film obtained by saponifying a triacetylcellulose film (TAC; KC2UA; manufactured by Konica Minolta Co., Ltd.) on one side of the polarizing layer, and a triacetylcellulose film (TAC; KC2UA; manufactured by Konica Minolta Corporation) on the other surface was a water-based adhesive. It bonded together to obtain a polarizing plate. A long laminate was prepared in the same manner as in Example 1, except that the unsaponified triacetylcellulose side of the obtained polarizing plate and the first retardation layer of the long laminate 1 were bonded with a water-based adhesive. Evaluated. Table 1 shows the results.

9. Example 9

In the same manner as in Example 1, except that the long laminate (1) was laminated so that the side opposite to the TAC film of the polarizing layer became the (second) retardation layer side composed of a liquid crystal cured film, the front transparent protective layer/adhesive layer/polarized light A long laminate (elliptically polarizing plate) composed of a retardation layer composed of a layer/adhesive layer/liquid crystal cured film/a retardation layer composed of a light alignment film/stretched film was prepared, and various physical properties were evaluated. Table 1 shows the results.

10. Comparative Example 1

The same as in Example 1 except that the smaller of the angles between the long direction and the slow axis of the first retardation layer, and the angle between the long direction of the first retardation layer and the slow axis of the second retardation layer is the angle shown in Table 1. Then, a long laminate was produced, and various physical properties were evaluated. Table 1 shows the results.

11. Comparative Example 2

The same as in Example 1 except that the smaller of the angles between the long direction and the slow axis of the first retardation layer, and the angle between the long direction of the first retardation layer and the slow axis of the second retardation layer is the angle shown in Table 1. Then, a long laminate was produced, and various physical properties were evaluated. Table 1 shows the results.

12. Comparative Example 3

The same as in Example 1 except that the smaller of the angles between the long direction and the slow axis of the first retardation layer, and the angle between the long direction of the first retardation layer and the slow axis of the second retardation layer is the angle shown in Table 1. Then, a long laminate was produced, and various physical properties were evaluated. Table 1 shows the results.

1: first phase difference layer
2: second phase difference layer
3: photoalignment layer
4: polarizing layer
5: adhesive layer
6: protective layer
11: long laminated body
12: phase difference plate
13: polarizing plate

Claims (9)

As a long laminate having a first retardation layer, a photoalignment film, and a second retardation layer in this order,
The elongate laminated body satisfies the following formulas (1) and (2), one of the first phase difference layer and the second phase difference layer is a stretched film, and the other is a liquid crystal cured film.
10° ≤ θa ≤ 30° or 60° ≤ θa ≤ 80° (1)
2θa + 40° ≤ θb ≤ 2θa + 50° (2)
[In the formula, θa is the smaller of the angles between the long direction of the long stacked body and the slow axis of the first phase difference layer, and θb is the angle between the long direction of the first retardation layer and the slow axis of the second phase difference layer. It's a small angle.] The method of claim 1,
A long laminated body in which the first phase difference layer satisfies the following equation (3), and the second phase difference layer satisfies the following equation (4).
200 ㎚ <Re(550) ＜ 320 ㎚ (3)
100 ㎚ <Re(550) ＜ 160 ㎚ (4)
[In the formula, Re(550) represents an in-plane retardation value at a wavelength of 550 nm.] The method according to claim 1 or 2,
The photoalignment film has a photoreactive group, and the photoreactive group is a dimerization reactive photoreactive group. The method according to any one of claims 1 to 3,
The number average molecular weight of a photoalignment film is 20000-100000, and a long laminated body. The method according to any one of claims 1 to 4,
A long laminate having a thickness of the photoalignment film of 100 to 300 nm. The method according to any one of claims 1 to 5,
The elongated laminate further has a transparent protective layer, an adhesive layer, and a polarizing layer,
Having a transparent protective layer, an adhesive layer, a polarizing layer, an adhesive layer, a first retardation layer, a photoalignment film, and a second retardation layer in this order,
The first phase difference layer is a stretched film, and the second phase difference layer is a liquid crystal cured film. The method of claim 6,
A long laminated body in which the total light transmittance in 380 nm of the transparent protective layer is 30% or less. The method according to claim 6 or 7,
Iodine is contained as a dichroic dye in a polarizing layer, and the absorption axis of a polarizing layer is a long picture direction of the said elongate laminated body. An organic EL display device comprising a sheet body obtained from the elongate laminate according to any one of claims 1 to 8.

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