TW201908781A - Elliptical polarizer - Google Patents

Abstract

The present invention provides an elliptical polarizing plate having excellent processing characteristics without defects such as waving on a cut end face even if cutting is performed. The present invention relates to an elliptical polarizing plate having a polarizing layer, a [lambda]/4 retardation layer, a vertically aligned liquid crystal cured layer, and a reinforcing layer; wherein the vertically aligned liquid crystal cured layer is composed of a polymer of a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound oriented in a direction perpendicular to the plane of the liquid crystal cured layer, the film thickness of the vertically aligned liquid crystal cured layer is 3 [mu]m or less, and the interlayer distance between the vertically aligned liquid crystal cured layer and the reinforcing layer is 5 [mu]m or less.

Description

   Elliptical polarizer   

The present invention relates to an elliptically polarizing plate that can be used in displays and the like, and an organic EL display device including the elliptically polarizing plate.

In recent years, with the diversification of displays, thinning of elliptically polarizing plates is required. As a method for thinning an elliptically polarizing plate, it is known to change the retardation plate used in the elliptically polarizing plate from an extended retardation plate to a liquid crystal obtained by curing a polymerized liquid crystal compound in an aligned state. A retardation plate made of hardened film. For example, Patent Document 1 discloses a combination of a λ / 4 retardation plate having a horizontal alignment formed by a liquid crystal cured film and a phase formed by the liquid crystal cured film having anisotropy (also referred to as anisotropy) in the film thickness direction. Circular polarizer with optical compensation function for differential plate.

    [Prior technical literature]         [Patent Literature]    

[Patent Document 1] Japanese Patent Laid-Open No. 2015-163935

However, in order to reduce the thickness of the liquid crystal cured film included in the elliptical polarizing plate, the liquid crystal cured film is formed on the base material and then transferred to the polarizing plate to peel off the base material. The mechanical strength of the liquid crystal cured film is insufficient. Therefore, if the liquid crystal cured film formed on the substrate is to be individually transferred to a polarizing plate to obtain an elliptical polarizing plate, when the obtained film is cut to a size suitable for the purpose, it may sometimes occur on the cut end surface. Defects such as undulations.

Therefore, the object of the present invention is an elliptically polarizing plate that does not cause defects such as wave undulations on the cutting end surface and has good processing characteristics, and an organic EL display device including the elliptically polarizing plate.

In order to solve the above-mentioned problems, the present inventors worked hard on the results of the review and completed the present invention. That is, the present invention includes the following.

[1] An elliptically polarizing plate comprising a polarizing layer, a λ / 4 retardation layer, a vertically aligned liquid crystal hardened layer, and a reinforcing layer, wherein the vertically aligned liquid crystal hardened layer is formed by The polymer of the polymerizable liquid crystal composition of the polymerizable liquid crystal compound in a state of vertical alignment is composed of a polymer of a polymerizable liquid crystal composition, and the film thickness of the vertically aligned liquid crystal hardened layer is 3 μm or less.

Here, the interlayer distance between the vertically aligned liquid crystal hardened layer and the reinforcing layer is, for example, 5 μm or less.

[2] The elliptically polarizing plate according to [1], wherein the film thickness of the reinforcing layer is 1 to 10 μm.

[3] The elliptical polarizing plate according to [1] or [2], wherein the λ / 4 retardation layer is a horizontally aligned liquid crystal hardened layer, and the horizontally aligned liquid crystal hardened layer is formed by A polymer of a polymerizable liquid crystal composition of a polymerizable liquid crystal compound aligned in a horizontal direction.

[4] The elliptical polarizing plate according to any one of [1] to [3], which has a polarizing layer, a λ / 4 retardation layer, a vertically aligned liquid crystal hardening layer, and a reinforcing layer in this order.

[5] The elliptical polarizing plate according to any one of [1] to [3], which has a polarizing layer, a vertical alignment liquid crystal hardening layer, a reinforcing layer, and a λ / 4 retardation layer in this order.

[6] The elliptical polarizing plate according to any one of [1] to [3], which sequentially includes a polarizing layer, a reinforcing layer, a vertically aligned liquid crystal hardened layer, and a λ / 4 retardation layer.

[7] The elliptical polarizing plate according to any one of [1] to [6], wherein the reinforcing layer is selected from the group consisting of acrylic resin, epoxy resin, oxetane resin, and amine ester resin. And at least one selected from the group consisting of melamine resin.

[8] The elliptical polarizer according to any one of [1] to [7], which has an alignment layer having a film thickness of 5 μm or less between the vertically aligned liquid crystal hardened layer and the reinforcing layer, and the alignment layer is composed of The element includes a layer composed of a compound of the Si element, the C element, and the O element.

[9] The elliptically polarizing plate according to any one of [1] to [8], in which the difference in the average refractive index between the adjacent layers in a plane of a wavelength of 550 nm is 0.20 or less.

[10] The elliptically polarizing plate according to any one of [1] to [9], wherein the λ / 4 retardation layer has a refractive index ellipsoid formed by the λ / 4 retardation layer at a wavelength The range of λ = 400 to 700nm has the relationship of nxQ (λ)> nyQ (λ) ≒ nzQ (λ) [where nxQ (λ) is the refractive index formed in the λ / 4 retardation layer In the ellipsoid, the principal refractive index of light with a wavelength of λ (nm) in a direction parallel to the plane of the retardation layer; nyQ (λ) represents the refractive index ellipsoid formed by the λ / 4 retardation layer, Refractive index of light of wavelength λ (nm) parallel to the plane of the retardation layer and orthogonal to the direction of the aforementioned nxQ (λ); nzQ (λ) represents the In the formed refractive index ellipsoid, the refractive index of light having a wavelength of λ (nm) in a direction perpendicular to the plane of the retardation layer]; and satisfying the relationship of the following formulae (1) to (3), ReQ (450 ) / ReQ (550) ≦ 1.00 (1)

1.00 ≦ ReQ (650) / ReQ (550) (2)

100nm ≦ ReQ (550) ≦ 160nm (3)

[In the formula, ReQ (450) represents the in-plane retardation value of the λ / 4 retardation layer for light having a wavelength of λ = 450 nm, and ReQ (550) represents the retardation value of the λ / 4 retardation layer for light having a wavelength of λ = 550 nm. In-plane retardation value, ReQ (650) represents the in-plane retardation value of a λ / 4 retardation layer for light having a wavelength of λ = 650 nm, and the in-plane retardation layer of λ / 4 retardation layer for a light having a wavelength of λ (nm) The retardation value ReQ (λ) is represented by ReQ (λ) = (nxQ (λ) -nyQ (λ)) × dQ, where dQ represents the thickness of the λ / 4 retardation layer].

[11] The elliptical polarizing plate according to any one of [1] to [10], wherein the vertical alignment liquid crystal hardened layer has a refractive index ellipsoid formed by the vertical alignment liquid crystal hardened layer at a wavelength λ = The range from 400 to 700 nm has the relationship of nzV (λ)> nxV (λ) ≒ nyV (λ)

[In the formula, nzV (λ) represents the refractive index in the refractive index ellipsoid formed by the liquid crystal hardened layer in a direction perpendicular to the plane of the liquid crystal hardened layer with respect to light having a wavelength of λ (nm); nxV (λ) Is the maximum refractive index of the refractive index ellipsoid formed by the liquid crystal hardened layer in the direction parallel to the plane of the liquid crystal hardened layer with respect to the wavelength λ (nm), and nyV (λ) is the In the formed refractive index ellipsoid, the refractive index of light having a wavelength of λ (nm) that is parallel to the plane of the liquid crystal hardened layer and orthogonal to the direction of the aforementioned nxV; however, nxV (λ) = nyV ( λ), nxV (λ) represents the refractive index in any direction parallel to the plane of the liquid crystal hardened layer]; and satisfies the relationship of the following formulas (4) to (6), RthV (450) / RthV (550) ≦ 1.00 (4)

1.00 ≦ RthV (650) / RthV (550) (5)

-120nm ≦ RthV (550) ≦ -50nm (6)

[In the formula, RthV (450) represents the retardation value in the thickness direction of the liquid crystal hardened layer for light having a wavelength of λ = 450nm, and RthV (550) represents the retardation value in the thickness direction of the liquid crystal hardened layer for light having a wavelength of λ = 550nm Value, RthV (650) represents the retardation value of the thickness direction of the liquid crystal hardened layer for light having a wavelength of λ = 650nm, and the retardation value of the thickness direction RthV (λ) of the liquid crystal hardened layer for light having a wavelength of λ (nm) is It is represented by RthV (λ) = [(nxV (λ) + nyV (λ)) / 2-nzV (λ)] × dV; here, in the refractive index ellipsoid formed by the liquid crystal hardened layer, nzV (λ) Represents the principal refractive index at a wavelength of λ (nm) in a direction perpendicular to the plane of the liquid crystal hardened layer, and "(nxV (λ) + nyV (λ)) / 2" indicates that at the wavelength of λ (nm) in the liquid crystal hardened layer The average refractive index in a plane; dV represents the thickness of the liquid crystal hardened layer].

[12] An organic EL display device including the elliptically polarizing plate according to any one of [1] to [11].

[13] An organic EL display device including the elliptically polarizing plate according to any one of [1] to [12].

The elliptically polarizing plate of the present invention does not cause defects such as undulations on the cutting end surface even when cutting, and has good processing characteristics.

1,10,100‧‧‧‧ellips

2‧‧‧ polarizing layer

3‧‧‧ Adhesive layer

4‧‧‧λ / 4 retardation layer

5‧‧‧Alignment layer

6‧‧‧ Vertically aligned liquid crystal hardened layer

7‧‧‧ vertical alignment layer

8‧‧‧ reinforcement layer

FIG. 1 is a schematic cross-sectional view showing an example of a layer configuration of an elliptical polarizing plate of the present invention.

Fig. 2 is a schematic cross-sectional view showing an example of a layer configuration of an elliptical polarizing plate of the present invention.

Fig. 3 is a schematic cross-sectional view showing an example of a layer configuration of an elliptical polarizing plate of the present invention.

The elliptical polarizing plate of the present invention includes a polarizing layer, a λ / 4 retardation layer, a vertical alignment liquid crystal hardening layer, and a reinforcing layer. The stacking order of each layer can be appropriately selected. In a preferred aspect, the layers are laminated in the following order. Polarizing layer, λ / 4 retardation layer, vertical alignment liquid crystal hardened layer, and reinforcing layer; polarizing layer, vertical alignment liquid crystal hardening layer, reinforcing layer, λ / 4 retardation layer; polarizing layer, reinforcing layer, vertical alignment liquid crystal hardening layer, λ / 4 retardation layer.

An example of the layer configuration of the elliptically polarizing plate of the present invention laminated in this order is shown in Figs. 1 to 3, but the present invention is not limited to these aspects.

The elliptical polarizing plate 1 shown in FIG. 1 is sequentially provided with a polarizing layer 2, an adhesive 3, a λ / 4 retardation layer 4, an alignment layer 5, an adhesive 3, a vertical alignment liquid crystal hardening layer 6, and a vertical alignment layer. 7. Reinforcement layer 8. The elliptical polarizing plate 10 shown in FIG. 2 is sequentially provided with a polarizing layer 2, an adhesive 3, a vertical alignment liquid crystal hardening layer 6, a vertical alignment layer 7, a reinforcing layer 8, an adhesive 3, and a λ / 4 retardation layer. 4. Alignment layer 5. The elliptical polarizing plate 100 shown in FIG. 3 is sequentially provided with a polarizing layer 2, an adhesive 3, a reinforcing layer 8, a vertical alignment layer 7, a vertical alignment liquid crystal hardening layer 6, an adhesive 3, and a λ / 4 retardation layer. 4. Alignment layer 5. The elliptically polarizing plates 1, 10, and 100 are bonded so that the absorption axis of the polarizing layer 2 becomes substantially 45 ° with respect to the slow axis (optical axis) of the λ / 4 retardation layer 4. The polarizing layer 2 may include a transparent protective film on one side of the polarizer (the side opposite to the adhesive 3). In the present specification, the term “substantially 45 °” is usually in a range of 45 ° ± 5 °.

[Reinforcement layer]

The elliptically polarizing plates 1, 10, and 100 of the present invention are provided with a reinforcing layer 8 having a function of reinforcing a layer included in the elliptically polarizing plate (particularly, a vertically aligned liquid crystal hardened layer 6). The elliptically polarizing plates 1, 10 and 100, even if the vertical alignment liquid crystal hardened layer 6 is a thin film, the reinforcing layer 8 can fully reinforce the strength of the vertical alignment liquid crystal hardened layer 6. , The strength of the vertically aligned liquid crystal hardened layer 6 can be further reinforced. Therefore, the processing characteristics of the elliptically polarizing plate are improved, and defects at the cutting end face can be effectively suppressed or prevented. In addition, in this specification, the "interlayer distance" means the shortest distance between the vertically aligned liquid crystal hardened layer 6 and the reinforcing layer 8, and the "processing characteristics" means that when the elliptical polarizing plate is cut, it can be prevented or prevented. Defects such as undulations on the cutting end surface.

The interlayer distance between the vertical alignment liquid crystal hardened layer 6 and the reinforcing layer 8 is, for example, 5 μm or less, preferably 3 μm or less, more preferably 1.5 μm or less, still more preferably 1.0 μm or less, still more preferably 500 nm or less, and particularly preferably 300 nm. the following. If there is no vertical alignment layer 7, the interlayer distance is 0 nm. The lower limit of the interlayer distance is necessarily determined by the film thickness of the layer between the vertical alignment liquid crystal hardened layer 6 and the reinforcing layer 8 (the film thickness of the vertical alignment layer 7 in the state of Figs. 1 to 3), so there is no special The limitation is preferably 1 nm or more. When the interlayer distance is below the above upper limit, the reinforcing layer 8 can more fully reinforce the vertical alignment liquid crystal hardened layer 6 and can exhibit good processing characteristics. Therefore, when the elliptical polarizing plate is cut, defects such as undulations on the cutting end face will not be generated. Moreover, the shorter the interlayer distance, the easier it is for the reinforcing layer 8 to contribute to the reinforcement of the vertically aligned liquid crystal hardened layer 6, so that the processing characteristics tend to be improved.

The reinforcing layer 8 is made of a material that can exert the strength capable of reinforcing the vertical alignment liquid crystal hardened layer 6. For example, the reinforcing layer 8 is selected from the group consisting of an acrylic resin, an epoxy resin, an oxetane resin, an amine ester resin, and a melamine resin. Made of at least 1 kind. Among these, from the viewpoint of easily forming the reinforcing layer 8 having high hardening property and high reinforcing property, it is preferably selected from the group consisting of acrylic resin, epoxy resin, oxetane resin, amine ester resin, and melamine resin. It is formed by at least 1 type of the group formed, and more preferably contains at least 1 type selected from the group which consists of an acrylic resin and an amine ester resin.

The reinforcing layer 8 is preferably a cured product of a curable composition containing a curable material that is cured by heat and light. Examples of the hardening material containing the reinforcing layer 8 made of an acrylic resin include monofunctional (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ( Hydroxybutyl meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate; polyfunctional (meth) acrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolmethane triacrylate, tetramethylol Methylmethane tetraacrylate, pentaerythritol triacrylate, neopentaerythritol triacrylate, neopentaerythritol tetraacrylate, glycerol triacrylate, dinepentaerythritol triacrylate, dinepentaerythritol Tetraacrylate, Dipentaerythritol pentaacrylate, Dipentaerythritol hexaacrylate, Ginseng (propylene ethoxyethyl) trimer isocyanate; ethylene glycol dimethacrylate, diethylene glycol dimethyl Acrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, Methylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane tetramethacrylate, pentyl glycerol trimethacrylate Ester, neopentaerythritol trimethacrylate, neopentaerythritol tetramethacrylate, glycerol trimethacrylate, dinepentaerythritol trimethacrylate, dinepentaerythritol tetramethyl Acrylates, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, ginsyl (methacryloxyethyl) trimer isocyanate, and the like. The (meth) acrylate can be used alone or in combination of two or more kinds, from the viewpoint of suppressing curl caused by heating during and after curing, from the viewpoint of improving processing characteristics, and from the viewpoint of ensuring sufficient reinforcement of the reinforcing layer 8 See, a (meth) acrylate may be appropriately selected. From the same viewpoint, it can be mixed with epoxy resin, oxetane resin, amine ester resin, melamine resin, and the like. In addition, in this specification, an acrylic acid ester and a methacrylic acid ester may be collectively called (meth) acrylic acid ester, and an acrylic acid and methacrylic acid may be collectively called (meth) acrylic acid.

Examples of the hardening material containing the reinforcing layer 8 made of an amine ester resin include an amine (meth) acrylate of a reaction product of (meth) acrylic acid and / or (meth) acrylate, a polyol, and a diisocyanate. Wait. Specifically, the amine ester (meth) acrylate can be prepared from (meth) acrylic acid and / or (meth) acrylate and a polyhydric alcohol by modulating a hydroxy (meth) acrylate having at least one hydroxyl group in the molecule, It is produced by reacting with diisocyanate. The urethane (meth) acrylate can be used alone or in combination of two or more.

The (meth) acrylate may be a chain or cyclic alkyl ester of (meth) acrylic acid. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and the like ) Cycloalkyl (meth) acrylates such as alkyl acrylate and cyclohexyl (meth) acrylate. The polyol is a compound having at least two hydroxyl groups in a molecule. Examples include ethylene glycol, propylene glycol, 1,3-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1, 6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl-1 , 3-pentanediol, neopentyl glycol ester of hydroxypivalic acid, cyclohexanedimethylol, 1,4-cyclohexanediol, spiroglycol, tricyclodecanediol Base, hydrogenated bisphenol A, ethylene oxide addition to bisphenol A, propylene oxide addition to bisphenol A, trimethylolethane, trimethylolpropane, glycerol, 3-methylpentane- 1,3,5-triol, neopentaerythritol, dipentaerythritol, trinepentaerythritol, glucose, etc.

As the diisocyanate-based compound having two isocyanate groups (-NCO) in the molecule, various diisocyanates of aromatic, aliphatic, or alicyclic types can be used. Specific examples include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-toluene diisocyanate, 4,4'-diphenyl diisocyanate, and 1,5-naphthalene diisocyanate. Isocyanate, 3,3'-dimethyl-4,4'-diphenyl diisocyanate, xylylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4'-diphenylmethane diisocyanate And nuclear hydrides of diisocyanates having aromatic rings among them.

From the viewpoint of suppressing curl caused by heating during and after curing, from the viewpoint of improving processing characteristics, and from the viewpoint of ensuring sufficient reinforcing properties of the reinforcing layer 8, an amine ester (meth) acrylate can be appropriately selected. From the same viewpoint, it may be mixed with an acrylic resin, an epoxy resin, an oxetane resin, a melamine resin, or the like.

Examples of the hardening material containing a reinforcing layer made of an epoxy resin include an alicyclic epoxy compound, an aromatic epoxy compound, a hydrogenated epoxy compound, and an aliphatic epoxy compound.

An alicyclic epoxy compound is a compound having at least one epoxy group directly bonded to an alicyclic ring in a molecule. For example, 3,4-epoxycyclohexanecarboxylic acid, 3,4-epoxycyclohexylmethyl ester, 3,4-epoxy-6-methylcyclohexanecarboxylic acid, 3,4-epoxy- 6-methylcyclohexyl methyl ester, ethylidene bis (3,4-epoxycyclohexaneformate), adipic acid bis (3,4-epoxycyclohexylmethyl) ester, adipic acid Acid bis (3,4-epoxy-6-methylcyclohexylmethyl) ester, diethylene glycol bis (3,4-epoxycyclohexylmethyl ether), ethylene glycol bis (3,4 -Epoxycyclohexylmethyl) ether and the like. These alicyclic epoxy compounds can be used individually or in combination of 2 or more types.

The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in the molecule. Specific examples thereof include bisphenol epoxy compounds such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S, or oligomers thereof. Products; novolac epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, hydroxybenzaldehyde phenol novolac epoxy resin; 2,2 ', 4,4'-tetrahydroxydiphenylmethane Polyfunctional epoxy compounds such as epoxypropyl ether, 2,2 ', 4,4'-tetrahydroxybenzophenone and other polyfunctional epoxy compounds; polyfunctional epoxy resins such as epoxidized polyvinyl phenol Wait. These aromatic epoxy compounds can be used individually or in combination of 2 or more types.

The hydrogenated epoxy compound is a core hydride of the above-mentioned aromatic epoxy compound to become a hydrogenated epoxy compound. These can be produced by a method in which an aromatic polyhydroxy compound (typically, bisphenols) for a raw material belonging to a corresponding aromatic epoxy compound is selectively used in the presence of a catalyst and under pressure. A method in which a polyhydric alcohol (typically hydrogenated bisphenols) obtained by performing a hydrogenation reaction is reacted with epichlorohydrin to form a chlorohydrin ether, and a method for performing ring closure in a molecule using a base is further performed. These hydrogenated epoxy compounds can be used individually or in combination of 2 or more types.

The aliphatic epoxy compound is an aliphatic polyhydric alcohol or a polyoxypropyl ether of an alkylene oxide adduct thereof. Specific examples thereof include diglycidyl ether of neopentyl glycol, diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, Triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of propylene glycol, etc. Polyepoxides and the like of polyether polyols obtained by adding one or two or more kinds of alkylene oxides (ethylene oxide, propylene oxide) to aliphatic polyhydric alcohols such as alcohols, propylene glycol, and glycerin. These aliphatic epoxy compounds can be used individually or in combination of 2 or more types.

From the viewpoint of suppressing curl caused by heating during and after curing, from the viewpoint of improving processing characteristics, from the viewpoint of ensuring sufficient reinforcement of the reinforcing layer 8, and from the viewpoint of adjusting the adhesiveness to the substrate and the liquid crystal cured layer, The epoxy resin can be appropriately selected. From the same viewpoint, it may be mixed with an acrylic resin, an amine ester resin, an oxetane resin, a melamine resin, or the like.

Examples of the curable material containing the reinforcing layer 8 made of an oxetane resin include a compound containing at least one oxetanyl group in the molecule. Specific examples thereof include 3-ethyl-3-hydroxymethyloxetane (also referred to as oxetanol), 2-ethylhexyloxetane, 1,4-bis [ {(3-ethyloxetane-3-yl) methoxy} methyl] benzene (also known as diphenyldimethyldioxetane), 3-ethyl-3 [{( 3-ethyloxetane-3-yl) methoxy} methyl] oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3- ( Cyclohexyloxy) methyl-3-ethyloxetane and the like.

Examples of the hardening material containing the reinforcing layer 8 made of melamine resin include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxymethyl melamine. And other melamine compounds.

The hardening composition for forming a reinforcing layer may further include a photopolymerization initiator, a thermal polymerization initiator, a solvent, a polymerization inhibitor, a photosensitizer, a leveling agent, an antioxidant, a chain transfer agent, a light stabilizer, an adhesion-imparting agent, Additives such as fillers, flow regulators, plasticizers, defoamers, pigments, antistatic agents, and UV absorbers.

Regarding the photopolymerization initiator, in the case where a curable composition that is hardened by radical polymerization, such as (meth) acrylate, amine (meth) acrylate, is used as the curable material, photoradical polymerization can be used. When a curable composition such as an epoxy compound or an oxetane compound that is hardened by cationic polymerization is used as the curable composition, a photocationic polymerization initiator may be used. When a curable composition such as a melamine compound is used as the curable composition, a thermal polymerization initiator can be used.

Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. Examples of the photo-radical polymerization initiator include a benzoin compound, a benzophenone compound, a diphenylethylene ketal compound, an α-hydroxy ketone compound, an α-amino ketone compound, and Examples of the compound include a photocationic polymerization initiator such as an onium salt such as an aromatic diazonium salt, an aromatic sulfonium salt, or an aromatic sulfonium salt, and an iron-aromatic hydrocarbon complex. Specifically, for example: 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 Japan BASF Corporation) System); SEIKUOL BZ, SEIKUOL Z, SEIKUOL BEE (made by Seiko Chemical Co., Ltd.); Kayacure BP100 (made by Nippon Kayaku Co., Ltd.); Kayacure UVI-6992 (made by Dow); ADEKA Optomer SP-152, ADEKA Optomer SP -170, ADEKA Optomer N-1717, ADEKA Optomer N-1919, ADEKA ARKLS NCI-831, ADEKA ARKLS NCI-930 (above ADEKA Corporation); TAZ-A, TAZ-PP (above Japan Siber Hegner Corporation) and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.); KAYARAD (registered trademark) series (manufactured by Nippon Kayaku Co., Ltd.); CYRACURE UVI series (manufactured by Dow Chemical Co.); CPI series (manufactured by SAN-APRO Co., Ltd.); TAZ, BBI And DTS (Midori Chemical Co., Ltd.); RHODORSIL (registered trademark) (Rhodia Co., Ltd.) and so on. The photopolymerization initiator can be used alone or in combination of two or more. The photopolymerization initiator can be appropriately selected and used according to the materials used.

Since the energy emitted from the light source can be fully utilized and the productivity is good, the photopolymerization initiator preferably has a maximum absorption wavelength of 300 nm to 400 nm, and more preferably 300 nm to 380 nm. Among them, α-acetophenone-based polymerization initiators, An oxime-based photopolymerization initiator is preferred.

Examples of the α-acetophenone-based polymerization initiator include 2-methyl-2-morpholinyl-1- (4-methylthiophenyl) propane-1-one and 2-dimethylamino-1 -(4-morpholinylphenyl) -2-benzylbutane-1-one and 2-dimethylamino-1- (4-morpholinylphenyl) -2- (4-methyl Phenylmethyl) butane-1-one and the like, more preferably 2-methyl-2-morpholinyl- (4-methylthiophenyl) propane-1-one and 2-dimethylamino 1- (4-morpholinylphenyl) -2-benzylbutane-1-one. Commercially available products of the α-acetophenone compound include, for example, Irgacure 369, 379EG, and 907 (manufactured by BASF Corporation of Japan) and SEIKUOL BEE (manufactured by Seiko Chemical Co., Ltd.).

The oxime-based photopolymerization initiator generates radicals upon irradiation with light. This radical is suitable for polymerizing a hardenable composition in the deep part of the layer. Furthermore, from the viewpoint of more efficiently performing the polymerization reaction in the deep part of the layer, it is preferable to use a photopolymerization initiator that can efficiently use ultraviolet rays having a wavelength of 350 nm or more. The photopolymerization initiator which can efficiently use ultraviolet rays having a wavelength of 350 nm or more is preferably three. The compound and the oxime ester type carbazole compound are more preferably an oxime ester type carbazole compound from the viewpoint of sensitivity. Examples of oxime ester carbazole compounds include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzylhydrazine)], ethyl ketone, 1- [9- Ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -1- (O-acetamidooxime) and the like. Commercially available oxime ester carbazole compounds include, for example, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (above manufactured by BASF Corporation of Japan), ADEKA Optomer N-1919, ADEKA ARKLS NCI-831 (above ADEKA) Joint-stock company system) and so on.

Examples of the thermal polymerization initiator include: 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane- 1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile) ), 2,2'-azobis (2-methylpropionic acid) dimethyl, 2,2'-azobis (2-hydroxymethylpropionitrile) and other azo compounds; lauryl peroxide, Third butyl hydroperoxide, benzamyl peroxide, third butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, peroxidation Organic peroxides such as tert-butyl neodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexyl) peroxide; potassium persulfate, ammonium persulfate, peroxidation Inorganic peroxides such as hydrogen. These thermal polymerization initiators can be used alone or in combination of two or more.

The addition amount of the polymerization initiator is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass based on 100 parts by mass of the curable composition. If it is in the said range, a hardening reaction will fully advance easily.

The curable material is usually applied to the substrate in a state of being dissolved in a solvent. Therefore, the curable material preferably contains a solvent. The solvent is preferably a solvent that can dissolve the curable composition, and a solvent that is inert to the polymerization reaction of the curable material is more preferable. Examples of the solvent include water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, and 2-butoxyethanol. And alcohol solvents such as propylene 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; acetone, Ketone solvents such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; lipids such as ethyl cyclohexane Cyclic hydrocarbon solvents; 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; dimethylacetamide and dimethyl Amidamine-based solvents such as methylformamide, N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidone, and the like. These solvents can be used alone or in combination of two or more. Among these, an alcohol solvent, an ester solvent, a ketone solvent, a chlorine-containing solvent, a fluorene-based solvent, and an aromatic hydrocarbon solvent are preferred.

The content of the solvent is preferably 50 to 98 parts by mass, and more preferably 60 to 95 parts by mass based on 100 parts by mass of the curable composition. Therefore, the solid content in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. Within this range, the viscosity of the hardenable composition becomes low, so the thickness of the reinforcing layer becomes approximately uniform, and the reinforcing layer tends to be less likely to be uneven.

The hardenable composition can be obtained by stirring components other than hardenable materials such as hardenable materials and additives at a predetermined temperature.

The reinforcing layer 8 can be obtained by applying a curable composition to a substrate, removing the solvent, and curing the composition by heating and / or active energy rays.

The method of applying a curable composition to a substrate (hereinafter, referred to as a coating method A) may be, for example, an extrusion coating method, a direct gravure coating method, a trans-gravure coating method, or a CAP coating method. , Slit coating method, micro gravure method, die coating method, inkjet method, and the like. Further, for example, a method of applying using a coater such as a dip coater, a bar coater, or a spin coater may be used. Among them, in the case of continuous coating in a roll-to-roll type, a coating method by a micro gravure method, an inkjet method, a slit coating method, or a die coating method is preferred.

Examples of the method for removing the solvent (hereinafter referred to as solvent removal method A) include methods such as natural drying, ventilation drying, heating drying, drying under reduced pressure, and combinations thereof. Among them, natural drying or heating drying is preferred. The drying temperature is preferably in the range of 0 to 200 ° C, more preferably in the range of 20 to 150 ° C, and even more preferably in the range of 50 to 130 ° C. The drying time is preferably 10 seconds to 20 minutes, and more preferably 30 seconds to 10 minutes.

The irradiated active energy ray is appropriately selected depending on the type of the curable composition, the type of the photopolymerization initiator when the photopolymerization initiator is included, and the amount thereof. Specifically, for example, one or more kinds of light selected from the group consisting of visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays. Among them, in terms of the ease of controlling the progress of the polymerization reaction and the point that it can be widely used as a photopolymerization device in the field, ultraviolet light is preferred, and photopolymerization by ultraviolet light is preferred. The method selects the type of the polymerizable liquid crystal compound.

The aforementioned active energy ray light source may be, 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, and an emission wavelength range of 380 to 440 nm. LED light source for light, fluorescent lamp for insect trap, black light lamp, microwave excited mercury lamp, metal halide lamp, etc.

The ultraviolet irradiation intensity is usually 10 to 3000 mW / cm ² . The ultraviolet irradiation intensity is preferably an intensity in a wavelength region effective for activation of a photocationic polymerization initiator or a photoradical polymerization initiator. The time for irradiating light is usually from 0.1 seconds to 10 minutes, preferably from 0.1 seconds to 5 minutes, more preferably from 0.1 seconds to 3 minutes, and even more preferably from 0.1 seconds to 1 minute. When it is irradiated once or plural times with such an ultraviolet irradiation intensity, its cumulative light amount is 10 to 3000 mJ / cm ² , preferably 50 to 2000 mJ / cm ² , and more preferably 100 to 1000 mJ / cm ² . When the accumulated light amount is below this range, the curing of the curable composition becomes insufficient, and the processing characteristics of the elliptical polarizing plate may decrease. Conversely, when the amount of accumulated light is above this range, the elliptically polarizing plate may be colored.

In the case where the curable composition is hardened by heat, the heating temperature is appropriately selected depending on the type of the curable material, the type of the thermal polymerization initiator when the thermal polymerization initiator is included, and the amount thereof, for example, 50 to 200 ° C, preferably 50 to 130 ° C. The heating time is, for example, 10 seconds to 10 minutes, and preferably 10 seconds to 5 minutes. Furthermore, in the case of heating and drying, drying and hardening can be performed simultaneously.

The thickness of the reinforcing layer 8 is preferably from 1 to 10 μm from the viewpoint of reinforcement. When the thickness of the reinforcing layer 8 is greater than or equal to the above-mentioned lower limit value, the layers included in the elliptical polarizing plate, particularly the liquid crystal hardened layer 6 which is vertically aligned, can be sufficiently reinforced, and good processing characteristics can be exhibited. When the thickness of the reinforcing layer 8 is equal to or less than the above-mentioned upper limit value, it is preferable from the viewpoint of thinning the elliptically polarizing plate. The thickness of the reinforcing layer 8 is preferably from 1 to 5 μm, more preferably from 1 to 3 μm from the viewpoint of thinning the elliptically polarizing plate, and from 5 to 5 μm from the viewpoint of the processing characteristics of the elliptically polarizing plate. 10 μm, more preferably 7 to 10 μm. The film thickness of the reinforcing layer can be measured using an ellipsometer or a contact film thickness meter.

[Polarizing layer]

The polarizing layer 2 is a layer having a polarizing function. Such a layer may be, for example, a film containing a stretched film to which a pigment having an anisotropic absorption property is adsorbed or a film coated with a pigment having an anisotropic absorption property as a polarizer. Examples of the pigment having absorption anisotropy include a dichroic pigment.

A film containing a stretched film having an absorption anisotropic pigment as a polarizer is usually produced by sandwiching a transparent protective film with an adhesive on at least one side of the polarizer, and the polarizer is formed by A step of uniaxially stretching the polyvinyl alcohol-based resin film, a step of dyeing the polyvinyl alcohol-based resin film with a dichroic dye and adsorbing the dichroic dye, and a polyvinyl alcohol-based resin film having the dichroic dye adsorbed It is manufactured by the process using a boric-acid aqueous solution processing, and the process which wash | cleans with a boric-acid aqueous solution processing and water washing.

The polyvinyl alcohol-based resin can be obtained by saponifying a polyvinyl acetate-based resin. As for the polyvinyl acetate-based resin, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate, copolymers of vinyl acetate and other monomers copolymerizable therewith can also be 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 saponification degree of the polyvinyl alcohol-based resin is usually about 85 to 100 mol%, and preferably 98 mol% or more. This polyvinyl alcohol-based resin can be modified, and for example, polyvinyl acetal or polyvinyl acetal modified with aldehydes can be used. The degree of polymerization of the polyvinyl alcohol-based resin is usually about 1,000 to 10,000, and preferably in the range of 1500 to 5,000.

A film obtained by forming such a polyvinyl alcohol-based resin can be used as the original embryo film of the polarizing layer 2. The method for forming a polyvinyl alcohol-based resin into a film is not particularly limited, and a film can be formed by a known method. The film thickness of the polyvinyl alcohol-based protoembryonic membrane can be, for example, about 10 to 150 μm.

The uniaxial extension of the polyvinyl alcohol-based resin film can be performed before, simultaneously with, or after dyeing with a dichroic pigment. In the case of performing one-axis extension after dyeing, the one-axis extension may be performed before or during the boric acid treatment. Moreover, one-axis extension may be performed in these plural stages. When one axis is extended, it can be extended on one axis between rollers with different peripheral speeds, or it can be extended on one axis using hot rollers. In addition, the uniaxial stretching may be a dry stretching in the air, or a wet stretching using a solvent and stretching the polyvinyl alcohol resin film in a swollen state. The stretching ratio is usually about 3 to 8 times.

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

As the dichroic dye, specifically, iodine and a dichroic organic dye can be used. Examples of the dichroic organic dye include a dichroic direct dye made of a bisazo compound such as C.I. Direct Red 39 and a dichroic direct dye made of a compound such as trisazo or tetrasazo. The polyvinyl alcohol-based resin film is preferably subjected to a treatment of immersion in water before the dyeing treatment.

When using iodine as a dichroic dye, a method of dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is generally adopted. 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. The immersion time (dyeing time) in the aqueous solution is usually about 20 to 1800 seconds.

On the other hand, when a dichroic organic dye is used as a dichroic dye, a method of dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is generally adopted. The content of the dichroic organic dye in the aqueous solution is usually about 1 × 10 ^-4 to 10 parts by mass per 100 parts by mass of water, preferably about 1 × 10 ^-3 to 1 part by mass, and more preferably 1 × 10 ^-3 to 1 × 10 ^-2 parts by mass. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. The temperature of the dichroic dye aqueous solution used for dyeing is usually about 20 to 80 ° C. The immersion time (dyeing time) in the aqueous solution is usually about 10 to 1800 seconds.

The boric acid treatment after the dichroic dye is dyed is usually performed by a method of immersing the dyed polyvinyl alcohol-based resin film in an aqueous boric acid solution. The content of boric acid in the boric acid aqueous 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. In the case of using iodine as a dichroic pigment, the boric acid aqueous solution preferably contains potassium iodide, and the content of potassium iodide in this case is usually about 0.1 to 15 parts by mass, and preferably 5 to 12 parts by mass per 100 parts by mass of water. about. The immersion time in the boric acid aqueous solution is usually about 60 to 1200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the boric acid aqueous solution 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 the boric acid treatment is usually subjected to a water washing treatment. The water washing treatment can be performed, for example, by immersing a boric acid-treated polyvinyl alcohol-based resin film in water. The temperature of the water for the water washing treatment is usually about 5 to 40 ° C. The immersion time is usually about 1 to 120 seconds.

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

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

Examples of the film coated with an anisotropic dye include a film obtained by coating a composition containing a dichroic dye having liquid crystallinity or a composition containing a dichroic dye and a polymerizable liquid crystal. The film preferably has a protective film on one or both sides. The protective film may be, for example, the same as a substrate described later.

The film which has been coated with an anisotropic dye is preferably a thin film. However, when the film is too thin, the strength is reduced and the workability tends to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, and more preferably 0.5 to 3 μm.

The film which has been coated with an anisotropic pigment is specifically, for example, a film described in Japanese Patent Application Laid-Open No. 2012-33249.

The polarizing layer 2 is obtained by laminating a transparent protective film on at least one side of the polarizer obtained in this manner with an adhesive therebetween. As a transparent protective film, the same transparent film as a base material mentioned later can be used suitably.

[λ / 4 retardation layer]

The λ / 4 retardation layer is a layer having an anisotropy in the refractive index in the plane of the 4 series film. The λ / 4 retardation layer 4 can be formed by a method of extending or contracting a polymer film, but from the viewpoint of thinning an elliptically polarizing plate, it is preferable to include a polymerizable liquid crystal compound (also referred to as a polymer Polymerizable liquid crystal composition) is formed by polymerizing in an aligned state.

The three-dimensional refractive index ellipsoid formed by the λ / 4 retardation layer 4 may have biaxiality, but preferably has uniaxiality. The λ / 4 retardation layer 4 is preferably a horizontally aligned liquid crystal hardened layer composed of a polymer of a polymerizable liquid crystal composition including a polymerizable liquid crystal compound in a state aligned horizontally with respect to a plane of the λ / 4 retardation layer.

The horizontal alignment liquid crystal hardened layer is an optical axis of the polymerizable liquid crystal aligned horizontally with respect to the plane of the λ / 4 retardation layer. The polymerizable liquid crystal constituting the λ / 4 retardation layer may be a rod-shaped or disc-shaped polymerizable liquid crystal. When the rod-shaped polymerizable liquid crystal is aligned horizontally or vertically with respect to the plane of the λ / 4 retardation layer, the optical axis system of the polymerizable liquid crystal coincides with the long axis direction of the polymerizable liquid crystal. When the discotic polymerizable liquid crystal is aligned, the optical axis of the polymerizable liquid crystal exists in a direction orthogonal to the disc surface of the polymerizable liquid crystal.

The refractive index nx, ny, and nz of the three directions of the refractive index ellipsoid formed by the alignment of the polymerizable liquid crystal can be, for example, nx> ny ≒ nz (referred to as a positive A plate), nx ≒ ny <nz (referred to as Is a positive C plate), nx <ny ≒ nz (referred to as a negative A plate) or nx ≒ ny> nz (referred to as a negative C plate). nx represents the principal refractive index in the refractive index ellipsoid formed by the λ / 4 retardation layer in a direction parallel to the plane of the λ / 4 retardation layer. ny represents the refractive index in the refractive index ellipsoid formed by the λ / 4 retardation layer, which is parallel to the plane of the λ / 4 retardation layer and orthogonal to the direction of nx. nz represents the refractive index in the refractive index ellipsoid formed by the λ / 4 retardation layer, which is perpendicular to the plane of the λ / 4 retardation layer.

The λ / 4 retardation layer 4 may use either a rod-shaped polymerizable liquid crystal or a disc-shaped polymerizable liquid crystal, but a rod-shaped polymerizable liquid crystal is preferred, and a horizontally aligned liquid crystal is formed on the rod-shaped polymerizable liquid crystal. In the case of a hardened layer, the λ / 4 retardation layer is a positive A plate.

Regarding the λ / 4 retardation layer 4, in the refractive index ellipsoid formed by the λ / 4 retardation layer, the wavelength λ = 400 to 700 nm has a relationship of the following formula, nxQ (λ)> nyQ (λ) ≒ nzQ (λ)

[In the formula, nxQ (λ) represents the main refractive index of the refractive index ellipsoid formed by the λ / 4 retardation layer, which is parallel to the plane of the retardation layer with respect to the wavelength of λ (nm); nyQ (λ) refers to a pair of wavelengths λ () in a refractive index ellipsoid formed by a λ / 4 retardation layer, which is parallel to the plane of the retardation layer and orthogonal to the direction of the aforementioned nxQ (λ). nm) The refractive index of light; nzQ (λ) means that in the refractive index ellipsoid formed by the λ / 4 retardation layer, the direction of light with a wavelength of λ (nm) is perpendicular to the plane of the retardation layer Refractive index]; and satisfy the relationship of the following formulae (1) to (3), ReQ (450) / ReQ (550) ≦ 1.00 (1)

1.00 ≦ ReQ (650) / ReQ (550) (2)

100nm ≦ ReQ (550) ≦ 160nm (3)

[Where, ReQ (450) represents the in-plane retardation value of the λ / 4 retardation layer for light having a wavelength of λ = 450nm, and ReQ (550) represents the In-plane retardation value, ReQ (650) represents the in-plane retardation value of a λ / 4 retardation layer for light having a wavelength of λ = 650 nm, and the in-plane retardation layer of λ / 4 retardation layer for a light having a wavelength of λ (nm) The retardation value ReQ (λ) is represented by ReQ (λ) = (nxQ (λ) -nyQ (λ)) × dQ, where dQ represents the thickness of the λ / 4 retardation layer].

When the in-plane retardation value ReQ (550) of the λ / 4 retardation layer 4 exceeds the range of the formula (3), the hue of the front surface of the display including the elliptically polarizing plate may become red and blue. A more preferable range of the in-plane retardation value is 130 nm ≦ ReQ (550) ≦ 150 nm. When the ReQ (450) / ReQ (550) of the λ / 4 retardation layer exceeds 1.00, the ellipticity on the short wavelength side of the elliptically polarizing plate provided with the λ / 4 retardation layer is deteriorated. The ellipticity of the circular polarizer on the short-wavelength side deteriorates to 1.0 and becomes smaller, which impairs the function as a circular polarizer when viewed from the front on the short-wavelength side. The [ReQ (450) / ReQ (550)] is preferably 0.75 to 0.92, more preferably 0.77 to 0.87, and still more preferably 0.79 to 0.85.

The in-plane retardation value of the λ / 4 retardation layer 4 can be adjusted according to the thickness dQ of the λ / 4 retardation layer. The in-plane phase difference value is determined by the above formula ReQ (λ) = (nxQ (λ) -nyQ (λ)) × dQ. Therefore, the desired in-plane phase difference value (ReQ (λ): at the wavelength λ ( nm), the in-plane retardation value of the λ / 4 retardation layer), the 3-dimensional refractive index and the film thickness dQ may be adjusted. The three-dimensional refractive index depends on the molecular structure and the alignment state of the polymerizable liquid crystal compound described later.

From the viewpoint of thinning, the upper limit of the film thickness of the λ / 4 retardation layer 4 is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 2.5 μm or less. The lower limit of the film thickness of the λ / 4 retardation layer 4 is preferably 0.1 μm or more, more preferably 0.5 μm or more, and still more preferably 0.8 μm or more. The film thickness of the λ / 4 retardation layer can be measured using an ellipsometer or a contact film thickness meter.

(Vertical alignment liquid crystal hardened layer)

The vertical alignment liquid crystal cured layer 6 is a layer formed of a polymer of a polymerizable liquid crystal composition including a polymerizable liquid crystal compound in a state of being aligned in a vertical direction with respect to the plane of the liquid crystal cured layer. The three-dimensional refractive index ellipsoid formed by the vertically aligned liquid crystal hardened layer 6 may have biaxiality, but preferably has uniaxiality. The vertical alignment liquid crystal hardened layer 6 is a vertical alignment liquid crystal hardened layer formed of a polymer of a polymerizable liquid crystal composition including a polymerizable liquid crystal compound aligned in a vertical direction with respect to the plane of the vertical alignment liquid crystal hardened layer 6. The vertical alignment liquid crystal hardened layer 6 is preferably a rod-shaped liquid crystal, and more preferably a positive C plate.

In the case where the vertical alignment liquid crystal hardened layer 6 is a positive C plate, the vertical alignment liquid crystal hardened layer 6 is preferably a refractive index ellipsoid formed by the vertical alignment liquid crystal hardened layer 6 in a range of a wavelength λ = 400 to 700 nm. The relationship of the following formula, nzV (λ)> nxV (λ) ≒ nyV (λ)

[In the formula, nzV (λ) represents a refractive index in a refractive index ellipsoid formed by the liquid crystal hardened layer in a direction perpendicular to the plane of the liquid crystal hardened layer with respect to light having a wavelength of λ (nm). nxV (λ) represents the maximum refractive index of the refractive index ellipsoid formed by the liquid crystal hardened layer in a direction parallel to the plane of the liquid crystal hardened layer with respect to light having a wavelength of λ (nm). nyV (λ) represents the refractive index of light of a wavelength λ (nm) in a refractive index ellipsoid formed by the liquid crystal hardened layer, which is parallel to the plane of the liquid crystal hardened layer and orthogonal to the direction of the aforementioned nxV. . However, in the case of nxV (λ) = nyV (λ), nxV (λ) represents the refractive index in an arbitrary direction parallel to the plane of the liquid crystal hardened layer]; and the relationship of the following formulas (4) to (6) is satisfied; RthV (450) / RthV (550) ≦ 1.00 (4)

1.00 ≦ RthV (650) / RthV (550) (5)

-120nm ≦ RthV (550) ≦ -50nm (6)

[In the formula, RthV (450) represents the retardation value in the thickness direction of the liquid crystal hardened layer for light having a wavelength of λ = 450nm, and RthV (550) represents the retardation value in the thickness direction of the liquid crystal hardened layer for light having a wavelength of λ = 550nm. Value, RthV (650) represents the retardation value of the thickness direction of the liquid crystal hardened layer for light having a wavelength of λ = 650nm, and the retardation value of the thickness direction RthV (λ) of the liquid crystal hardened layer for light having a wavelength of λ (nm) is It is represented by RthV (λ) = [(nxV (λ) + nyV (λ)) / 2-nzV (λ)] × dV; here, in the refractive index ellipsoid formed by the liquid crystal hardened layer, nzV (λ) Represents the principal refractive index at a wavelength of λ (nm) in a direction perpendicular to the plane of the liquid crystal hardened layer, and "(nxV (λ) + nyV (λ)) / 2" indicates that at the wavelength λ (nm) of the The average refractive index in a plane; dV represents the thickness of the liquid crystal hardened layer].

When the retardation value RthV (550) in the thickness direction of the vertically aligned liquid crystal hardened layer 6 exceeds the range of the formula (6), the problem may be that the hue in the oblique direction of a display including an elliptical polarizing plate becomes red or blue. The more preferable range of the retardation value in the thickness direction is −95 nm ≦ RthV (550) ≦ −55 nm, and the more preferable range is −90 nm ≦ RthV (550) ≦ −60 nm. When the "RthV (450) / RthV (550)" of the vertical alignment liquid crystal hardened layer exceeds 1.0, the ellipticity of the elliptical polarizing plate including the vertical alignment hardened layer deteriorates when viewed from an oblique direction on the short wavelength side. The ellipticity of the circular polarizer on the short-wavelength side deteriorates to be smaller than 1.0 and becomes smaller, which impairs the function as a circular polarizer on the short-wavelength side. The "RthV (450) / RthV (550)" is preferably 0.75 to 0.92, more preferably 0.77 to 0.87, and still more preferably 0.79 to 0.85.

The retardation value in the thickness direction of the vertical alignment liquid crystal hardened layer 6 can be adjusted according to the thickness dV of the vertical alignment liquid crystal hardened layer. The phase difference value in the thickness direction is determined by the above formula RthV (λ) = [(nxV (λ) + nyV (λ)) / 2-nzV (λ)] × dV. Therefore, to obtain the desired phase difference in the thickness direction Value (RthV (λ): phase difference in the thickness direction of the liquid crystal hardened layer 6 in the vertical alignment of the wavelength λ (nm)), the 3-dimensional refractive index and the film thickness dV may be adjusted. The three-dimensional refractive index depends on the molecular structure and the alignment state of the polymerizable liquid crystal compound described later.

From the viewpoint of thinning, the upper limit of the film thickness of the vertical alignment liquid crystal cured layer 6 is preferably 3 μm or less, more preferably 2.5 μm or less, still more preferably 2.0 μm or less, and particularly preferably 1.5 μm or less. The lower limit of the film thickness of the vertical alignment liquid crystal hardened layer 6 is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 0.5 μm or more. The film thickness of the vertically aligned liquid crystal hardened layer can be measured using an elliptical polarimeter or a contact film thickness meter.

(Polymerizable liquid crystal composition)

The λ / 4 retardation layer 4 and the vertical alignment liquid crystal hardened layer 6 are each preferably composed of a polymer of a polymerizable liquid crystal composition including a polymerizable liquid crystal compound in an aligned state. The polymerizable liquid crystal compound is a liquid crystal compound having a polymerizable functional group (particularly, a photopolymerizable functional group). The photopolymerizable functional group refers to a group that can participate in a polymerization reaction by living radicals, acids, and the like generated from a photopolymerization initiator. Examples of the photopolymerizable functional group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, a propenyloxy group, a methacryloxy group, an ethylene oxide group, Oxetanyl and the like. Among them, acryloxy, methacryloxy, ethyleneoxy, ethylene oxide, and oxetanyl are preferred, and acryloxy is more preferred. The liquid crystal property may be a thermotropic liquid crystal or a lyotropic liquid crystal. In terms of a phase-ordered structure, it may be a nematic liquid crystal or a smectic liquid crystal.

In the present invention, the polymerizable liquid crystal compound preferably has the following formula from the viewpoint of exhibiting inverse wavelength dispersion, and from the viewpoint of satisfying the relationship of the aforementioned formulae (1) and (2) or (4) and (5). (I) Represented compounds.

In formula (I), Ar represents a divalent aromatic group which may have a substituent. Here, the aromatic group refers to a group having a planar cyclic structure, and the number of π electrons in the ring structure is [4n + 2] according to Huckel's law. Here, n represents an integer. In the case where heteroatoms such as -N = and -S- are included and a ring structure is formed, all cases including non-covalent electron pairs on these heteroatoms satisfy the Shocker's law and are also included in the case of aromaticity. The divalent aromatic group preferably contains at least one of a nitrogen atom, an oxygen atom, and a sulfur atom.

G ¹ and G ² each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group. Here, the hydrogen atom contained in the divalent aromatic group or the divalent alicyclic hydrocarbon group may be a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. The alkoxy group, cyano group or nitro group is substituted, and the carbon atom constituting the divalent aromatic group or the divalent alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom.

L ¹ , L ² , B ¹ and B ² are each independently a single bond or a divalent linking group.

k and l each independently represent an integer from 0 to 3, and satisfy the relationship of 1 ≦ k + l. Here, when 2 ≦ k + 1, B ¹ and B ² , G ¹ and G ² may be the same as each other or may be different.

E ¹ and E ² each independently represent an alkanediyl group having 1 to 17 carbon atoms. Here, the hydrogen atom contained in the alkanediyl group may be substituted with a halogen atom, and -CH ₂ -in the alkanediyl group may be replaced by- O-, -S-, -Si- substituted. P ¹ and P ² each independently represent a polymerizable group or a hydrogen atom, and at least one of them is a polymerizable group.

G ¹ and G ² are each independently preferably 1,4-phenylenediyl which may be substituted with at least one substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, and may be selected from the group consisting of 1,4-cyclohexanediyl substituted with at least one substituent in a group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably 1,4-phenylenediyl substituted with methyl, Unsubstituted 1,4-phenylenediyl or unsubstituted 1,4-trans-cyclohexanediyl, particularly preferably unsubstituted 1,4-phenylenediyl or unsubstituted 1,4-trans -Cyclohexanediyl. Furthermore, it is preferred that at least one of a plurality of G ¹ and G ² be a divalent alicyclic hydrocarbon group, and it is more preferable that at least one of G ¹ and G ² bonded to L ¹ or L ² be Divalent alicyclic hydrocarbon group.

L ¹ and L ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a1 OR ^a2- , -R ^a3 COOR ^a4- , -R ^a5 OCOR ^a6 -, R ^a7 OC = OOR ^a8- , -N = N-, -CR ^c = CR ^d- , or -C≡C-. Here, R ^a1 to R ^a8 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ^c and R ^d represent an alkyl group or hydrogen atom having 1 to 4 carbon atoms. L ¹ and L ² are each independently preferably a single bond, -OR ^a2-1- , -CH _2- , -CH ₂ CH _2- , ^{-COOR a4-1} -or -OCOR ^a6-1- . Here, R ^a2-1 , R ^a4-1 , and R ^a6-1 each independently represent a single bond, -CH _2- , or -CH ₂ CH _2- . L ¹ and L ² are each independently and preferably a single bond, -O-, -CH ₂ CH _2- , -COO-, -COOCH ₂ CH _2- , or -OCO-.

B ¹ and B ² are each independently preferably a single bond, an alkylene group having 1 to 4 carbon atoms, -O-, -S-, -R ^a9 OR ^a10- , -R ^a11 COOR ^a12- , -R ^a13 OCOR ^{a14 -Or} -R ^a15 OC = OOR ^a16- . Here, R ^a9 to R ^a16 each independently represent a single bond or an alkylene group having 1 to 4 carbon atoms. B ¹ and B ² are each independently preferably a single bond, -OR ^a10-1- , -CH _2- , -CH ₂ CH _2- , ^{-COOR a12-1} -or -OCOR ^a14-1- . Here, R ^a10-1 , R ^a12-1 , and R ^a14-1 each independently represent any one of a single bond, —CH ₂ —, and —CH ₂ CH ₂ —. B ¹ and B ² are each independently and preferably a single bond, -O-, -CH ₂ CH _2- , -COO-, -COOCH ₂ CH _2- , -OCO-, or -OCOCH ₂ CH _2- .

From the standpoint of inverse wavelength dispersion, k and l are preferably in a range of 2 ≦ k + l ≦ 6, k + l = 4 is more preferable, and k = 2 and l = 2 are more preferable. When k = 2 and l = 2, it is more preferable because it has a symmetrical structure.

E ¹ and E ² are each independently preferably an alkyldiyl group having 1 to 17 carbon atoms, and more preferably an alkyldiyl group having 4 to 12 carbon atoms.

Examples of the polymerizable group represented by P ¹ or P ² include epoxy groups, vinyl groups, vinyloxy groups, 1-chlorovinyl groups, isopropenyl groups, 4-vinylphenyl groups, acryloxy groups, and methacrylic groups. Ethoxy, oxiranyl and oxetanyl. Among these, acryloxy, methacryloxy, ethyleneoxy, ethylene oxide, and oxetanyl are preferable, and acryloxy is more preferable.

Ar preferably has at least one selected from an aromatic hydrocarbon ring which may have a substituent, an aromatic heterocyclic ring which may have a substituent, and an electron attracting group. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring, and a benzene ring and a naphthalene ring are preferred. Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a pyrrole ring, an indole ring, a thiophene ring, a benzothiophene ring, a pyridine ring, and a pyridine. Ring, pyrimidine ring, triazole ring, triazole Ring, pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring, Azole ring, benzo Azole ring and phenanthroline ring. Among these, a thiazole ring, a benzothiazole ring, or a benzofuran ring is preferable, and a benzothiazole ring is more preferable. When Ar contains a nitrogen atom, the nitrogen atom preferably has a π electron.

In the formula (I), the total number of π electrons N _x contained in the divalent aromatic group represented by Ar is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, and particularly preferably 16 or more. Furthermore, it is preferably 30 or less, more preferably 26 or less, and still more preferably 24 or less.

Examples of the aromatic group represented by Ar include the following groups.

In the formulae (Ar-1) to (Ar-22), the * symbol indicates a connecting portion, and Z ⁰ , Z ^1, and Z ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group. , Nitro, alkylsulfinyl having 1 to 12 carbons, alkylsulfinyl having 1 to 12 carbons, carboxyl, fluoroalkyl having 1 to 12 carbons, alkoxy having 1 to 6 carbons , Alkylthio groups having 1 to 12 carbon atoms, N-alkylamino groups having 1 to 12 carbon atoms, N, N-dialkylamino groups having 2 to 12 carbon atoms, and N-alkyl groups having 1 to 12 carbon atoms Aminosulfonyl or N, N-dialkylaminesulfonyl having 2 to 12 carbons.

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

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

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

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

Examples of the aromatic hydrocarbon group in Y ¹ , Y ² and Y ³ include aromatic hydrocarbon groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthracenyl, phenanthryl, and biphenyl, and phenyl and naphthyl are preferred. , More preferably phenyl. Examples of the aromatic heterocyclic group include a furanyl group, a pyrrolyl group, a thienyl group, a pyridyl group, a thiazolyl group, a benzothiazolyl group and the like having 4 to 20 carbon atoms including at least one hetero atom such as a nitrogen atom, an oxygen atom, and a sulfur atom. The aromatic heterocyclic group is preferably a furyl group, a thienyl group, a pyridyl group, a thiazolyl group, or a benzothiazolyl group.

Y ¹ and Y ² may be each independently a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group which may be substituted. The polycyclic aromatic hydrocarbon group refers to a fused polycyclic aromatic hydrocarbon group or a group derived from a diaromatic ring. The polycyclic aromatic heterocyclic group refers to a fused polycyclic aromatic heterocyclic group or a group derived from a biaromatic heterocyclic ring.

Z ⁰ , Z ¹ and Z ² are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 12 carbon atoms, and Z ^{0 is more} preferably A hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group, and Z ¹ and Z ^{2 are more} preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, and a cyano group.

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

Examples of the aromatic group represented by Ar ¹ include a group represented by the following formula (Ar-23).

In the formula (Ar-23), *, Z ¹ , Z ² , Q ¹ and Q ^{2 have the} same meanings as described above, and U ¹ represents a non-metal atom of a group 14 to a group 16 to which a substituent may be bonded. Examples of the non-metal atoms of Groups 14 to 16 include carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms. Preferred examples include = O, = S, = NR ', and = C (R') R '. . Examples of the substituent R ′ include a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an aromatic group, a cyano group, an amino group, a nitro group, a nitroso group, a carboxyl group, and an alkylene group having 1 to 6 carbon atoms. Sulfonyl, alkylsulfonyl having 1 to 6 carbons, fluoroalkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons, alkylthio having 1 to 6 carbons, carbon 1 N-alkylamino groups of 6 to 6, N, N-dialkylamino groups of 2 to 12 carbons, N-alkylaminosulfonyl groups of 1 to 6 carbon atoms, dialkyl groups of 2 to 12 carbon atoms In the case of sulfamoyl and the like, the two R's in the case where the non-metal atom is a carbon atom (C) may be the same as or different from each other.

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

In the formulae (Ar-16) to (Ar-22), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom and Z ⁰ to which it is bonded. Examples of the aromatic heterocyclic group include those described above as the aromatic heterocyclic group which Ar may have, and examples thereof include pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, and pyr Ring, pyrimidine ring, indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring and the like. The aromatic heterocyclic group may have a substituent. Furthermore, Y ¹ together with the nitrogen atom and Z ⁰ to which it is bonded may be the aforementioned polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group which may be substituted. Examples include benzofuran ring, benzothiazole ring, benzo Azole ring and so on. The compound represented by the formula (I) can be produced, for example, by a method described in Japanese Patent Application Laid-Open No. 2010-31223.

The polymerizable liquid crystal compound can be used alone or in combination of two or more kinds. When two or more types are used in combination, the content of the compound represented by the formula (I) is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and still more preferably 80 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. More than mass parts.

The polymerizable liquid crystal composition may further contain additives such as a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, an adhesion improver, and a dichroic pigment. These additives can be used alone or in combination of two or more.

The content of the polymerizable liquid crystal compound with respect to 100 parts by mass of the solid content of the polymerizable liquid crystal composition is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, and more preferably 90 to 98 parts by mass. When the content is within the above range, the alignment of the layer tends to be high. Here, the solid content means the total amount of components obtained by removing the solvent from the composition.

As the solvent, the solvents exemplified in the item of the reinforcing layer can be used. The content of the solvent is preferably 50 to 98 parts by mass, and more preferably 70 to 95 parts by mass based on 100 parts by mass of the polymerizable liquid crystal composition. Therefore, the solid content in 100 parts by mass of the composition is preferably 2 to 50 parts by mass. When the solid content of the composition is 50 parts by mass or less, the viscosity of the composition becomes low, so that the thickness of the layer becomes approximately uniform, and the layer tends to be less likely to be uneven. The solid content can be appropriately determined in consideration of the thickness of the layer to be produced.

As the photopolymerization initiator, the photopolymerization initiator exemplified in the item of the reinforcing layer can be used. The addition amount of the photopolymerization initiator is usually 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, and more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. If it exists in the said range, reaction of a polymerizable group will fully advance and it will become difficult to disturb the orientation of a polymerizable liquid crystal compound.

The polymerization reaction of a polymerizable liquid crystal compound can be controlled by blending a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinones and hydroquinones having substituents such as alkyl ethers; butylcatechols and other catechols having substituents such as alkyl ethers; catechols; 2 , 2,6,6-tetramethyl-1-piperidinyloxy radicals and other free radical scavengers; thiophenols; β-naphthylamines and β-naphthols. In order not to disturb the alignment of the polymerizable liquid crystal compound and polymerize the polymerizable liquid crystal compound, the content of the polymerization inhibitor is usually 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 100 parts by mass of the polymerizable liquid crystal compound. It is 0.1 to 3 parts by mass. A polymerization inhibitor can be used individually or in combination of 2 or more types.

Furthermore, by using a photosensitizer, the sensitivity of a photopolymerization initiator can be made high. Examples of the photosensitizer include: xanthones such as xanthones and thioanthone; anthracenes and anthracenes having substituents such as alkyl ethers; phenanthrene ; Rubrene. The photosensitizer 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 with respect to 100 parts by mass of the polymerizable liquid crystal compound.

The so-called leveling agent is an additive having the function of adjusting the flowability of the hardening composition and making the layer obtained by coating the composition flat, and examples thereof include polysiloxanes such as silane coupling agents, polyacrylates, and perfluoroalkanes. Base leveling agent. Specifically, for example: DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of which are manufactured by Toray. Dow Corning), KP321, KP323, KP324, KP326, KP340, KP341, X22-161A, KF6001, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM- 503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBE-585, KBM-802, KBM-802, KBM-803, KBE-846, KBE-9007 (all above are made by Shin-Etsu Chemical Industry Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (above All are made by Momentive Performance Materials Japan LLC); Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (all of which are made by Sumitomo 3M (shares) company); Megafac (registered (Trademark) R-08, Megafac R-30, Megafac R-90, Megafac F-410, Megafac F-411, Megafac F-443, Megafac F-445, Megafac F-470, Megafac F-477, Megafac F-479, Megafac F-482, Megafac F-483 (the above are all made by DIC (stock) company); EFTOP (trade name) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (all of the above are electronically formed by Mitsubishi Materials ( Shares) company system); SURFLON (registered trademark) S-381, SURFLON S-382, SURFLON S-383, SURFLON S-393, SURFLON SC-101, SURFLON SC-105, KH-40, SA-100 (all of the above (Made by AGC Seimi Chemical (stock) company); trade name E1830, trade name W5844 (made by DAIKIN Fine Chemicals Research Institute (stock)); BM-1000, BM-1100, BYK-352, BYK-353, and BYK-361N ( All are trade names: BM Chemie). Leveling agents can be used alone or in combination of two or more.

The content of the leveling agent is preferably 0.01 to 5 parts by mass, and more preferably 0.05 to 3 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, the resulting layer tends to be smoother, so it is preferable. The so-called dichroic pigment refers to a pigment having a property in which the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction. The range has the absorption maximum wavelength (λMAX). Examples of such dichroic pigments include acridine pigments, Among pigments, cyanine pigments, naphthalene pigments, azo pigments, and anthraquinone pigments, azo pigments are preferred. Examples of the azo pigment include a monoazo pigment, a diazo pigment, a triazo pigment, a tetraazo pigment, and a stilbene azo pigment, and the like, and a diazo pigment and a triazo pigment are preferred. The dichroic pigments may be used alone or in combination. In order to obtain absorption in the entire visible light region, it is preferable to combine three or more dichroic pigments, and it is more preferable to combine three or more azo pigments.

Examples of the azo pigment include a compound represented by the following formula (II) (hereinafter sometimes referred to as "compound (II)").

T ¹ -A ¹ (-N = NA ² ) _p -N = NA ³ -T ² (II) [In the formula (II), A ¹ , A ² and A ³ each independently represent a group which may have a substituent, 4-phenylene, naphthalene-1,4-diyl or a divalent heterocyclic group which may have a substituent, T ¹ and T ² are electron-attracting or electron-releasing groups, and are relative to the azo bond in-plane It has a position of substantially 180 °. p represents an integer from 0 to 4. When p is 2 or more, each A ² may be the same as each other or different. -N = N-bond may be replaced by -C = C-, -COO-, -NHCO-, or -N = CH- bond in the range showing absorption in the visible light region]

Examples of the optional substituents of 1,4-phenylene, naphthalene-1,4-diyl and divalent heterocyclic group in A ¹ , A ² and A ³ include methyl, ethyl and butyl. Alkyl groups having 1 to 4 carbons; alkoxy groups having 1 to 4 carbons such as methoxy, ethoxy and butoxy; fluoroalkyl groups having 1 to 4 carbons such as trifluoromethyl; cyano; Nitro; halogen atom such as chlorine atom, fluorine atom; substituted or unsubstituted amino group such as amine group, diethylamino group and pyrrolidinyl group (the so-called substituted amino group refers to those having 1 or 2 carbon numbers of 1 to 6 An amine group of an alkyl group, or an amine group having an alkyldiyl group having 2 to 8 carbon atoms by bonding two substituted alkyl groups to each other. The unsubstituted amine group is -NH ₂ ). Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, and hexyl. Examples of the alkanediyl group having 2 to 8 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, and pentane-1, 5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl and the like. In order to be included in highly ordered liquid crystal structures such as smectic liquid crystals, A ¹ , A ² and A ^{3 are} preferably 1,4-phenylene which is unsubstituted or hydrogen substituted with methyl or methoxy, or A divalent heterocyclic group, and p is preferably 0 or 1. Among them, p is 1 and at least two of the three structures of A ¹ , A ^2, and A ³ are 1,4-phenylene, which is more preferable in terms of both the simplicity of molecular synthesis and high performance. .

Examples of the divalent heterocyclic group include quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, Azole and benzo A radical obtained by removing two hydrogen atoms from an azole. In the case where A ² is a divalent heterocyclic group, a structure having a molecular bonding angle of substantially 180 ° is preferred, and more specifically, benzothiazole and benzo formed by condensing two 5-membered rings are more preferred. Imidazole, benzo Azole structure.

T ¹ and T ² are electron-attracting or electron-emitting groups, preferably having different structures, and more preferably T ¹ is an electron-attracting group and T ² is an electron-releasing group or T ¹ is an electron-releasing group and T ² In order to attract electron-based relationships. Specifically, T ¹ and T ² independently of each other are preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, and 1 or 2 carbon atoms having 1 to 2 carbon atoms. An amine group of an alkyl group of 6 or two substituted alkyl groups are bonded to each other to form an alkanoyl group of 2 to 8 carbon atoms, or a trifluoromethyl group. The ordered liquid crystal structure must be a structure with a smaller molecular exclusion volume. Therefore, it is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, and one or two. An amine group of an alkyl group having 1 to 6 carbon atoms or two substituted alkyl groups are bonded to each other to form an amine group of an alkyldiyl group having 2 to 8 carbon atoms.

Examples of such an azo pigment include the following.

In the formulae (2-1) to (2-6), B ¹ to B ²⁰ each independently represent a hydrogen 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. , A substituted or unsubstituted amine group (the definition of a substituted amine group and an unsubstituted amine group is as described above), a chlorine atom or a trifluoromethyl group. Furthermore, from the viewpoint of obtaining high polarization performance, B ² , B ⁶ , B ⁹ , B ¹⁴ , B ¹⁸ , and B ^{19 are} preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

n1 to n4 each independently represent an integer of 0 to 3.

When n1 is 2 or more, a plurality of B ² may be the same or different; when n2 is 2 or more, the plurality of B ⁶ may be the same or different; and when n3 is 2 or more, In the case, the plurality of B ⁹ may be the same or different; in the case where n4 is 2 or more, the plurality of B ¹⁴ may be the same or different.

The anthraquinone pigment is preferably a compound represented by the formula (2-7).

[In the formula (2-7), R ¹ to R ⁸ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x, or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aromatic group having 6 to 12 carbon atoms] The pigment is preferably a compound represented by the formula (2-8).

[In the formula (2-8), R ⁹ to R ¹⁵ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x, or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aromatic group having 6 to 12 carbon atoms]

The acridine dye is preferably a compound represented by the formula (2-9).

[In the formula (2-9), R ¹⁶ to R ²³ each independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x, or a halogen atom.

R ^x represents an alkyl group having 1 to 4 carbon atoms or an aromatic group having 6 to 12 carbon atoms]

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^x in formula (2-7), formula (2-8) and formula (2-9) include methyl, ethyl, propyl, butyl, Examples of the aryl group having 6 to 12 carbon atoms include pentyl, hexyl, and the like.

The cyanine pigment is preferably a compound represented by the formula (2-10) and a compound represented by the formula (2-11).

[In formula (2-10), D ¹ and D ² each independently represent a group represented by any one of formulas (2-10a) to (2-10d).

n5 represents an integer from 1 to 3]

[In formula (2-11), D ³ and D ⁴ each independently represent a group represented by any one of formulas (2-11a) to (2-11h).

n6 represents an integer from 1 to 3]

From the viewpoint of obtaining good light absorption characteristics, the content of the dichroic pigment (the total amount in the case of plural types is included) is usually 0.1 to 30 parts by mass based on 100 parts by mass of the polymerizable liquid crystal compound, and it is preferably It is 1 to 20 parts by mass, and more preferably 3 to 15 parts by mass. When the content of the dichroic pigment is less than this range, the light absorption becomes insufficient, and sufficient polarization performance cannot be obtained. When the content is more than this range, the alignment of the liquid crystal molecules may be hindered.

The polymerizable liquid crystal composition can be obtained by stirring components other than the polymerizable liquid crystal compound such as the polymerizable liquid crystal compound and the additive at a predetermined temperature.

The λ / 4 retardation layer 4 and the vertical alignment liquid crystal hardened layer 6 are preferably formed on an alignment layer that will give an alignment control force. In more detail, the λ / 4 retardation layer 4 can apply the aforementioned polymerizable liquid crystal composition to the alignment layer 5 and then remove the solvent to pass the polymerizable liquid crystal composition including the polymerizable liquid crystal compound in an aligned state by It is obtained by heating and / or activating energy rays to harden. In the vertical alignment liquid crystal hardened layer 6, the aforementioned polymerizable liquid crystal composition can be coated on the vertical alignment layer 7, and then the solvent can be removed, and the polymerizable liquid crystal composition including the polymerizable liquid crystal compound in an aligned state can be heated and / or activated. The energy rays are obtained by hardening it.

The method of coating the polymerizable liquid crystal composition on the alignment layer 5 or the vertical alignment layer 7 may be, for example, the coating method A illustrated in the item of the reinforcing layer. As a method of removing a solvent, the solvent removing method A illustrated in the item of a reinforcement layer is mentioned, for example. The irradiated active energy ray is appropriately selected depending on the type of the polymerizable liquid crystal compound, the type of the photopolymerization initiator when the photopolymerization initiator is included, and the amount thereof. The active energy ray and the light source can be exemplified in the project using a reinforcing layer. When the polymerizable liquid crystal composition is irradiated with ultraviolet rays, the ultraviolet irradiation intensity, irradiation time, and accumulated light amount can also be used in the ranges exemplified in the item of the reinforcing layer. When the accumulated light amount is below the range described above, curing of the polymerizable liquid crystal compound becomes insufficient, and reinforcing properties are insufficient. On the contrary, when the amount of accumulated light is above the range described above, the elliptically polarizing plate may be colored.

[Alignment layer]

The alignment layer 5 has an alignment control force that aligns the polymerizable liquid crystal compound in a predetermined direction. For example, if the alignment layer 5 is a material that exhibits a horizontal alignment control force as the alignment control force, the polymerizable liquid crystal compound may form a horizontal alignment or a mixed alignment, and if it is a material that exhibits a vertical alignment control force, the polymerizable liquid crystal compound may Form vertical alignment or oblique alignment. In addition, since the polymerizable liquid crystal compound contained in the vertical alignment liquid crystal hardened layer 6 forms a vertical alignment, the vertical alignment layer 7 is made of a material that exhibits a vertical alignment control force. The alignment control force can be arbitrarily adjusted by the type, surface state, friction conditions, etc. of the alignment layer, and when formed by a photo-alignment polymer, it can be arbitrarily adjusted by polarized light irradiation conditions and the like. Furthermore, the liquid crystal alignment can be controlled by selecting physical properties such as the surface tension and liquid crystallinity of the polymerizable liquid crystal compound.

The alignment layer 5 or the alignment layer 7 preferably has solvent resistance that does not dissolve due to application of a polymerizable liquid crystal composition, etc., and has heat resistance during heat treatment to remove the solvent or the alignment of the polymerizable liquid crystal compound. .

Examples of the horizontal alignment layer that exhibits an alignment control force that aligns the λ / 4 retardation layer 4 in the horizontal direction include a friction alignment layer, a light alignment layer, a groove alignment layer having a concave-convex pattern on the surface, and a plurality of grooves. For example, in the case where it is applied to a long roll film, a photo-alignment layer is preferred because the alignment direction can be easily controlled.

The friction alignment layer may be formed by applying a composition containing an alignment polymer and a solvent (hereinafter also referred to as a composition for forming a friction alignment layer) to a substrate, removing the solvent to form a coating film, and rubbing the coating film. And give the alignment control force.

Examples of the alignment polymer include polyamines having a fluorene bond, gelatins, polyimide having a fluorene imine bond, and a polyamic acid of a hydrolyzate thereof, polyvinyl alcohol, and an alkyl-modified polyvinyl alcohol. , Polyacrylamide, Poly Azole, polyethylenimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid and polyacrylates. These alignment polymers can be used individually or in combination of 2 or more types.

The concentration of the alignment polymer in the composition for forming a frictional alignment layer may be a range in which the alignment polymer is completely dissolved in the solvent. The content of the alignment polymer is preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the composition.

A composition for forming a friction alignment layer is commercially available. Examples of commercially available products include SUNEVER (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), OPTOMER (registered trademark, manufactured by JSR (corporation)), and the like.

As the solvent, for example, the solvents exemplified in the item of the reinforcing layer can be used. The method of applying the composition for forming a friction alignment layer to a substrate may be, for example, the aforementioned coating method A, and the method of removing the solvent may be, for example, the aforementioned solvent removing method A.

The rubbing method may be, for example, a method in which the coating film is brought into contact with a rubbing roller around which a rubbing cloth is wound and rotated. When performing the rubbing treatment, if the masking is performed, a plurality of regions (patterns) with different alignment directions can be formed on the alignment film.

The photo-alignment layer is usually coated with a composition (also referred to as a composition for forming a photo-alignment layer) containing a polymer or a monomer having a photoreactive group and a solvent, and after removing the solvent, it is irradiated with polarized light (compared with (Better for polarized UV). The light alignment layer can arbitrarily control the direction of the alignment control force by selecting the polarization direction of the polarized light to be irradiated.

The photoreactive group refers to a group that generates an alignment ability by light irradiation. Specifically, for example, a group that induces a photoreaction such as an alignment-induced reaction, an isomerization reaction, a photodimerization reaction, a photocrosslinking reaction, or a photodecomposition reaction of a molecule generated by light irradiation that is involved in the origin of the alignment ability. The photoreactive group is preferably a group having an unsaturated bond (especially a double bond), and particularly preferably a group selected from a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), A group of at least one of a group formed by a nitrogen-nitrogen double bond (N = N bond) and a carbon-oxygen double bond (C = O bond).

Examples of the photoreactive group having a C = C bond include a vinyl group, a polyalkenyl group, a distyryl group, a stilbazole group, an oxazolium group, a chalcone group, and a cinnamyl group. Examples of the photoreactive group having a C = N bond include a group having a structure such as an aromatic Schiff base and an aromatic fluorene. Examples of the photoreactive group having an N = N bond include azophenyl, azonaphthyl, aromatic heterocyclic azo, diazo, and Formazan and a group having an oxazobenzene structure. Examples of the photoreactive group having a C = O bond include a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have substituents such as alkyl, alkoxy, aromatic, allyloxy, cyano, alkoxycarbonyl, hydroxyl, sulfonic acid, and haloalkyl.

A group participating in a photodimerization reaction or a photocrosslinking reaction is preferable in terms of good alignment. Among them, a photoreactive group participating in a photodimerization reaction is preferable, and in terms of a small amount of polarized light irradiation required for alignment, and easy to obtain a light alignment layer having good thermal stability and stability over time, it is preferably Cinnamyl and chalcone. The polymer having a photoreactive group is particularly preferably one having a cinnamyl group at the end portion of the side chain of the polymer, which will form a cinnamic acid structure or a cinnamate structure.

The content of the polymer or monomer having a photoreactive group can be adjusted according to the type of the polymer or monomer and the thickness of the intended photo-alignment layer. It is preferably at least 100 parts by mass relative to the composition for forming the photo-alignment layer. The content is 0.2 parts by mass or more, and more preferably 0.3 to 10 parts by mass.

As the solvent, for example, the solvents exemplified in the item of the reinforcing layer can be used. The method of applying the composition for forming a photo-alignment layer to a substrate may be, for example, the aforementioned coating method A, and the method of removing the solvent may be, for example, the aforementioned solvent removing method A.

The polarized light may be irradiated with polarized light directly, for example, by removing the solvent from the composition for forming a photo-alignment layer applied on a substrate. The polarized light is preferably substantially parallel light. The wavelength of the polarized light to be irradiated may be a wavelength region in which a polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet) having a wavelength in the range of 250 to 400 nm is particularly preferred. Examples of the light source for irradiating the polarized light include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, KrF, and ArF ultraviolet lasers. Among them, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp are preferred because of their high light emission intensity at a wavelength of 313 nm. By passing light from the aforementioned light source through a suitable polarizing element and irradiating it, polarized light UV can be irradiated. Examples of the polarizing element include polarizing filters such as polarizing filters, Glan-Thompson, Glan-Taylor, and wire grids. Among these, from the viewpoints of an increase in area and heat resistance, a wire grid polarizing element is preferred.

In addition, when rubbing or polarizing light irradiation is performed, a plurality of regions (patterns) with different liquid crystal alignment directions can be formed by shielding.

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

The method for obtaining the groove alignment layer may be, for example, a method for forming a concave-convex pattern on the surface of a photosensitive polyimide film through an exposure mask through a slit having a pattern shape, and performing development and washing treatment after exposure. A method of forming a layer of a UV-curable resin before hardening on a plate-like master having grooves on the surface, and moving the formed resin layer to a substrate and curing; and a method of curing the UV-curing resin formed on the substrate before curing A method of crimping a roller-shaped master having a plurality of grooves to form unevenness, and then hardening the film.

The vertical alignment layer exhibiting an alignment control force that causes the vertical alignment liquid crystal hardened layer 6 to align in the vertical direction is preferably a material that reduces the surface tension of the surface of the alignment layer. Such materials may include, for example, the above-mentioned directional polymers, such as fluorinated polymers such as polyimide, polyamidine, polyamic acid of its hydrolyzate, perfluoroalkyl, and silane compounds, and the like Polysiloxane compound obtained by condensation reaction. The vertical alignment layer may be formed by applying a composition (hereinafter also referred to as a composition for forming a vertical alignment layer) containing a material and a solvent such as a solvent exemplified in the item of the reinforcing layer, to the substrate, and removing the solvent. The coating film is obtained by heating or the like.

In the case where a silane compound is used for the vertical alignment layer, it is preferable that at least the vertical alignment layer 7 be a compound containing Si elements and C elements from the viewpoint of easily reducing the surface tension and improving the adhesion with the adjacent layer. The formed layer is preferably a silane compound. When at least the vertical alignment layer 7 is composed of a compound containing Si and C as constituent elements, the adhesion to the adjacent layer can be improved, and the processing characteristics of the formed elliptical polarizer can be improved.

Silane compounds can be suitably used with the above-mentioned polysiloxanes such as silane coupling agents, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, N -(2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3 -Chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropylethoxydimethylsilane, and the like.

The silane compound may be a polysiloxane monomer type or a polysiloxane oligomer (polymer) type. When the polysiloxane oligomer is expressed as a (monomer)-(monomer) copolymer, for example, 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyl Trimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer, and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer Copolymers containing mercaptopropyl; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane -Mercaptomethyl-containing copolymers such as tetramethoxysilane copolymers and mercaptomethyltriethoxysilane-tetraethoxysilane copolymers; 3-methacryloxypropyltrimethoxysilane-tetramethoxysilane Methoxysilane copolymer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetramethoxy Silane copolymer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldi Oxysilane-tetramethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyl Diethoxysilane-tetramethoxysilane copolymers and 3-methacryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymers, etc. Copolymer; 3-propenyloxypropyltrimethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-propenyloxysilane Propyltriethoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-propenyloxypropylmethyldi Methoxysilane-tetramethoxysilane copolymer, 3-propenyloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-propyleneoxypropylmethyldiethoxy Copolymers containing acryloxypropyl groups, such as silane-tetramethoxysilane copolymers and 3-propenyloxypropylmethyldiethoxysilane-tetraethoxysilane copolymers; vinyl triethylene Ethoxysilane-tetramethoxysilane copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane -Tetraethoxysilane copolymer, vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldi Vinyl-containing copolymers such as ethoxysilane-tetramethoxysilane copolymer and vinyl methyldiethoxysilane-tetraethoxysilane copolymer; 3-aminopropyltrimethoxysilane-tetramethoxysilane Methoxysilane copolymer, 3-aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-amine group Propyltriethoxysilane-tetraethoxysilane copolymer, 3-aminopropylmethyldimethoxysilane-tetramethoxysilane copolymer, 3-aminopropylmethyldimethoxy Silane-tetraethoxysilane copolymer, 3-aminopropylmethyldiethoxysilane, tetramethoxysilane and 3-aminopropylmethyldiethoxysilane Amine-containing copolymers such as alkane-tetraethoxysilane copolymers and the like. Silane compounds can be used alone or in combination of two or more. In addition, it is sometimes used as a leveling agent, and a silane coupling agent or the like may be used.

Among these, a silane compound having an alkyl group at the molecular terminal is preferred, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferred.

In a preferred embodiment of the present invention, a vertical alignment layer 7 having a film thickness of 5 μm or less is provided between the vertical alignment liquid crystal hardened layer 6 and the reinforcing layer 8, and the vertical alignment layer 7 is composed of a Si element and a C element. And O compound. From the standpoint of improving the adhesion with the adjacent layers and the coatability of the composition for forming the vertical alignment liquid crystal hardened layer 6, the vertical alignment layer 7 preferably contains Si, C, and It is composed of a compound of element O, and a silane compound can be suitably used. The substituent containing the C atom bonded to the Si atom of the silane compound forming the vertical alignment layer 7 is preferably an alkyl group or an alkoxy group, and the number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and more It is preferably 3 to 20. That is, the ratio of the Si element to the C element (Si / C, molar ratio) is preferably 0.03 to 1.00, more preferably 0.04 to 0.50, and still more preferably 0.05 to 0.33. When the Si / C ratio is greater than or equal to the above lower limit, the coatability of the composition for forming the vertical alignment liquid crystal hardened layer 6 is improved. When the Si / C ratio is less than or equal to the upper limit, adhesion to the adjacent layer can be improved.

As the solvent, for example, the solvents exemplified in the item of the reinforcing layer 8 can be used. The method of applying the composition for forming a vertical alignment layer to a substrate may be, for example, the aforementioned coating method A, and the method of removing the solvent may be, for example, the aforementioned solvent removing method A.

The composition for forming the alignment layer, that is, the composition for forming the frictional alignment layer, the composition for forming the photo-alignment layer, and the composition for forming the vertical alignment layer, and the composition for forming the vertical alignment layer may include, in addition to a solvent, a composition For example, the same additives as those contained in the polymerizable liquid crystal composition.

From the viewpoint of thinning, the film thicknesses of the alignment layer 5 and the vertical alignment layer 7 are each preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less. In addition, the film thicknesses of the alignment layer 5 and the vertical alignment layer 7 are preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, and particularly preferably 30 nm or more. The film thicknesses of the alignment layer 5 and the vertical alignment layer 7 can be measured using an ellipsometer or a contact film thickness meter.

[Adhesive]

Examples of the adhesive 3 include a pressure-sensitive adhesive, a dry-curing adhesive, and a chemically reactive adhesive. Examples of the chemically reactive adhesive include an active energy ray-curable adhesive.

The pressure-sensitive adhesive usually includes a polymer and may also include a solvent. Examples of the polymer include an acrylic polymer, a silicone polymer, a polyester, a polyurethane, or a polyether. Among them, acrylic adhesives containing acrylic polymers have good optical transparency, suitable wetting and aggregating power, good adhesion, and high weather resistance and heat resistance. Under heating and humidifying conditions It is not likely to cause floating, peeling, etc., so it is preferred.

The acrylic polymer is preferably a (meth) acrylate, a (meth) acrylic acid, or a (meth) acrylic acid hydroxyl group in which the alkyl group of the ester portion is an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, or butyl A copolymer of a (meth) acrylic monomer having a functional group such as ethyl ester.

A pressure-sensitive adhesive containing such a copolymer is preferable because it has good adhesion and can be easily removed without causing residues or the like on the transferred object even when it is removed after being adhered to the transferred object. . The glass transition temperature of the acrylic polymer is preferably 25 ° C or lower, and more preferably 0 ° C or lower. The mass average molecular weight of such an acrylic polymer is preferably 100,000 or more.

Examples of the solvent include the solvents listed above. The pressure-sensitive adhesive may contain a light diffusing agent. The light diffusing agent is an additive that imparts light diffusibility to the adhesive, and any fine particles having a refractive index different from that of the polymer contained in the adhesive may be used. Examples of the light diffusing agent include fine particles composed of an inorganic compound and fine particles composed of an organic compound (polymer). Since the polymer containing an acrylic polymer and the adhesive as an active ingredient often has a refractive index of about 1.4 to 1.6, it is preferable to appropriately select a light diffusing agent having a refractive index of 1.2 to 1.8. The refractive index difference between the polymer contained in the adhesive as an active ingredient and the light diffusing agent is usually 0.01 or more, and from the viewpoint of brightness and display properties of the display device, it is preferably 0.01 to 0.2. The fine particles used as the light diffusing agent are preferably spherical fine particles and close to monodisperse fine particles, and more preferably fine particles having an average particle diameter of 2 to 6 μm. The refractive index is measured by a general minimum declination method or an Abbe refractometer.

Examples of the fine particles composed of an inorganic compound include aluminum oxide (refractive index 1.76) and silicon oxide (refractive index 1.45). Examples of the fine particles composed of an organic compound (polymer) include melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), and methyl methacrylate / styrene copolymer resin beads. (Refractive index 1.50 to 1.59), polycarbonate beads (refractive index 1.55), polyethylene beads (refractive index 1.53), polystyrene beads (refractive index 1.6), polyvinyl chloride beads (refractive index 1.46) And silicone beads (refractive index 1.46). The content of the light diffusing agent is usually 3 to 30 parts by mass based on 100 parts by mass of the polymer.

The thickness of the pressure-sensitive adhesive is determined by its adhesion, etc., and is not particularly limited, but is usually 1 μm to 40 μm. In view of processability, durability, and the like, the thickness is preferably 3 μm to 25 μm, and more preferably 5 μm to 20 μm. By setting the thickness of the adhesive layer formed from the adhesive to 5 μm to 20 μm, the brightness of the case where the display device is viewed from the front and the case where the display device is viewed from an oblique direction is maintained, and bleeding of the displayed image is less likely to occur , blurry.

The dry-curable adhesive may include a solvent. Examples of the dry-curing type adhesive include a polymer containing a monomer having a proton functional group such as a hydroxyl group, a carboxyl group, or an amine group and an ethylenically unsaturated group, or an amine ester resin as a main component, and further containing a polyaldehyde and an epoxy resin. Compounds such as compounds, epoxy resins, melamine compounds, zirconia compounds, and zinc compounds, or compositions of hardening compounds. Examples of the polymer having a protonic functional group such as a hydroxyl group, a carboxyl group, or an amine group, and an ethylenically unsaturated group include ethylene-maleic acid copolymer, itaconic acid copolymer, acrylic copolymer, and acrylamide. Copolymers, saponified products of polyvinyl acetate, and polyvinyl alcohol resins.

Examples of the polyvinyl alcohol-based resin include polyvinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxyl-modified polyvinyl alcohol, acetoacetic acid-modified polyvinyl alcohol, and methylol-modified poly (vinyl alcohol). Vinyl alcohol and amine-modified polyvinyl alcohol. The content of the polyvinyl alcohol-based resin in the water-based adhesive is usually 1 to 10 parts by mass, and preferably 1 to 5 parts by mass with respect to 100 parts by mass of water.

Examples of the urethane resin include polyester-based ionic polymer-type urethane resins. Here, the polyester-based ionic polymer amine ester resin refers to an amine ester resin having a polyester skeleton and a resin into which a small amount of an ionic component (a hydrophilic component) is introduced. Such an ionic polymer amine ester resin can be used as an aqueous adhesive because it does not use an emulsifier and is emulsified into latex in water. When using a polyester-based ionic polymer amine ester resin, it is effective to mix a water-soluble epoxy compound as a crosslinking agent.

Examples of the epoxy resin include polyamine polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine or triethylenetetraamine with dicarboxylic acids such as adipic acid, and epoxy resins. Polyamine epoxy resin obtained by the reaction of chloropropane. Examples of such commercially available polyamine epoxy resins include "Sumirez resin (registered trademark) 650" and "Sumirez resin 675" (manufactured by Sumitomo Chemical Co., Ltd.) and "WS-525" (manufactured by Japan PMC Co., Ltd.) )Wait. In the case of blending an epoxy resin, the amount of the epoxy resin added is usually 1 to 100 parts by mass, and preferably 1 to 50 parts by mass, relative to 100 parts by mass of the polyvinyl alcohol resin.

The thickness of the adhesive layer formed from the dry-curing type adhesive is usually 0.001 to 5 μm, preferably 0.01 to 2 μm, and more preferably 0.01 to 0.5 μm. When the thickness of the adhesive layer formed from the dry-curing type adhesive is too thick, the appearance tends to be poor.

The active energy ray-curable adhesive may include a solvent. The active energy ray-curable adhesive refers to an adhesive that hardens upon irradiation with active energy rays. Examples of the active energy ray-curable adhesive include a cationic polymerizable adhesive containing an epoxy compound and a cationic polymerization initiator, a radical polymerizable adhesive containing an acrylic hardening component and a radical polymerization initiator, and an epoxy compound. Both a cationic polymerizable hardening component and a radical polymerizable hardening component such as an acrylic compound, and an adhesive further containing a cationic polymerization initiator and a radical polymerization initiator, and an electron beam irradiated without containing such a polymerization initiator And hardened adhesives and so on.

Among these, a radically polymerizable active energy ray hardening type adhesive containing an acrylic hardening component and a photo radical polymerization initiator, and a cationic polymerizable active energy ray hardening containing an epoxy compound and a photocationic polymerization initiator are preferred. Type adhesive. Examples of the acrylic curing component include (meth) acrylates such as methyl (meth) acrylate and hydroxyethyl (meth) acrylate, and (meth) acrylic acid. The epoxy compound-containing active energy ray-curable adhesive may further contain a compound other than the epoxy compound. Examples of the compound other than the epoxy compound include an oxetane compound and an acrylic compound.

Examples of the photo-radical polymerization initiator and the photo-cationic polymerization initiator include the photo-radical polymerization initiator and the photo-cationic polymerization initiator described above. The content of the radical polymerization initiator and the cationic polymerization initiator is usually 0.5 to 20 parts by mass, and preferably 1 to 15 parts by mass with respect to 100 parts by mass of the active energy ray-curable adhesive.

The active energy ray-curable adhesive may further contain an ion trapping agent, an antioxidant, a chain transfer agent, an adhesion-imparting agent, a thermoplastic resin, a filler, a flow modifier, a plasticizer, and an antifoaming agent.

In the present specification, an active energy ray is defined as an energy ray that can decompose a compound that generates an active species to generate an active species. Examples of such active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, alpha rays, beta rays, gamma rays, and electron beams, and ultraviolet rays and electron beams are preferred. The preferable ultraviolet irradiation conditions are the same as the polymerization of the aforementioned polymerizable liquid crystal compound.

[Elliptical polarizer]

The elliptic polarizing plates 1, 10, and 100 of the present invention have a vertical alignment liquid crystal hardened layer 6 that sufficiently strengthens the film because the interlayer distance between the vertical alignment liquid crystal hardened layer 6 and the reinforcing layer 8 is 5 μm or less, which can suppress or prevent Defects such as undulations. Therefore, it can be applied to display applications.

In the elliptically polarizing plate of the present invention, the reinforcing layer 8, the alignment layer 5, and the vertical alignment layer 7 are preferably isotropic (also referred to as isotropic) layers having a three-dimensional refractive index.

The film thicknesses of the elliptically polarizing plates 1, 10, and 100 of the present invention are preferably 10 to 300 μm, more preferably 20 to 200 μm, and even more preferably 30 to 100 μm. When the film thickness of the elliptically polarizing plate is greater than or equal to the above-mentioned lower limit, it is advantageous from the viewpoint of processing characteristics, and when the film thickness of the elliptically-polarizing plate is less than the aforementioned upper limit, it is advantageous from the viewpoint of thinning.

The elliptically polarizing plates 1, 10, and 100 of the present invention preferably have a difference in average refractive index within a plane of a wavelength of 550 nm in each of the adjacent layers, which is 0.20 or less. When the difference in the in-plane average refractive index is equal to or less than the above-mentioned upper limit, the reflection at the interface between the layers becomes small. The in-plane average refractive index can be measured by the method described in Examples.

[Manufacturing method of elliptical polarizing plate]

The elliptical polarizing plate 1 shown in FIG. 1 can be formed by forming a polarizing layer 2, a laminated body A of a λ / 4 retardation layer 4 and an alignment layer 5, and a vertically aligned liquid crystal hardened layer 6 and a vertical alignment layer 7 and a reinforcing layer. Laminated body B of 8 was obtained by bonding together through adhesive 3. For example, a laminated body A having an alignment layer 5 and a λ / 4 retardation layer 4 sequentially formed on the substrate is formed on the substrate, and a reinforcing layer 8, a vertical alignment layer 7, and a vertical alignment liquid crystal hardened layer are formed on the substrate sequentially. In the multilayer body B of 6, the polarizer 2 and the λ / 4 retardation layer 4 side of the multilayer body A are separated by an adhesive 3 so that the absorption axis of the polarizing layer 2 and the slow axis of the λ / 4 retardation layer 4 are separated. Lamination was performed so that the angle became 45 °, and only the base material was peeled to produce a laminated body C. Then, the side of the alignment layer 5 of the laminated body C and the side of the vertically aligned liquid crystal hardened layer 6 of the laminated body B are bonded together with an adhesive 3 therebetween, and only the substrate is peeled off, whereby the elliptic polarizing plate 1 can be manufactured.

The elliptical polarizing plate 10 shown in FIG. 2 can be made into a polarizing layer 2, the laminated body A, and the laminated body B, respectively. The polarizing layer 2 and the laminated body B are vertically aligned with the liquid crystal hardened layer 6 side with an adhesive therebetween. 3 bonding, peeling off only the base material, and producing a laminated body D. Then, the side of the reinforcing layer 8 of the laminated body D and the side of the λ / 4 retardation layer 4 of the laminated body A may be separated by the adhesive 3 so that the absorption axis of the polarizing layer 2 is relative to that of the λ / 4 retardation layer 4. The slow axis (optical axis) is bonded at a substantially 45 ° angle, and is produced by peeling only the substrate.

The elliptically polarizing plate 100 shown in FIG. 3 can prepare the polarizing layer 2, the laminated body A, and the laminated body B, respectively, to vertically align the liquid crystal layer 4 of the laminated body A with the λ / 4 retardation layer 4 side and the laminated body B. Laminated body E was produced by laminating the hardened layer 6 side with an adhesive 3 therebetween, and peeling off both substrates. Next, the reinforcing layer 8 side of the multilayer body E and the polarizing layer 2 are separated by an adhesive 3 so that the absorption axis of the polarizing layer 2 is substantially relative to the slow axis (optical axis) of the λ / 4 retardation layer 4. It can be produced by bonding at 45 °.

(Base material)

The substrate may be, for example, a glass substrate or a film substrate. From the viewpoint of processability, a film substrate is preferred, and in terms of continuous production, a long roll film is more preferred. Examples of the resin constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norbornene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate Polyacrylates; cellulose esters such as triethyl cellulose, diethyl cellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polyfluorene; polyether fluorene ; Polyether ketone; polyphenylene sulfide and polyphenylene ether plastics. A release treatment such as a polysiloxane treatment can be performed on the bonding surface of the substrate and the adhesive layer. Commercially available cellulose ester substrates include "FUJITAC FILM" (manufactured by FUJIFILM Co., Ltd.); "KC8UX2M", "KC8UY", and "KC4UY" (manufactured by Konica Minolta Optical Co., Ltd.). Such a resin can be formed into a base material by a conventional method such as a solvent casting method and a melt extrusion method.

Commercially available cyclic olefin-based resins include, for example, "Topas" (registered trademark) (made by Ticona (independent)), "ARTON" (registered trademark) (made by JSR Corporation), "ZEONOR" (registered trademark), " "ZEONEX" (registered trademark) (above the Japanese ZEON Corporation) and "APEL" (registered trademark) (Mitsui Chemical Corporation). A commercially available cyclic olefin-based resin substrate can be used. Examples of commercially available cyclic olefin-based resin substrates include "Escena" (registered trademark), "SCA40" (registered trademark) (manufactured by Sekisui Chemical Industry Co., Ltd.), and "ZEONOR FILM" (registered trademark) (OPTES Corporation) System) and "ARTON FILM" (registered trademark) (JSR Corporation).

It is preferable that the base material has a thickness that can be easily laminated and easily peeled. The thickness of such a substrate is usually 5 to 300 μm, and preferably 10 to 150 μm.

[Other Aspects of Elliptical Polarizer]

Although the elliptically polarizing plates 1, 10, and 100 shown in FIGS. 1 to 3 include an adhesive 3, an alignment layer 5, and a vertical alignment layer 7, the elliptically polarizing plate of the present invention has at least a polarizing layer, a λ / 4 retardation layer, The vertical alignment liquid crystal hardened layer and the reinforcing layer may be sufficient, and layers other than these may be included, for example, other alignment liquid crystal hardened layers, protective layers, and the like.

Other alignment liquid crystal hardened layers include, for example, the positive A plate, the positive C plate, the negative A plate, the negative C plate, and the like exemplified in the item of the λ / 4 retardation layer.

In a preferred aspect, the other alignment liquid crystal hardened layer has the optical characteristics represented by the formula (6), and preferably has the optical characteristics represented by the formula (6-1). The in-plane retardation value Re (550) can be adjusted by the same method as the above-mentioned adjustment method of the in-plane retardation value of the λ / 4 retardation layer.

200nm <Re (550) <320nm (6)

265nm <Re (550) <285nm (6-1)

In addition, the Re (450) / Re (550) of the other alignment liquid crystal hardened layer may be 1.00 or more, and may also be 1.00 or less. From the viewpoint of increasing the ellipticity of the elliptically polarizing plate, the closer it is to the λ / 4 retardation layer 4 The better the ReQ (450) / ReQ (550) is, the better the ReQ (650) / ReQ (550) value for Re (650) / Re (550) is similar to the λ / 4 retardation layer 4.

The film thickness of the other alignment liquid crystal hardened layer is preferably 0.5 μm to 5.0 μm, and more preferably 2.0 μm to 4.5 μm.

The protective layer is preferably formed of a composition for forming a protective layer. The composition for forming a protective layer usually contains a polyfunctional acrylate (methacrylate), an urethane acrylate, a polyester acrylate, and a ring. Acrylic oligomers or polymers composed of oxyacrylate, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylpyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, alginic acid Water-soluble polymers such as sodium and solvents.

Examples of the solvent contained in the protective layer-forming composition include the same solvents as those exemplified in the item of the polymerizable liquid crystal composition, and at least one solvent selected from the group consisting of water, alcohol solvents, and ether solvents, The point which does not dissolve the layer which forms a protective layer is preferable. Examples of the alcohol solvent include methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether. Examples of the ether solvent include ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate. Among them, ethanol, isopropanol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferred.

The film thickness of the protective layer is 0.1 μm to 10 μm, and more preferably 0.3 μm to 5.0 μm.

The elliptically polarizing plate of the present invention may be the elliptically polarizing plate shown in Figs. 1 to 3, and after the layers are formed, the layers are bonded via an adhesive, or the layers may be directly laminated without the adhesive or the like. The method of bonding each layer may be, for example, a method of laminating each layer on a substrate, and then bonding the layers through an adhesive, and then peeling the substrate; or a method of bonding the layers through the adhesive after peeling the substrate. . In addition, as the method of directly stacking each layer or the method of stacking each layer on a substrate, the same method as the method of forming each layer on the substrate can be used. In addition, before the layers are laminated on the substrate and before the layers are bonded together with an adhesive, surface treatments such as corona treatment and plasma treatment may be performed on the surface of the substrate or the surface of each layer.

[Display device]

The elliptical polarizing plate of the present invention can be used in a display device. The display device is a device having a display mechanism and includes a light-emitting element or a light-emitting device as a light-emitting source. Examples of the display device include a liquid crystal display device, an organic electroluminescent (EL) display device, an inorganic electroluminescent (EL) display device, a touch panel display device, an electron emission display device (electric field emission display device (FED, etc.), surface) Electric field emission display device (SED)), electronic paper (display device using electronic printing ink, electrophoretic elements), plasma display device, projection display device (grating light valve (GLV) display device, digital micromirror device ( DMD) display devices, etc.) and piezoelectric ceramic displays. The liquid crystal display device includes any one of 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. These display devices may be a display device that displays a two-dimensional image or a stereoscopic display device that displays a three-dimensional image. In particular, the display device provided with the elliptically polarizing plate of the present invention is preferably an organic EL display device and a touch panel display device, and particularly preferably an organic EL display device. The present invention also includes an organic EL display device including the elliptically polarizing plate of the present invention.

A preferred aspect of the organic EL display device of the present invention includes, for example, a device in which the reinforcing layer 8 side of the elliptical polarizing plate shown in FIG. 1 is bonded to an organic EL panel with an adhesive therebetween, and FIG. 2 Or the device in which the alignment layer 5 of the elliptically polarizing plate shown in FIG. 3 is bonded to an organic EL panel via an adhesive.

    [Example]    

Hereinafter, the present invention will be described more specifically with reference to examples. In addition, "%" and "part" in the examples mean mass% and mass part unless otherwise stated. The polymer films, devices, and measurement methods used in the following examples are as follows.

‧The corona treatment device uses AGF-B10 manufactured by Kasuga Electric Co., Ltd.

‧Corona treatment can be appropriately performed when applying a composition to a substrate. Using the above-mentioned corona treatment device, it was performed once under the conditions of an output of 0.3 kW and a processing speed of 3 m / min.

‧Polarized UV irradiation equipment uses SPOT CURE SP-9 with a polarizer unit manufactured by Ushio Electric Co., Ltd.

‧Unicure VB-15201BY-A manufactured by Ushio Electric Co., Ltd. is used for the high-pressure mercury lamp.

‧The phase difference value Re (λ) in the in-plane direction was measured using KOBRA-WPR manufactured by Oji Measurement Co., Ltd.

‧The retardation value Rth (λ) and film thickness in the thickness direction are measured using an ellipsometry M-220 or a contact film thickness meter (MH-15M, Counter TC101, MS-5C, manufactured by Nikon Corporation) . Moreover, the Si / C ratio is calculated by elemental analysis of the vertical alignment layer 7 and measurement of surface constituent elements using X-ray photoelectric spectrometry, or the structural formula of the compound used in the formation of the vertical alignment layer 7 is complete Known conditions can be calculated from the structural formula.

(Example 1)

The elliptically polarizing plate 1 having the layer structure shown in FIG. 1 was produced as follows.

    [Manufacture of Polarizing Layer 2]    

A polyvinyl alcohol film having an average degree of polymerization of about 2400, a degree of saponification of 99.9 mol% or more, and a thickness of 75 μm was immersed in pure water at 30 ° C, and then the mass ratio of iodine / potassium iodide / water was 0.02 / 2/100 at 30 ° C. The aqueous solution was subjected to iodine staining (iodine staining step). Then, the polyvinyl alcohol film subjected to the iodine dyeing step was immersed in an aqueous solution having a mass ratio of potassium iodide / boric acid / water of 12/5/100 at 56.5 ° C. to perform a boric acid treatment (boric acid treatment step). The polyvinyl alcohol film that had undergone the boric acid treatment step was washed with pure water at 8 ° C., and then dried at 65 ° C. to obtain a polarizer (the thickness after stretching was 27 μm) aligned with polyvinyl alcohol by iodine adsorption. At this time, stretching is performed in the iodine staining step and the boric acid treatment step. The total stretching ratio of such stretching is 5.3 times. The obtained polarizer and a saponified triethylsulfonyl cellulose film (KC4UYTAC manufactured by Konica Minolta Co., Ltd. 40 μm) were bonded together via a water-based adhesive using a pinch roller. While maintaining the tension of the obtained paste at 430 N / cm, drying was performed at 60 ° C. for 2 minutes to obtain a polarizing layer having a triethylfluorenyl cellulose film on one side as a protective film. The water-based adhesive was added to 100 parts of water with 3 parts of a carboxyl-modified polyvinyl alcohol (Kuraray, "Kuraray Poval KL318") and a water-soluble polyamine epoxy resin (Sumika Chemtex, "Sumirez" resin 650 ", 30% solids solution in water)).

The obtained polarizing layer 2 was measured for optical characteristics. The measurement was performed using the surface of the polarizer of the polarizing layer obtained above as the incident surface, using a spectrophotometer ("V7100", manufactured by Japan Spectroscopy). The absorption axis of the polarizing layer is the same as the extension direction of the polyvinyl alcohol. The obtained polarized layer has a visually-corrected monochromatic transmittance of 42.1%, a visually-corrected polarized degree of 99.996%, and a monomer hue a of -1.1. Hue b is 3.7.

[Modulation of Composition (a) for Forming Alignment Layer 5 for Forming λ / 4 Phase Difference Layer 4]

5 parts (weight average molecular weight: 30,000) of photo-alignment material having the following structure and 95 parts of cyclopentanone (solvent) were mixed as components, and the obtained mixture was stirred at 80 ° C for 1 hour, thereby obtaining a λ / 4 phase. Composition (a) for forming alignment layer 5 for forming differential layer 4.

[Modulation of composition for forming λ / 4 retardation layer 4 and composition for forming vertical alignment liquid crystal hardened layer 6]

To a mixture of the polymerizable liquid crystal compound A and the polymerizable liquid crystal compound B shown below at a mass ratio of 90:10, 1.0 part of a leveling agent (F-556; manufactured by DIC Corporation) and 2 of a polymerization initiator were added. -6 parts of dimethylamino-2-benzyl-1- (4-morpholinylphenyl) butane-1-one ("Irgacure 369 (Irg369)", manufactured by Japan BASF Corporation).

Furthermore, N-methyl-2-pyrrolidone (NMP) was added so that the solid content concentration became 13%, and the mixture was stirred at 80 ° C for 1 hour, thereby obtaining a composition for forming a λ / 4 retardation layer 4 and A composition for forming a vertical alignment liquid crystal cured layer 6.

The polymerizable liquid crystal compound A is produced using the method described in Japanese Patent Application Laid-Open No. 2010-31223. The polymerizable liquid crystal compound B is produced by a method described in Japanese Patent Application Laid-Open No. 2009-173893. The respective molecular structures are shown below.

[Polymerizable liquid crystal compound A]

[Polymerizable liquid crystal compound B]

[Manufacturing of a multilayer body A composed of a base material, an alignment layer 5 and a λ / 4 retardation layer 4]

The composition (a) for forming an alignment layer was coated on a cycloolefin polymer film (COP) (ZF-14-50, film thickness 50 μm) made by Japan Zeon Co., Ltd. using a bar coater, and dried at 80 ° C. for 1 minute. Using a polarized UV irradiation device ("SPOT CURE SP-9", manufactured by Ushio Denki Co., Ltd.), the polarized UV exposure was performed with a cumulative light quantity at a wavelength of 313 nm: 100 mJ / cm ² and an axial angle of 45 °. When the film thickness of the obtained alignment layer 5 was measured using an ellipsometer, it was 100 nm.

Then, on the alignment layer 5, a composition for forming the λ / 4 retardation layer 4 was applied using a bar coater, and after drying at 120 ° C for 1 minute, a high-pressure mercury lamp ("Unicure VB-15201BY-A", Ushio Denki Co., Ltd.) was used. (Manufactured) by irradiating ultraviolet rays (accumulated light amount at a wavelength of 365 nm in a nitrogen environment: 500 mJ / cm ² ), thereby forming a λ / 4 retardation layer 4, and obtaining a substrate, an alignment layer 5, and a λ / 4 retardation layer 4. Composition of laminated body A. When the film thickness of the λ / 4 retardation layer 4 of the multilayer body A was measured using an ellipsometer, it was 2.3 μm.

[Modulation of composition (b) for forming vertical alignment layer for forming vertical alignment liquid crystal hardened layer]

A silane coupling agent "KBE-3103" manufactured by Shin-Etsu Chemical Industry Co., Ltd. was dissolved in a mixed solvent in which ethanol and water were mixed at a ratio of 9: 1 (mass ratio) to obtain a vertical alignment liquid crystal hardened layer having a solid content of 0.5%. Composition (b) for forming a vertical alignment layer.

[Preparation of composition for forming reinforcing layer 8 made of acrylic resin]

Prepare 50 parts of dipentaerythritol hexaacrylate (ARONIX M-403, polyfunctional acrylate manufactured by Toa Synthesis Co., Ltd.), 50 parts of acrylic resin (EBECRYL 4858, manufactured by DAICEL UCB Co., Ltd.), and 2-methyl A solution prepared by dissolving 3 parts of -1- [4- (methylthio) phenyl] -2-morpholinylpropan-1-one (Irgacure 907; manufactured by Ciba Specialty Chemicals) in 250 parts of isopropanol, and preparing Contains a composition for forming a reinforcing layer made of an acrylic resin.

[Manufacturing of a laminated body B composed of a base material, a reinforcing layer 8, an alignment layer 7, and a vertical alignment liquid crystal hardened layer 6]

On a polyethylene terephthalate film (manufactured by Lintec, Ltd., SP-PLR382050, hereinafter referred to as "separator"), which has been subjected to a release treatment, manufactured by Japan Zeon Co., Ltd., a bar coater is used to coat the film. The composition for forming a reinforcing layer made of an acrylic resin was dried at 50 ° C for 1 minute, and then irradiated with ultraviolet rays (under a nitrogen atmosphere, at a wavelength of 365 nm under a nitrogen environment, using a high-pressure mercury lamp ("Unicure VB-15201BY-A", manufactured by Ushio Electric Corporation) Cumulative light amount: 500 mJ / cm ² ), thereby forming a reinforcing layer 8 made of an acrylic resin. When the film thickness of the obtained reinforcement layer 8 was measured using a contact-type film thickness meter, it was 10 micrometers. Then, the composition (b) for forming a vertical alignment layer was applied on the reinforcing layer 8 using a bar coater, and dried at 80 ° C. for 1 minute to obtain a vertical alignment layer 7. The film thickness of the obtained vertical alignment layer 7 was 50 nm when measured using an ellipsometer.

Furthermore, the vertical alignment layer 7 was coated with a composition for forming the vertical alignment liquid crystal hardened layer 6 using a bar coater, and dried at 120 ° C for 1 minute, and then a high-pressure mercury lamp ("Unicure VB-15201BY-A", Ushio Electric Co., Ltd.) was used. (Manufactured by the company) by irradiating ultraviolet rays (accumulated light quantity at a wavelength of 365 nm in a nitrogen environment: 500 mJ / cm ² ), thereby forming a vertically aligned liquid crystal hardened layer 6, and obtaining a substrate, a reinforcing layer 8, an aligned layer 7, and a vertically aligned liquid crystal hardened The laminated body B consisting of the layers 6. The film thickness of the vertically aligned liquid crystal hardened layer 6 of the multilayer body B was 1.2 μm when measured using an ellipsometer. The interlayer distance between the reinforcing layer 8 and the vertically aligned liquid crystal hardened layer 6 is 50 nm. The constituent element ratio of the vertical alignment layer 7 is Si / C = 0.33.

[Re measurement of λ / 4 retardation layer 4 and vertical alignment liquid crystal hardened layer 6]

The in-plane retardation values (Re1 (λ) and Re2 (λ)) of the λ / 4 retardation layer 4 and the vertical alignment liquid crystal hardened layer 6 manufactured by the above method are after confirming that the COP film belonging to the substrate has no retardation. The measurement was performed by a measuring machine ("KOBRA-WPR", manufactured by Oji Measurement Co., Ltd.). As a result of measuring the retardation values ReQ (λ) at each wavelength, ReQ (450) = 119nm, ReQ (550) = 140nm, ReQ (650) = 146nm, ReQ (450) / ReQ (550) = 0.85.

[Rth measurement of vertical alignment liquid crystal hardened layer 6]

The thickness direction retardation value (RthV (λ)) of the vertically aligned liquid crystal hardened layer 6 manufactured by the above method is that the vertical aligned liquid crystal hardened layer 6 is laminated with an adhesive (pressure-sensitive adhesive made by Lintec Corporation 15 μm) and glass. After the separators belonging to the substrate are peeled off, and a measurement sample is produced, after confirming that there is no phase difference between the alignment layer 7 and the reinforcing layer 8, the angle of incidence of the light on the sample is measured by an ellipsometer. The average refractive index of the wavelengths λ of 450 nm and 550 nm was measured using a refractive index meter (manufactured by Atago Corporation, "multi-wavelength Abbe refractometer DR-M4"). The RthV calculated from the obtained film thickness, average refractive index, and measurement results of an ellipsometer are RthV (450) =-60nm, RthV (550) =-70nm, and RthV (450) / RthV (550) = 0.85.

[Manufacturing of Elliptical Polarizer 1]

After applying the corona treatment to the coating surface of the polymerizable liquid crystal composition of the λ / 4 retardation layer 4 of the multilayer body A, the polarizing layer 2 manufactured as described above and the λ / 4 retardation layer 4 of the multilayer body A are adhered to each other through the adhesion. Agent 3 (pressure-sensitive adhesive 15 μm made by Lintec) is bonded so that the angle formed by the absorption axis of the polarizing layer 2 and the slow axis of the λ / 4 retardation layer 4 becomes 45 °, and only the substrate is peeled off. Laminated body C was produced. Then, after the corona treatment is performed on the vertical alignment liquid crystal hardened layer 6 of the multilayer body B, the alignment layer 5 of the multilayer body C and the vertical alignment liquid crystal hardened layer 6 of the multilayer body B are sandwiched with an adhesive 3 (pressure sensitive type manufactured by Lintec). An adhesive (15 μm) was bonded together, and only the base material was peeled off to produce an elliptically polarizing plate 1.

[Difference in In-Plane Average Refractive Index of Each Layer]

Each layer was coated on glass according to the method described above, and the average refractive index of each layer was calculated using a refractometer (manufactured by Atago Co., Ltd., "Multiwavelength Abbe Refractometer DR-M4") or an ellipsometry, and the surface of each layer was confirmed The difference in the internal average refractive index is 0.2 or less.

    [Observation of cutting end face]    

The obtained elliptical polarizing plate was placed on a cutting pad, and a 3 cm × 3 cm square was cut out using a cutter, and then the end surface was visually observed with a 10-times magnifying glass to confirm whether defects such as undulations and cracks occurred. The same operation was performed three times, and even if one of them was observed, the case where a defect was observed was set to X, the case where no defect was observed was set to ○, and the results are shown in Table 1.

(Examples 2 and 3)

An elliptically polarizing plate was produced in the same manner as in Example 1 except that the film thickness of the reinforcing layer 8 was changed to that described in Table 1, and observation of the cut end surface was performed.

(Example 4)

In addition to 0.5% by weight of polyimide ("SUNEVER SE-610", manufactured by Nissan Chemical Industries, Ltd.), 72.3% by weight of N-methyl-2-pyrrolidone, and 18.1% by weight of 2-butoxy Ethanol, 9.1% by weight of ethylcyclohexane, and 0.01% by weight of DPHA (manufactured by Shin Nakamura Chemical Co., Ltd.) to prepare a composition (b) for forming a vertical alignment layer, and use the composition (b) for forming a vertical alignment layer and An elliptically polarizing plate was produced in the same manner as in Example 1 except that the thickness of the reinforcing layer 8 was set to 5 μm, and observation of the cut end surface was performed. The results are shown in Table 1. The thickness of the vertical alignment layer 7 was 0.5 μm when measured using an ellipsometer. Accordingly, the interlayer distance between the reinforcing layer 8 and the vertically aligned liquid crystal hardened layer 6 is 0.5 μm.

(Example 5)

As shown below, except that the composition for forming the reinforcing layer 8 and the manufacturing method of the reinforcing layer 8 were changed, an elliptic polarizing plate was produced in the same manner as in Example 1, and observation of the cut end face was performed. The results are shown in Table 1.

    [Preparation of composition for forming reinforcing layer 8 made of epoxy resin]    

80 parts of 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester, 20 parts of 2-ethylhexyl glycidyl ether, 2.25 parts of CPI-100P manufactured by SAN-APRO company, 2.25 parts of propylene carbonate, to prepare a composition for forming a reinforcing layer 8 made of epoxy resin.

    [Manufacturing of a laminated body B composed of a base material, a reinforcing layer 8, an alignment layer 7, and a vertical alignment liquid crystal hardened layer 6 (only the manufacturing portion of the reinforcing layer 8)]    

The release sheet was coated with a composition for forming a reinforcing layer 8 made of epoxy resin using a bar coater, and dried at 50 ° C for 1 minute, and then a high-pressure mercury lamp ("Unicure VB-15201BY-A" was used). ", Manufactured by Ushio Electric Co., Ltd.) to irradiate ultraviolet rays (cumulative light amount at a wavelength of 365 nm in a nitrogen environment: 400 mJ / cm ² ), thereby forming a reinforcing layer 8 made of epoxy resin. When the film thickness of the obtained reinforcement layer 8 was measured using a contact-type film thickness meter, it was 5 micrometers.

(Example 6)

As shown below, except that the composition for forming the reinforcing layer 8 and the manufacturing method of the reinforcing layer 8 were changed, an elliptically polarizing plate was produced in the same manner as in Example 1, and observation of the cut end face was performed. The results are shown in Table 1.

    [Preparation of composition for forming reinforcing layer 8 made of amine ester resin]    

100 parts of acrylate resin (EBECRYL 4858, manufactured by Daicel UCB Co., Ltd.) and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one (Irgacure 907 ; Manufactured by Ciba Specialty Chemicals) 3 parts of a solution dissolved in 250 parts of isopropyl alcohol to obtain a composition for forming a reinforcing layer 8 made of an amine ester resin.

    [Manufacturing of a laminated body B composed of a base material, a reinforcing layer 8, an alignment layer 7, and a vertical alignment liquid crystal hardened layer 6 (only the manufacturing portion of the reinforcing layer 8)]    

On the separator subjected to the release treatment, a composition for forming a reinforcing layer 8 containing an amine ester resin was applied using a bar coater, and dried at 50 ° C for 1 minute, and then a high-pressure mercury lamp ("Unicure VB-15201BY-A" was used). ", Manufactured by Ushio Electric Co., Ltd.) by irradiating ultraviolet rays (cumulative light amount at a wavelength of 365 nm in a nitrogen environment: 400 mJ / cm ² ), thereby forming a reinforcing layer 8 made of an amine ester resin. When the film thickness of the obtained reinforcement layer 8 was measured using a contact-type film thickness meter, it was 5 micrometers.

(Examples 7 to 9)

Except that the thickness of the reinforcing layer 8 was changed and the method of manufacturing the elliptically polarizing plate was changed as described below, the elliptically polarizing plate 10 having the layer structure shown in FIG. 2 was produced in the same manner as in Example 1, and observation of the cut end face was performed.

[Manufacturing method of elliptically polarizing plate 10]

First, after the corona treatment is performed on the vertical alignment liquid crystal hardened layer 6 of the multilayer body B, the vertical alignment liquid crystal hardened layer 6 side of the multilayer body B and the polarizing layer 2 obtained above are interposed with an adhesive 3 (pressure sensitive type manufactured by Lintec). Adhesive (15 μm) was adhered, and the substrate was peeled to produce a laminated body D. Then, after applying a corona treatment to the coating surface of the polymerizable liquid crystal composition of the λ / 4 retardation layer 4 of the multilayer body A, the reinforcing layer 8 of the multilayer body D and the λ / 4 retardation layer 4 of the multilayer body A, With the adhesive 3 (pressure-sensitive adhesive manufactured by Lintec Corporation 15 μm), the absorption axis of the polarizing layer 2 is substantially 45 ° with respect to the slow axis (optical axis) of the λ / 4 retardation layer 4 The substrates were bonded and peeled to produce an elliptically polarizing plate 10.

(Examples 10 to 12)

Except that the thickness of the reinforcing layer 8 was changed and the method of manufacturing the elliptically polarizing plate was changed as described below, the elliptically polarizing plate 100 having the layer structure shown in FIG. 3 was produced in the same manner as in Example 1, and observation of the cut end face was performed.

[Manufacturing method of elliptically polarizing plate 100]

First, after performing corona treatment on the λ / 4 phase difference layer 4 of the multilayer body A and the vertical alignment liquid crystal hardened layer 6 of the multilayer body B, the vertical alignment of the λ / 4 phase difference layer 4 of the multilayer body A and the multilayer body B is performed. The liquid crystal hardened layer 6 was bonded together via an adhesive 3 (15 μm pressure-sensitive adhesive manufactured by Lintec), and the base material of the laminated body B was peeled off to produce a laminated body E. Next, the reinforcing layer 8 and the polarizing layer 2 of the laminated body E are interposed with an adhesive 3 (pressure-sensitive adhesive made by Lintec Corporation 15 μm) so that the absorption axis of the polarizing layer 2 is relative to that of the λ / 4 retardation layer 4. After the slow axis (optical axis) is bonded so as to be substantially 45 °, the base material included in the laminated body A is peeled off to produce an elliptically polarizing plate 100.

(Comparative example 1)

An elliptical polarizing plate was produced in the same manner as in Example 1 except that the step of manufacturing the reinforcing layer was omitted, and observation of the cut end face was performed.

(Comparative example 2)

An elliptical polarizing plate was produced in the same manner as in Examples 7 to 9 except that the step of manufacturing the reinforcing layer was omitted, and observation of the cut end face was performed.

In the following, the results of observation of the cut end faces are shown for the examples and comparative examples. In addition, in Table 1, the interlayer distance means the interlayer distance between the vertically aligned liquid crystal hardened layer 6 and the reinforcing layer 8.

The elliptically polarizing plates of Examples 1 to 12 can be processed without causing undulations, cracks, and other defects during cutting, and are elliptically polarizing plates with good processing characteristics.

Claims (13)

    An elliptically polarizing plate comprising a polarizing layer, a λ / 4 retardation layer, a vertically aligned liquid crystal hardened layer and a reinforcing layer, wherein the vertically aligned liquid crystal hardened layer is vertically aligned with respect to the plane of the liquid crystal hardened layer. The polymer film of the polymerizable liquid crystal composition of the polymerizable liquid crystal compound is in a state where the film thickness of the vertically aligned liquid crystal hardened layer is 3 μm or less.         The elliptical polarizer according to item 1 of the scope of the patent application, wherein the interlayer distance between the vertically aligned liquid crystal hardened layer and the reinforcing layer is 5 μm or less.         The elliptically polarizing plate according to item 1 or 2 of the scope of patent application, wherein the film thickness of the reinforcing layer is 1 to 10 μm.         The elliptical polarizer according to any one of claims 1 to 3, wherein the λ / 4 retardation layer is a horizontally aligned liquid crystal hardened layer, and the horizontally aligned liquid crystal hardened layer is made of The layer plane is composed of a polymer of a polymerizable liquid crystal composition in a state where the polymerizable liquid crystal compound is aligned in a horizontal direction.         The elliptical polarizing plate according to any one of the first to fourth items of the patent application scope, which has a polarizing layer, a λ / 4 retardation layer, a vertically aligned liquid crystal hardening layer, and a reinforcing layer in this order.         The elliptical polarizing plate according to any one of the first to fourth items of the patent application scope, which has a polarizing layer, a vertically aligned liquid crystal hardening layer, a reinforcing layer, and a λ / 4 retardation layer in this order.         The elliptically polarizing plate according to any one of claims 1 to 4 of the scope of patent application, which has a polarizing layer, a reinforcing layer, a vertically aligned liquid crystal hardening layer, and a λ / 4 retardation layer in this order.         The elliptical polarizing plate according to any one of claims 1 to 7, wherein the reinforcing layer is selected from the group consisting of acrylic resin, epoxy resin, oxetane resin, amine ester resin, and melamine resin. At least one member of the group.         The elliptical polarizing plate according to any one of claims 1 to 8 of the scope of patent application, which has an alignment layer with a film thickness of 5 μm or less between the vertically aligned liquid crystal hardened layer and the reinforcing layer, and the alignment layer is composed of The element includes a layer composed of a compound of the Si element, the C element, and the O element.         The elliptically polarizing plate according to any one of claims 1 to 9, in which the difference in the average refractive index between the adjacent layers in a plane of a wavelength of 550 nm is 0.20 or less.         The elliptically polarizing plate according to any one of claims 1 to 10 in the scope of the patent application, wherein the λ / 4 retardation layer is formed in a refractive index ellipsoid formed by the λ / 4 retardation layer at a wavelength The range of λ = 400 to 700nm has the relationship of the following formula. nxQ (λ)> nyQ (λ) ≒ nzQ (λ) In the formula, nxQ (λ) represents the refractive index ellipse formed in the λ / 4 retardation layer. In the body, the principal refractive index of light having a wavelength of λ (nm) in a direction parallel to the plane of the retardation layer; nyQ (λ) means that in the refractive index ellipsoid formed by the λ / 4 retardation layer, the relative The refractive index of light with a wavelength of λ (nm) parallel to the plane of the retardation layer and orthogonal to the direction of the aforementioned nxQ (λ); nzQ (λ) means that the retardation layer is formed in the λ / 4 retardation layer In the refractive index ellipsoid, the refractive index of light having a wavelength of λ (nm) in a direction perpendicular to the plane of the retardation layer; and satisfying the relationship of the following formulas (1) to (3), ReQ (450) / ReQ (550) ≦ 1.00 (1) 1.00 ≦ ReQ (650) / ReQ (550) (2) 100nm ≦ ReQ (550) ≦ 160nm (3) In the formula, ReQ (450) represents the wavelength of light with a wavelength of λ = 450nm. In-plane retardation of λ / 4 retardation layer, ReQ (550) table Shows the in-plane retardation value of the λ / 4 retardation layer for light with a wavelength of λ = 550nm, and ReQ (650) shows the in-plane retardation value of the λ / 4 retardation layer for light with a wavelength of λ = 650nm. The in-plane retardation value ReQ (λ) of the λ / 4 retardation layer of λ (nm) light is expressed by ReQ (λ) = (nxQ (λ) -nyQ (λ)) × dQ, where dQ represents λ / 4 thickness of the retardation layer.         The elliptical polarizing plate as described in any one of claims 1 to 11 in the patent application scope, wherein, regarding the vertically aligned liquid crystal hardened layer, in a refractive index ellipsoid formed by the vertically aligned liquid crystal hardened layer, at a wavelength λ = The range from 400 to 700 nm has a relationship of the following formula. NzV (λ)> nxV (λ) (nyV (λ) where nzV (λ) is the refractive index ellipsoid formed by the liquid crystal hardened layer. The refractive index of light of λ (nm) in a direction perpendicular to the plane of the liquid crystal hardened layer; nxV (λ) represents the relative of light with a wavelength of λ (nm) in the refractive index ellipsoid formed by the liquid crystal hardened layer The maximum refractive index in a direction parallel to the plane of the liquid crystal hardened layer, nyV (λ) refers to the refractive index ellipsoid formed by the liquid crystal hardened layer, which is parallel to the plane of the liquid crystal hardened layer and is positive with respect to the aforementioned nxV direction Refractive index of light in the direction of intersection with wavelength λ (nm); but in the case of nxV (λ) = nyV (λ), nxV (λ) represents the refractive index in any direction parallel to the plane of the liquid crystal hardened layer; And satisfy the relationship of the following formulae (4) to (6), RthV (450) / RthV (550) ≦ 1.00 (4) 1.00 ≦ Rth V (650) / RthV (550) (5) -120nm ≦ RthV (550) ≦ -50nm (6) In the formula, RthV (450) represents the retardation in the thickness direction of the liquid crystal hardened layer for light having a wavelength of λ = 450nm. Value, RthV (550) represents the retardation value in the thickness direction of the liquid crystal hardened layer for light having a wavelength of λ = 550nm, and RthV (650) represents the retardation value in the thickness direction of the liquid crystal hardened layer for light having a wavelength of λ = 650nm. The retardation value RthV (λ) in the thickness direction of the liquid crystal hardened layer of light having a wavelength of λ (nm) is given by RthV (λ) = [(nxV (λ) + nyV (λ)) / 2-nzV (λ)] × dV represents; here, in the refractive index ellipsoid formed by the liquid crystal hardened layer, nzV (λ) represents the principal refractive index at a wavelength λ (nm) in a direction perpendicular to the plane of the liquid crystal hardened layer, and "(nxV (λ) + nyV (λ)) / 2 ″ represents the average refractive index on the plane of the liquid crystal hardened layer at the wavelength λ (nm); dV represents the thickness of the liquid crystal hardened layer.         An organic EL display device includes the elliptical polarizer described in any one of the first to twelfth patent applications.