TWI796342B - Elliptical polarizing plate - 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 λ/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 μm or less, and the interlayer distance between the vertically aligned liquid crystal cured layer and the reinforcing layer is 5 μm 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, along with diversification of displays, thinning of elliptically polarizing plates has been demanded. As a method for thinning an elliptically polarizing plate, it is known to change the retardation plate used in an elliptically polarizing plate from a stretched retardation plate to a liquid crystal obtained by hardening a polymerizable liquid crystal compound in an aligned state. Retardation plate made of cured film. For example, Patent Document 1 discloses a combination of a horizontally aligned λ/4 retardation plate made of a cured liquid crystal film and a phase plate having anisotropy (also called anisotropy) in the film thickness direction made of a cured liquid crystal film. Circular polarizer with optical compensation function.

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2015-163935

However, the liquid crystal cured film included in the elliptically polarizing plate is formed by forming a liquid crystal cured film on the base material, transferring it to the polarizing plate, and peeling off the base material in order to reduce the film thickness. The mechanical strength of the liquid crystal cured film is insufficient. Therefore, if the liquid crystal cured film formed on the base material is to be transferred separately to the polarizer to obtain an elliptical polarizer, when the obtained film is cut into a size suitable for the intended product, there may be problems at the cut end surface. Defects such as undulations.

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

The inventors of the present invention completed the present invention as a result of intensive examinations in order to solve the above-mentioned problems. That is, the present invention includes the following.

[1] An elliptical polarizing plate, which has 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 composed of a layer relative to the plane of the liquid crystal hardened layer. The polymerizable liquid crystal composition of the polymerizable liquid crystal compound in the state of homeotropic alignment is composed of polymers, and the film thickness of the homeotropic alignment liquid crystal cured layer is 3 μm or less.

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

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

[3] The elliptically polarizing plate as described in [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 including The polymerizable liquid crystal composition of the polymerizable liquid crystal compound in the state aligned in the horizontal direction is composed of polymers.

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

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

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

[8] The elliptically polarizing plate as described in any one of [1] to [7], 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 A layer composed of compounds containing Si, C, and O among the elements.

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

[10] The elliptically polarizing plate according to any one of [1] to [9], wherein, with respect to the λ/4 retardation layer, in the refractive index ellipsoid formed by the λ/4 retardation layer, at wavelength The range of λ=400 to 700nm has the relationship of the following formula, nxQ(λ)>nyQ(λ)≒nzQ(λ) [wherein, nxQ(λ) represents the refractive index formed in the λ/4 retardation layer In the ellipsoid, the main refractive index of the light of wavelength λ (nm) is 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 refractive index to the light of the wavelength λ (nm) that is parallel to the plane of the phase difference layer and is orthogonal to the direction of the aforementioned nxQ (λ); In the refractive index ellipsoid that forms, to the light of wavelength λ (nm) being the refractive index of the direction perpendicular to the retardation layer plane]; And satisfy the relation of following formula (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 to the light of wavelength λ=450nm, and ReQ(550) represents the in-plane retardation value of the λ/4 retardation layer to the light of wavelength λ=550nm In-plane retardation value, ReQ(650) represents the in-plane retardation value of the λ/4 retardation layer for light with wavelength λ=650nm, and the in-plane retardation value for λ/4 retardation layer for light with wavelength 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 elliptically polarizing plate as described in any one of [1] to [10], wherein, regarding the vertically aligned liquid crystal hardened layer, in the refractive index ellipsoid formed by the vertically aligned liquid crystal hardened layer, at wavelength λ= The range of 400 to 700nm has the following relationship, nzV(λ)>nxV(λ)≒nyV(λ)

[In the formula, nzV (λ) means that in the refractive index ellipsoid formed by the liquid crystal hardening layer, the refractive index of the light of wavelength λ (nm) is perpendicular to the plane of the liquid crystal hardening layer; nxV (λ) It means that in the refractive index ellipsoid formed by the liquid crystal hardening layer, the maximum refractive index of the light of wavelength λ (nm) in the direction parallel to the plane of the liquid crystal hardening layer, nyV (λ) means that in the liquid crystal hardening layer In the formed refractive index ellipsoid, the refractive index to the light of the wavelength λ (nm) is parallel to the plane of the liquid crystal hardening layer and perpendicular to the direction of the aforementioned nxV; but in nxV(λ)=nyV( In the case of λ), nxV (λ) represents the refractive index in any direction parallel to the plane of the liquid crystal hardening 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 of wavelength λ=450nm, and RthV(550) represents the retardation value of the thickness direction of the liquid crystal hardened layer for light of wavelength λ=550nm Value, RthV(650) represents the retardation value in the thickness direction of the liquid crystal hardened layer for light with wavelength λ=650nm, and the retardation value RthV(λ) for the thickness direction of the liquid crystal hardened layer for light with wavelength λ(nm) Expressed by RthV(λ)=[(nxV(λ)+nyV(λ))/2-nzV(λ)]×dV; here, in the refractive index ellipsoid formed by the liquid crystal hardening layer, nzV(λ) Indicates the main refractive index in the direction perpendicular to the plane of the liquid crystal hardening layer at the wavelength λ (nm), and "(nxV(λ)+nyV(λ))/2" means the main refractive index at the wavelength λ (nm) in the liquid crystal hardening layer The average refractive index of the plane; dV represents the thickness of the liquid crystal hardening layer].

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

[13] An organic EL display device comprising 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 waviness on the cut end surface even if it is cut, and has good processing characteristics.

1,10,100‧‧‧elliptical polarizer

2‧‧‧Polarizing layer

3‧‧‧adhesive layer

4‧‧‧λ/4 retardation layer

5‧‧‧Alignment layer

6‧‧‧Vertically aligned liquid crystal hardening layer

7‧‧‧Vertical alignment layer

8‧‧‧reinforcing layer

Fig. 1 is a schematic cross-sectional view showing an example of the layer constitution of the elliptically polarizing plate of the present invention.

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

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

The elliptically polarizing plate of the present invention has a polarizing layer, a λ/4 retardation layer, a vertically aligned liquid crystal hardening layer, and a reinforcing layer, and the lamination sequence of each layer can be appropriately selected. In a preferred aspect, each layer is laminated in the following order. Polarizing layer, λ/4 retardation layer, vertical alignment liquid crystal hardening layer, 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 these order is shown in Figs. 1 to 3, but the present invention is not limited to these aspects.

The elliptically polarizing plate 1 shown in FIG. 1 is sequentially equipped 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. Reinforcing layer8. The elliptical polarizing plate 10 shown in FIG. 2 is sequentially equipped 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 equipped 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 together 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 . Furthermore, the polarizing layer 2 may have a transparent protective film on one side of the polarizer (the side opposite to the adhesive 3). In this specification, the term "substantially 45°" is usually within the range of 45°±5°.

[reinforcing layer]

The elliptically polarizing plates 1, 10, and 100 of the present invention include a reinforcing layer 8 that has a function of reinforcing the layers included in the elliptically polarizing plate (in particular, the vertical alignment liquid crystal cured layer 6). For the elliptical polarizers 1, 10 and 100, even if the vertically aligned liquid crystal hardening layer 6 is a thin film, the reinforcing layer 8 can still fully reinforce the strength of the vertically aligned liquid crystal hardening layer 6. If the interlayer distance between the vertically aligned liquid crystal hardening layer 6 and the reinforcing layer 8 is small , the strength of the vertically aligned liquid crystal cured layer 6 can be more fully reinforced. Therefore, the processing characteristics of the elliptically polarizing plate are improved, and defects of cut end faces can be effectively suppressed or prevented. Furthermore, in this specification, the so-called "interlayer distance" means the shortest distance between the vertically aligned liquid crystal hardened layer 6 and the reinforcing layer 8, and the so-called "processing characteristics" means that when cutting an elliptical polarizer, it can be suppressed or prevented. The characteristics of defects such as undulations on the cutting end surface.

The interlayer distance between vertically aligned liquid crystal hardening layer 6 and reinforcing layer 8 is, for example, 5 μm or less, preferably 3 μm or less, more preferably 1.5 μm or less, more preferably 1.0 μm or less, still more preferably 500 nm or less, most preferably 300 nm the following. If there is no vertical alignment layer 7, the interlayer distance is 0 nm. The lower limit of the distance between layers will inevitably be determined by the film thickness of the layer between the vertically aligned liquid crystal hardening layer 6 and the reinforcing layer 8 (the film thickness of the vertical alignment layer 7 in the aspects of Figures 1 to 3), so there is no special limit. The limit is preferably more than 1nm. When the interlayer distance is below the above upper limit, the reinforcing layer 8 can more fully reinforce the vertically aligned liquid crystal cured layer 6, and can exhibit good processing characteristics, so when cutting an elliptically polarizing plate, defects such as waviness will not occur on the cut end surface. Furthermore, the shorter the interlayer distance, the easier it is for the reinforcement layer 8 to contribute to the reinforcement of the vertically aligned liquid crystal cured layer 6, so the processing characteristics tend to be improved.

The reinforcing layer 8 is made of a material capable of reinforcing the strength of the vertically aligned liquid crystal cured layer 6, such as a material selected from the group consisting of acrylic resin, epoxy resin, oxetane resin, urethane resin and melamine resin. Made of at least 1 type. Among them, from the viewpoint of easy formation of a highly curable and highly reinforcing reinforcing layer 8, it is preferable to include a resin selected from acrylic resins, epoxy resins, oxetane resins, urethane resins, and melamine resins. At least one kind selected from the group formed, more preferably at least one selected from the group consisting of acrylic resins and urethane resins.

The reinforcing layer 8 is preferably a cured product of a curable composition including a curable material cured by heat or light. The hardening material of the reinforcing layer 8 comprising acrylic resin can be exemplified: 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, Tetrahydroxy Methylmethane tetraacrylate, Pentyl glycerin triacrylate, Neopentylthritol triacrylate, Neopentylthritol tetraacrylate, Glycerin triacrylate, Dineopentylthritol triacrylate, Dineopentylthritol Tetraacrylate, diperythritol pentaacrylate, diperythritol hexaacrylate, ginseng (acryloxyethyl) isocyanurate; ethylene glycol dimethacrylate, diethylene glycol dimethyl Acrylate, 1,6-Hexanediol Dimethacrylate, Neopentyl Glycol Dimethacrylate, Trimethylolpropane Trimethacrylate, Trimethylolethane Trimethacrylate , Tetramethylolmethane Trimethacrylate, Tetramethylolmethane Tetramethacrylate, Pentyl Glycerin Trimethacrylate, Neopentylthritol Trimethacrylate, Neopentylthritol Tetramethacrylate , Glycerin Trimethacrylate, Dineopentylthritol Trimethacrylate, Dineopentylthritol Tetramethacrylate, Dineopentylthritol Pentamethacrylate, Dineopentylthritol Hexamethacrylate acrylate, ginseng (methacryloxyethyl) isocyanurate, etc. (Meth)acrylates can be used alone or in combination of two or more, from the viewpoint of suppressing curling caused by heating during curing or after curing, from the viewpoint of improving processing characteristics, and from the viewpoint of ensuring sufficient reinforcement of the reinforcing layer 8 See, the (meth)acrylate can be chosen appropriately. Furthermore, from the same viewpoint, it can be mixed with epoxy resin, oxetane resin, urethane resin, melamine resin, and the like. In addition, in this specification, acrylate and methacrylate may be collectively referred to as (meth)acrylate, and acrylic acid and methacrylic acid may be collectively referred to as (meth)acrylic acid.

The curable material of the reinforcing layer 8 made of urethane resin can be, for example, urethane (meth)acrylate which is a reaction product of (meth)acrylic acid and/or (meth)acrylate, polyol and diisocyanate wait. Specifically, the urethane (meth)acrylate can be prepared from (meth)acrylic acid and/or (meth)acrylate and polyhydric alcohol to prepare a hydroxyl (meth)acrylate having at least one hydroxyl group in the molecule, And make it react with diisocyanate to manufacture. Urethane (meth)acrylate can be used individually or in combination of 2 or more types.

The aforementioned (meth)acrylate may be a chain or cyclic alkyl ester of (meth)acrylate. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, etc. ) alkyl acrylate and cycloalkyl (meth)acrylate such as cyclohexyl (meth)acrylate. The aforementioned polyol-based compound has at least two hydroxyl groups in its molecule. For example, 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, spiroglycerin (spiroglycol), tricyclodecane dimethylol Hydrogenated bisphenol A, ethylene oxide added bisphenol A, propylene oxide added bisphenol A, trimethylolethane, trimethylolpropane, glycerol, 3-methylpentane- 1,3,5-triol, neopentylthritol, diperythritol, trineopentylthritol, glucose, etc.

The diisocyanate-based compound has two isocyanate groups (-NCO) in its molecule, and various aromatic, aliphatic, or alicyclic diisocyanates can be used. Specific examples include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-toluene diisocyanate, 4,4'-diphenyl diisocyanate, 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 an aromatic ring among them, and the like.

Urethane (meth)acrylate can be appropriately selected from the viewpoint of suppressing curling caused by heating during and after curing, improving processability, and ensuring sufficient reinforcement of the reinforcing layer 8 . Furthermore, from the same viewpoint, it may also be mixed with an acrylic resin, an epoxy resin, an oxetane resin, a melamine resin, or the like.

Examples of curable materials for the reinforcing layer including epoxy resins include alicyclic epoxy compounds, aromatic epoxy compounds, hydrogenated epoxy compounds, and aliphatic epoxy compounds.

The alicyclic epoxy compound is a compound having at least one epoxy group directly bonded to an alicyclic ring in a molecule. Examples include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate 6-methylcyclohexylmethyl ester, ethylidene bis(3,4-epoxycyclohexanecarboxylate), adipate bis(3,4-epoxycyclohexylmethyl)ester, adipate 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-type epoxy compounds such as bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, and bisphenol-S diglycidyl ether, or their oligomers. phenol novolac epoxy resin, cresol novolak epoxy resin, hydroxybenzaldehyde phenol novolak epoxy resin and other novolac epoxy resins; 2,2',4,4'-tetrahydroxydiphenylmethane Polyfunctional epoxy compounds such as glycidyl ether and glycidyl ether of 2,2',4,4'-tetrahydroxybenzophenone; multifunctional epoxy resins such as epoxidized polyvinylphenol wait. These aromatic epoxy compounds can be used individually or in combination of 2 or more types.

The hydrogenated epoxy compound is a nuclear hydrogenated product of the above-mentioned aromatic epoxy compound to be a hydrogenated epoxy compound. These can be produced by the following method: by selectively dissolving aromatic polyhydroxy compounds (typically bisphenols) which are the raw materials of the corresponding aromatic epoxy compounds in the presence of a catalyst and under pressure A method in which a polyol (typically hydrogenated bisphenols) obtained by hydrogenation is used as a raw material, reacted with epichlorohydrin to form a chlorohydrin ether, and further intramolecularly closed using a base. These hydrogenated epoxy compounds can be used individually or in combination of 2 or more types.

Aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts. Specific examples thereof include, for example, the dielycidyl ether of neopentyl glycol, the dielycidyl ether of 1,4-butanediol, the dielycidyl ether of 1,6-hexanediol, Triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of propylene glycol, Polyglycidyl ethers of polyether polyols obtained by adding one or more than two kinds of alkylene oxides (ethylene oxide, propylene oxide) to aliphatic polyols such as alcohol, 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 curling caused by heating during curing and after curing, improving the processing characteristics, ensuring sufficient reinforcement of the reinforcing layer 8, and adjusting the adhesiveness with the base material and the liquid crystal cured layer, Epoxy resins can be appropriately selected. Furthermore, from the same viewpoint, it may also be mixed with an acrylic resin, an urethane resin, an oxetane resin, a melamine resin, or the like.

The curable material of the reinforcing layer 8 made of oxetane resin may, for example, be a compound containing at least one oxetane group in its molecule. Specific examples thereof include, for example, 3-ethyl-3-hydroxymethyloxetane (also known as oxetanol), 2-ethylhexyloxetane, 1,4-bis[ {(3-Ethyloxetan-3-yl)methoxy}methyl]benzene (also known as xylylenebisoxetane), 3-ethyl-3[{( 3-Ethyloxetane-3-yl)methoxy}methyl]oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-( cyclohexyloxy)methyl-3-ethyloxetane, etc.

As for the curable material of the reinforcing layer 8 made of melamine resin, for example, hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine and other melamine compounds.

The curable composition for forming the reinforcing layer may further contain 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 of using a curable composition cured by radical polymerization such as (meth)acrylate, urethane (meth)acrylate as a curable material, photoradical polymerization initiator can be used agent, in the case of using a curable composition hardened by cationic polymerization such as epoxy compound and oxetane compound as the curable composition, a photocationic polymerization initiator can be used, and when using a curable composition hardened by heat When a curable composition such as a melamine compound is used as the curable composition, a thermal polymerization initiator can be used.

化合物等，光陽離子聚合引發劑可舉例如芳香族重氮鹽、芳香族錪鹽、芳香族鋶鹽等的鎓鹽、鐵-芳烴錯合物等。具體而言，可舉例如：Irgacure(註冊商標)907、Irgacure 184、Irgacure 651、Irgacure 819、Irgacure 250、Irgacure 369、Irgacure 379、 Irgacure 127、Irgacure 2959、Irgacure 754、Irgacure 379EG(以上日本BASF股份公司製)；SEIKUOL BZ、SEIKUOL Z、SEIKUOL BEE(以上精工化學股份公司製)；Kayacure BP100(日本化藥股份公司製)；Kayacure UVI-6992(Dow公司製)；ADEKA Optomer SP-152、ADEKA Optomer SP-170、ADEKA Optomer N-1717、ADEKA Optomer N-1919、ADEKA ARKLS NCI-831、ADEKA ARKLS NCI-930(以上ADEKA股份公司製)；TAZ-A、TAZ-PP(以上日本Siber Hegner公司製)及TAZ-104(三和化學公司製)；KAYARAD(註冊商標)系列(日本化藥股份公司製)；CYRACURE UVI系列(Dow Chemical公司製)；CPI系列(SAN-APRO股份公司製)；TAZ、BBI及DTS(以上Midori化學股份公司製)；RHODORSIL(註冊商標)(Rhodia股份公司製)等。光聚合引發劑可單獨使用或組合2種以上使用。光聚合引發劑可配合所使用的材料，適當地選擇使用。 As a photopolymerization initiator, a photoradical polymerization initiator, a photocationic polymerization initiator, etc. are mentioned, for example. The photoradical polymerization initiator can be exemplified by benzoin compounds, benzophenone compounds, diphenyl diketone ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, three

Compounds etc., photocationic polymerization initiators, for example, onium salts such as aromatic diazonium salts, aromatic iodonium salts, and aromatic permeic acid salts, iron-arene complexes, and the like. 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 379 EG (the above Japan BASF Co., Ltd. SEIKUOL BZ, SEIKUOL Z, SEIKUOL BEE (manufactured by Seiko Chemical Co., Ltd. above); Kayacure BP100 (manufactured by Nippon Kayaku Co., Ltd.); Kayacure UVI-6992 (manufactured by Dow Corporation); ADEKA Optomer SP-152, ADEKA Optomer SP -170, ADEKA Optomer N-1717, ADEKA Optomer N-1919, ADEKA ARKLS NCI-831, ADEKA ARKLS NCI-930 (made by ADEKA Co., Ltd. above); TAZ-A, TAZ-PP (made by Siber Hegner Corporation in Japan above) 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., Ltd.); CPI series (manufactured by San-Apro Co., Ltd.); TAZ, BBI And DTS (the above Midori Chemical Co., Ltd.); RHODORSIL (registered trademark) (Rhodia Co., Ltd.), etc. A photoinitiator can be used individually or in combination of 2 or more types. A photopolymerization initiator can be suitably selected and used according to the material to be 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 300nm to 400nm, more preferably 300nm to 380nm, wherein the α-acetophenone-based polymerization initiator, An oxime-based photopolymerization initiator is preferred.

Examples of α-acetophenone-based polymerization initiators include 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1 -(4-morpholinylphenyl)-2-benzylbutan-1-one and 2-dimethylamino-1-(4-morpholinylphenyl)-2-(4-methyl phenylmethyl) butane-1-one, etc., more preferably 2-methyl-2-morpholinyl-(4-methylthiophenyl)propane-1-one and 2-dimethylamino -1-(4-morpholinylphenyl)-2-benzylbutan-1-one. Commercially available α-acetophenone compounds include, for example, Irgacure 369, 379EG, and 907 (manufactured by BASF Co., Ltd.), SEIKUOL BEE (manufactured by Seiko Chemical Co., Ltd.).

化合物、肟酯型咔唑化合物，從感度的觀點來看，更佳為肟酯型咔唑化合物。肟酯型咔唑化合物可舉例如1,2-辛烷二酮、1-[4-(苯硫基)-2-(O-苯甲醯基肟)]、乙酮，1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-1-(O-乙醯基肟)等。肟酯型咔唑化合物的市售品可舉例如Irgacure OXE-01、Irgacure OXE-02、Irgacure OXE-03(以上日本BASF股份公司製)、ADEKA Optomer N-1919、ADEKA ARKLS NCI-831(以上ADEKA股份公司製)等。 Oxime-based photopolymerization initiators generate free radicals when irradiated with light. The polymerization of the curable composition in the deep part of the layer is suitably performed by the free radicals. Furthermore, from the viewpoint of more efficiently advancing the polymerization reaction in the deep part of the layer, it is preferable to use a photopolymerization initiator that can efficiently utilize ultraviolet light having a wavelength of 350 nm or more. The photopolymerization initiator that can efficiently utilize ultraviolet light with a wavelength of 350nm or more is preferably three

The compound, the oxime ester type carbazole compound, is more preferably an oxime ester type carbazole compound from the viewpoint of sensitivity. Oxime ester type carbazole compounds can be exemplified by 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethyl ketone, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like. Commercially available products of the oxime ester type carbazole compound include, for example, Irgacure OXE-01, Irgacure OXE-02, Irgacure OXE-03 (manufactured by the above-mentioned Japan BASF Co., Ltd.), ADEKA Optomer N-1919, ADEKA ARKLS NCI-831 (the above-mentioned ADEKA joint stock company), etc.

Examples of thermal polymerization initiators 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-methylpropionate) dimethyl ester, 2,2'-azobis(2-hydroxymethylpropionitrile) and other azo compounds; lauryl peroxide, tertiary butyl hydroperoxide, benzoyl peroxide, tertiary butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, peroxide Organic peroxides such as tert-butyl neodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexyl) peroxide; potassium persulfate, ammonium persulfate, peroxide Inorganic peroxides such as hydrogen, etc. These thermal polymerization initiators can be used individually or in combination of 2 or more types.

The amount of the polymerization initiator added is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the curable composition. If it is in the said range, hardening reaction will fully progress easily.

Since the curable material is usually applied to the substrate in a state of being dissolved in a solvent, it is preferable that the curable material contains the solvent. The solvent is preferably a solvent that can dissolve the curable composition, and is preferably a solvent that is inert to the polymerization reaction of the curable material. Examples of solvents include: water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, 2-butoxyethanol and propylene glycol monomethyl ether and other alcohol solvents; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate and ethyl lactate and other ester solvents; 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; fatty acids 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; chlorinated solvents such as chloroform and chlorobenzene; dimethylacetamide, dimethyl Amide-based solvents such as methylformamide, N-methyl-2-pyrrolidone (NMP), and 1,3-dimethyl-2-imidazolidinone, etc. These solvents can be used individually or in combination of 2 or more types. Among these, alcohol solvents, ester solvents, ketone solvents, chlorine-containing solvents, amide-based solvents, and aromatic hydrocarbon solvents are preferable.

The content of the solvent is preferably from 50 to 98 parts by mass, more preferably from 60 to 95 parts by mass, relative to 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. In this range, since the viscosity of the curable composition becomes low, the thickness of the reinforcing layer becomes approximately uniform, and unevenness tends to be less likely to occur in the reinforcing layer.

The curable composition can be obtained by, for example, stirring components other than the curable material such as the curable material and additives at a predetermined temperature.

The reinforcing layer 8 can be obtained by coating a curable composition on a base material, removing the solvent, and curing it by heating and/or active energy rays.

The method of coating a curable composition on a base material (hereinafter referred to as coating method A) includes, for example, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a CAP coating method. , Slit coating method, micro gravure method, die coating method, inkjet method, etc. Moreover, the method etc. which apply using coaters, such as a dip coater, a bar coater, and a spin coater, can also be mentioned, for example. Among them, in the case of continuous coating in a roll-to-roll (Roll to Roll) type, coating methods by microgravure method, inkjet method, slit coating method, and die coating method are preferable.

The method for removing the solvent (hereinafter sometimes referred to as solvent removal method A) includes, for example, natural drying, ventilation drying, heat drying, reduced-pressure drying, and a combination of these methods. Among them, natural drying or heating drying is preferable. The drying temperature is preferably in the range of 0 to 200°C, more preferably in the range of 20 to 150°C, and more preferably in the range of 50 to 130°C. The drying time is preferably from 10 seconds to 20 minutes, more preferably from 30 seconds to 10 minutes.

The active energy ray to be irradiated is appropriately selected depending on the type of the curable composition, the type of the photopolymerization initiator when the photopolymerization initiator is contained, 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 can be mentioned. Among them, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction and a photopolymerization device widely used in this field can be used, and it is preferable to use one that can be photopolymerized by ultraviolet light. The method selects the type of polymerizable liquid crystal compound.

The light sources of the aforementioned active energy lines can be, for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, xenon lamps, halogen lamps, carbon arc lamps, tungsten lamps, gallium lamps, excimer lasers, and those with wavelengths ranging from 380 to 440 nm. Light LED light source, 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 intensity of ultraviolet irradiation is preferably an intensity in a wavelength region effective for activating a photocationic polymerization initiator or a photoradical polymerization initiator. The time for irradiating light is usually 0.1 second to 10 minutes, preferably 0.1 second to 5 minutes, more preferably 0.1 second to 3 minutes, and more preferably 0.1 second to 1 minute. When irradiated with such an intensity of ultraviolet radiation for one time or multiple times, the cumulative light intensity is 10 to 3000 mJ/cm ² , preferably 50 to 2000 mJ/cm ² , 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 elliptically polarizing plate may decrease. Conversely, when the cumulative light intensity is more than this range, the elliptically polarizing plate may be colored.

In the case of hardening the curable composition by heat, the heating temperature is appropriately selected depending on the kind of the curable material, the kind and the amount of the thermal polymerization initiator in the case of including the thermal polymerization initiator, for example 50 to 200°C, preferably 50 to 130°C. The heating time is, for example, 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes. In addition, in the case of heat drying, drying and hardening may be performed simultaneously.

The film thickness of the reinforcing layer 8 is preferably 1 to 10 μm from the viewpoint of reinforcing properties. When the film thickness of the reinforcing layer 8 is more than the above lower limit, the layers included in the elliptically polarizing plate, especially the vertically aligned liquid crystal hardened layer 6 can be sufficiently reinforced, and good processing characteristics can be exhibited. It is preferable that the film thickness of the reinforcement layer 8 is below the said upper limit from a viewpoint of thinning an elliptically polarizing plate. The film thickness of the reinforcing layer 8 is preferably 1 to 5 μm, more preferably 1 to 3 μm from the viewpoint of thinning the elliptically polarizing plate, and preferably 5 to 3 μm from the viewpoint of 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 includes, for example, a stretched film on which an absorption anisotropic dye is adsorbed or a film coated with an absorption anisotropic dye as a polarizer. Examples of dyes having absorption anisotropy include dichroic dyes.

A film comprising a stretched film adsorbed with an anisotropic absorption pigment as a polarizer is usually produced by sandwiching at least one side of the polarizer with a transparent protective film via an adhesive. A step of uniaxially stretching a polyvinyl alcohol-based resin film, a step of dyeing a polyvinyl alcohol-based resin film with a dichroic dye to adsorb the dichroic dye, and making the polyvinyl alcohol-based resin film with the dichroic dye adsorbed Manufactured using a step of treating with an aqueous boric acid solution and a step of washing with water after treatment with an aqueous solution of boric acid.

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

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

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

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

The dyeing of a polyvinyl alcohol-type resin film with a dichroic dye can be performed by the method of immersing a polyvinyl alcohol-type resin film in the aqueous solution containing a dichroic dye, for example.

As the dichroic dye, iodine and a dichroic organic dye can be used specifically. Dichroic organic dyes include, for example, dichroic direct dyes made of disazo compounds such as C.I. Direct Red 39 and dichroic direct dyes made of compounds such as trisazo and 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, the method of immersing and dyeing a polyvinyl-alcohol-type resin film in the aqueous solution containing iodine and potassium iodide is employ|adopted normally. The content of iodine in the aqueous solution is usually about 0.01 to 1 part by mass per 100 parts by mass of water. In addition, 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 about 20-40 degreeC normally. And, the immersion time (dyeing time) in this aqueous solution is about 20 to 1800 seconds normally.

On the other hand, when using a dichroic organic dye as a dichroic dye, the method of immersing and dyeing a polyvinyl-alcohol-type resin film in the aqueous solution containing a water-soluble dichroic dye is employ|adopted normally. 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, more preferably 1 ×10 ^-3 to 1×10 ^-2 parts by mass. The aqueous solution may contain inorganic salts such as sodium sulfate as dyeing aids. The temperature of the dichroic dye aqueous solution used for dyeing is about 20-80 degreeC normally. And, the immersion time (dyeing time) in this aqueous solution is about 10 to 1800 seconds normally.

The boric acid treatment after dyeing with a dichroic dye can be generally performed by a method of immersing a dyed polyvinyl alcohol-based resin film in a boric acid aqueous solution. The content of boric acid in the boric acid aqueous solution is usually about 2 to 15 parts by mass, preferably 5 to 12 parts by mass, per 100 parts by mass of water. In the case of using iodine as a dichroic dye, 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, 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 generally about 60 to 1200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds. The temperature of the boric acid aqueous solution is usually above 50°C, preferably 50 to 85°C, more preferably 60 to 80°C.

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

After washing with water, drying treatment 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 generally about 60 to 600 seconds, preferably 120 to 600 seconds. By drying, the moisture content of the polarizer is reduced to a practical level. The moisture content is usually about 5 to 20% by weight, 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 cracked after drying. Furthermore, when the moisture content exceeds 20% by weight, the thermal stability of the polarizer may deteriorate.

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

The film coated with a dye having absorption anisotropy includes, for example, a film coated with a composition containing a liquid crystalline dichroic dye or a composition containing a dichroic dye and a polymerizable liquid crystal. The film preferably has a protective film on one or both sides. As this protective film, the thing similar to the base material mentioned later is mentioned, for example.

The film coated with an anisotropic absorption dye is preferably thin, but if it is too thin, the strength will decrease and the processability will tend to be poor. The thickness of the film is usually 20 μm or less, preferably 5 μm or less, more preferably 0.5 to 3 μm.

The aforementioned film coated with a dye having absorption anisotropy specifically includes films described in JP-A-2012-33249 and the like.

The polarizing layer 2 is obtained by laminating a transparent protective film on at least one surface of the polarizer thus obtained via an adhesive. As a transparent protective film, it is preferable to use the same transparent film as the base material mentioned later.

[λ/4 retardation layer]

The λ/4 retardation layer 4 is a layer having an anisotropic refractive index in the film plane. The λ/4 retardation layer 4 can be formed by stretching or shrinking a polymer film, but from the viewpoint of thinning the elliptically polarizing plate, it is preferable to include a polymerizable liquid crystal compound (also called a polymerizable liquid crystal compound). The polymerizable liquid crystal composition is formed by polymerizing in an aligned state.

The 3-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 horizontal alignment liquid crystal cured layer composed of a polymer of a polymerizable liquid crystal composition including a polymerizable liquid crystal compound aligned in the horizontal direction with respect to the plane of the λ/4 retardation layer.

The horizontally aligned liquid crystal hardening layer is for aligning the optical axis of the polymerizable liquid crystal in the horizontal direction relative to the plane of the λ/4 retardation layer. The polymerizable liquid crystal constituting the λ/4 retardation layer may be rod-shaped or disk-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 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 perpendicular to the disc surface of the polymerizable liquid crystal.

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

The λ/4 phase difference layer 4 can use any one of rod-shaped polymerizable liquid crystals and disc-shaped polymerizable liquid crystals, but rod-shaped polymerizable liquid crystals are preferred, and horizontally aligned liquid crystals are formed on the rod-shaped polymerizable liquid crystals. 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, in the range of wavelength λ=400 to 700nm, there is the following relationship, nxQ(λ)>nyQ(λ) ≒nzQ(λ)

[In the formula, nxQ(λ) means that in the refractive index ellipsoid formed by the λ/4 retardation layer, the main refractive index of the light of the wavelength λ (nm) is parallel to the plane of the retardation layer; nyQ(λ) represents the pair wavelength λ( nm) of light; nzQ(λ) means that in the refractive index ellipsoid formed by the λ/4 retardation layer, the direction perpendicular to the plane of the retardation layer for the light of wavelength λ(nm) Refractive index]; And satisfy the relation of following formula (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 to the light of wavelength λ=450nm, and ReQ(550) represents the in-plane retardation value of the λ/4 retardation layer to the light of wavelength λ=550nm In-plane retardation value, ReQ(650) represents the in-plane retardation value of the λ/4 retardation layer for light with wavelength λ=650nm, and the in-plane retardation value for λ/4 retardation layer for light with wavelength 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), there may be a problem that the hue of the front surface of the display including the elliptically polarizing plate becomes red or blue. A more preferable range of the in-plane retardation value is 130nm≦ReQ(550)≦150nm. When 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 including the λ/4 retardation layer deteriorates. When the ellipticity of the circular polarizing plate on the short wavelength side deteriorates and becomes smaller than 1.0, the function of the circular polarizing plate when viewed from the front on the short wavelength side is impaired. The [ReQ(450)/ReQ(550)] is preferably from 0.75 to 0.92, more preferably from 0.77 to 0.87, and still more preferably from 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 retardation value is determined by the above formula ReQ(λ)=(nxQ(λ)-nyQ(λ))×dQ, so to obtain the desired in-plane retardation value (ReQ(λ): at wavelength λ( nm) λ/4 retardation layer in-plane retardation value), then adjust the three-dimensional refractive index and film thickness dQ. In addition, the three-dimensional refractive index depends on the molecular structure and alignment state of the polymerizable liquid crystal compound described later.

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, still more preferably 2.5 μm or less, from the viewpoint of thinning. Furthermore, the lower limit of the film thickness of the λ/4 retardation layer 4 is preferably at least 0.1 μm, more preferably at least 0.5 μm, and still more preferably at least 0.8 μm. 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 Hardening Layer)

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

In the case that the vertical alignment liquid crystal hardening layer 6 is a positive C plate, the vertical alignment liquid crystal hardening layer 6 is preferably in the refractive index ellipsoid formed by the vertical alignment liquid crystal hardening layer 6, and has The following relationship, nzV(λ)>nxV(λ)≒nyV(λ)

[In the formula, nzV(λ) represents the refractive index in the direction perpendicular to the plane of the liquid crystal hardening layer for light of wavelength λ (nm) in the refractive index ellipsoid formed by the liquid crystal hardening layer. nxV(λ) represents the maximum refractive index in the direction parallel to the plane of the liquid crystal hardening layer for light of wavelength λ (nm) in the refractive index ellipsoid formed by the liquid crystal hardening layer. nyV(λ) represents the refractive index of light with wavelength λ (nm) in a direction parallel to the plane of the liquid crystal hardening layer and perpendicular to the aforementioned nxV direction in the refractive index ellipsoid formed by the liquid crystal hardening layer . 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 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 of wavelength λ=450nm, and RthV(550) represents the retardation value of the thickness direction of the liquid crystal hardened layer for light of wavelength λ=550nm Value, RthV(650) represents the retardation value in the thickness direction of the liquid crystal hardened layer for light with wavelength λ=650nm, and the retardation value RthV(λ) for the thickness direction of the liquid crystal hardened layer for light with wavelength λ(nm) Expressed by RthV(λ)=[(nxV(λ)+nyV(λ))/2-nzV(λ)]×dV; here, in the refractive index ellipsoid formed by the liquid crystal hardening layer, nzV(λ) Indicates the main refractive index in the direction perpendicular to the plane of the liquid crystal hardening layer at the wavelength λ (nm), and "(nxV(λ)+nyV(λ))/2" means the main refractive index at the wavelength λ (nm) in the liquid crystal hardening layer The average refractive index of the plane; dV represents the thickness of the liquid crystal hardening layer].

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

The retardation value in the thickness direction of the vertically aligned liquid crystal hardening layer 6 can be adjusted according to the thickness dV of the vertically aligned liquid crystal hardening 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, so it is desired to obtain the desired phase difference in the thickness direction value (RthV(λ): the retardation value in the thickness direction of the vertically aligned liquid crystal cured layer 6 at the wavelength λ(nm)), it is only necessary to adjust the three-dimensional refractive index and the film thickness dV. In addition, the three-dimensional refractive index depends on the molecular structure and alignment state of the polymerizable liquid crystal compound described later.

The upper limit of the film thickness of the vertically aligned liquid crystal hardened layer 6 is preferably 3 μm or less, more preferably 2.5 μm or less, still more preferably 2.0 μm or less, and most preferably 1.5 μm or less from the viewpoint of thinning. Furthermore, the lower limit of the film thickness of the vertically aligned liquid crystal cured layer 6 is preferably at least 0.1 μm, more preferably at least 0.3 μm, and still more preferably at least 0.5 μm. The film thickness of the vertically aligned liquid crystal cured layer can be measured using an ellipsometer or a contact film thickness meter.

(polymerizable liquid crystal composition)

The λ/4 retardation layer 4 and the vertically aligned liquid crystal hardening layer 6 are preferably composed of polymers 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 (especially a photopolymerizable functional group). The photopolymerizable functional group refers to a group that can participate in a polymerization reaction by active radicals, acids, etc. generated from a photopolymerization initiator. Photopolymerizable functional groups include, for example, vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloxy, methacryloxy, oxiranyl, Oxetanyl, etc. Among them, acryloxy, methacryloxy, ethyleneoxy, oxiranyl and oxetanyl are preferred, and acryloxy is more preferred. The liquid crystal can be thermotropic liquid crystal or lyotropic liquid crystal. In terms of phase ordered structure, it can be nematic liquid crystal or smectic liquid crystal.

表示的化合物。 In the present invention, the polymerizable liquid crystal compound is preferably of the following formula from the viewpoint of exhibiting inverse wavelength dispersion, preferably from the viewpoint of satisfying the relationship between the aforementioned formulas (1) and (2) or (4) and (5). (I)

indicated compound.

In formula (I), Ar represents a divalent aromatic group which may have a substituent. Here, the term "aromatic group" refers to a group having a planar ring 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 of containing heteroatoms such as -N=, -S- and forming a ring structure, the non-covalent electron pairs on these heteroatoms all satisfy Huckel's law, and the case of aromaticity is also included. 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 replaced by a halogen atom, an alkyl group having 1 to 4 carbons, a fluoroalkyl group having 1 to 4 carbons, or a fluoroalkyl group having 1 to 4 carbons. The carbon atoms constituting the divalent aromatic group or divalent alicyclic hydrocarbon group can be replaced by oxygen atom, sulfur atom or 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 of 0 to 3, and satisfy the relationship of 1≦k+l. Here, in the case of 2≦k+l, B ¹ and B ² , G ¹ and G ² may be the same as or different from each other.

E ¹ and E ² independently represent an alkanediyl group with 1 to 17 carbon atoms, where the hydrogen atom contained in the alkanediyl group may be replaced by a halogen atom, and the -CH ₂ - contained in the alkanediyl group may be replaced by - O-, -S-, -Si-substitution. ^P1 and ^P2 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 independently preferably 1,4-phenylenediyl groups that may be substituted by at least one substituent selected from the group consisting of halogen atoms and alkyl groups with 1 to 4 carbons, and may be selected from A 1,4-cyclohexanediyl group substituted by at least one substituent consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms, more preferably a 1,4-phenylenediyl group substituted by a methyl group, 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 preferable that at least one of the plurality of G ¹ and G ² is a divalent alicyclic hydrocarbon group, and more preferably at least one of the G ¹ and G ² bonded to L ¹ or L ² is Divalent alicyclic hydrocarbon group.

L ¹ and L ² are each independently preferably a single bond, an alkylene group with 1 to 4 carbons, -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 carbons, and R ^c and R ^d represent an alkyl group having 1 to 4 carbons or a hydrogen atom. L ¹ and L ² are each independently more 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 any of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. L ¹ and L ² are each independently 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 with 1 to 4 carbons, -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 more 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 of a single bond, -CH ₂ -, and -CH ₂ CH ₂ -. B ¹ and B ² are each independently a single bond, -O-, -CH ₂ CH ₂ -, -COO-, -COOCH ₂ CH ₂ -, -OCO- or -OCOCH ₂ CH ₂ -.

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

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

The polymerizable group represented by ^P1 or ^P2 can be, for example, epoxy group, vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloxy group, methacrylic group Acyloxy group, oxirane group and oxetanyl group, etc. Among these, acryloxy, methacryloxy, vinyloxy, oxiranyl and oxetanyl are preferred, and acryloxy is more preferred.

環、嘧啶環、三唑環、三

環、吡咯啉環、咪唑環、吡唑環、噻唑環、苯並噻唑環、噻吩並噻唑環、

唑環、苯並

唑環及啡啉(phenanthroline)環等。該等之中，較佳為具有噻唑環、苯並噻唑環或苯並呋喃環，更佳為具有苯並噻唑環。而且，於Ar包含氮原子的情況，該氮原子較佳具 有π電子。 Ar preferably has at least one selected from an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, and an electron-attracting group. The aromatic hydrocarbon ring may, for example, be a benzene ring, a naphthalene ring, an anthracene ring, etc., preferably a benzene ring or a naphthalene ring. The aromatic heterocycle can be, for example, furan ring, benzofuran ring, pyrrole ring, indole ring, thiophene ring, benzothiophene ring, pyridine ring, pyridine ring,

ring, pyrimidine ring, triazole ring, three

ring, pyrroline ring, imidazole ring, pyrazole ring, thiazole ring, benzothiazole ring, thienothiazole ring,

Azole ring, benzo

Azole ring and phenanthroline (phenanthroline) ring, etc. Among these, it is preferable to have a thiazole ring, a benzothiazole ring, or a benzofuran ring, and it is more preferable to have a benzothiazole ring. Also, in the case where Ar contains a nitrogen atom, the nitrogen atom preferably has π electrons.

In formula (I), the total number N _x of π electrons 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, particularly preferably 16 or more. And, it is preferably 30 or less, more preferably 26 or less, and still more preferably 24 or less.

The aromatic group represented by Ar includes, for example, the following groups.

In the formula (Ar-1) to the formula (Ar-22), the symbol * represents a linking part, and Z ⁰ , Z ¹ and Z ² independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and a cyano group , nitro, alkylsulfinyl with 1 to 12 carbons, alkylsulfonyl with 1 to 12 carbons, carboxyl, fluoroalkyl with 1 to 12 carbons, alkoxy with 1 to 6 carbons , Alkylthio with 1 to 12 carbons, N-alkylamino with 1 to 12 carbons, N,N-dialkylamino with 2 to 12 carbons, N-alkyl with 1 to 12 carbons sulfamoyl group or N,N-dialkylsulfamoyl group with 2 to 12 carbon atoms.

Q ¹ and Q ² independently represent -CR ^2' R ^3' -, -S-, -NH-, -NR ^2' -, -CO- or -O-, R ^2' and R ^3' are 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.

The aromatic hydrocarbon groups in Y ¹ , Y ² and Y ³ can be, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl and other aromatic hydrocarbon groups with 6 to 20 carbons, preferably phenyl and naphthyl , more preferably phenyl. The aromatic heterocyclic group can be, for example, furyl, pyrrolyl, thienyl, pyridyl, thiazolyl, benzothiazolyl, etc., containing at least one heteroatom such as nitrogen atom, oxygen atom, sulfur atom, etc., having 4 to 20 carbon atoms. The aromatic heterocyclic group is preferably furyl, thienyl, pyridyl, thiazolyl, and benzothiazolyl.

Y ¹ and Y ² may each independently be an optionally substituted polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group. The polycyclic aromatic hydrocarbon group refers to a condensed polycyclic aromatic hydrocarbon group or a group derived from a double aromatic ring. The polycyclic aromatic heterocyclic group refers to a condensed polycyclic aromatic heterocyclic group or a group derived from a biaromatic heterocyclic ring.

Z ⁰ , Z ¹ and Z ² are independently preferably a hydrogen atom, a halogen atom, an alkyl group with 1 to 12 carbons, a cyano group, a nitro group, an alkoxy group with 1 to 12 carbons, and Z ⁰ is more preferably A hydrogen atom, an alkyl group with 1 to 12 carbons, and a cyano group, and ^Z1 and ^Z2 are more preferably a hydrogen atom, a fluorine atom, a chlorine atom, a methyl group, or 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-.

The aromatic group represented by Ar ¹ includes, for example, a group represented by the following formula (Ar-23).

In formula (Ar-23), *, Z ¹ , Z ² , Q ¹ and Q ² have the same meanings as above, and U ¹ represents a non-metallic atom of Group 14 to Group 16 to which a substituent may be bonded. The non-metallic atoms of Groups 14 to 16 can be, for example, carbon atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, and more preferred examples include =O, =S, =NR', and =C(R')R', etc. . The substituent R' can be, for example, a hydrogen atom, a halogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an aryl group, a cyano group, an amino group, a nitro group, a nitroso group, a carboxyl group, an alkylene group having 1 to 6 carbon atoms, Sulfonyl, alkylsulfonyl with 1 to 6 carbons, fluoroalkyl with 1 to 6 carbons, alkoxy with 1 to 6 carbons, alkylthio with 1 to 6 carbons, 1 to 6 carbons N-alkylamine groups with 2 to 6 carbons, N,N-dialkylamino groups with 2 to 12 carbons, N-alkylsulfamoyl groups with 1 to 6 carbons, dialkyl groups with 2 to 12 carbons When the nonmetal atom is a carbon atom (C) such as a sulfamoyl group, two R's may be the same or different from each other.

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

環、嘧啶環、吲哚環、喹啉環、異喹啉環、嘌呤環、吡咯啶環等。該芳香族雜環基可具有取代基。而且，Y¹可與其所鍵結的氮原子及Z⁰一起為前述可被取代的多環系芳香族烴基或多環系芳香族雜環基。可舉例如苯並呋喃環、苯並噻唑環、苯並

唑環等。再者，前述式(I)所表示的化合物可例如根據日本特開2010-31223號公報記載的方法製造。 In formulas (Ar-16) to (Ar-22), Y ¹ may form an aromatic heterocyclic group together with the nitrogen atom to which it is bonded and Z ⁰ . The aromatic heterocyclic group can be, for example, those mentioned above as the aromatic heterocyclic group that Ar can have, such as pyrrole ring, imidazole ring, pyrroline ring, pyridine ring, pyrroline ring,

ring, pyrimidine ring, indole ring, quinoline ring, isoquinoline ring, purine ring, pyrrolidine ring, etc. This aromatic heterocyclic group may have a substituent. Furthermore, Y ¹ may be the aforementioned polycyclic aromatic hydrocarbon group or polycyclic aromatic heterocyclic group which may be substituted, together with the nitrogen atom to which it is bonded and Z ⁰ . For example, benzofuran ring, benzothiazole ring, benzo

Azole ring etc. In addition, the compound represented by said formula (I) can be manufactured according to the method described in Unexamined-Japanese-Patent No. 2010-31223, for example.

A polymeric liquid crystal compound can be used individually or in combination of 2 or more types. When two or more are used in combination, the content of the compound represented by the aforementioned formula (I) is preferably at least 50 parts by mass, more preferably at least 70 parts by mass, and still more preferably 80 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. parts by mass or more.

The polymerizable liquid crystal composition may further include additives such as a solvent, a photopolymerization initiator, a polymerization inhibitor, a photosensitizer, a leveling agent, an adhesion improving agent, and a dichroic pigment. These additives can be used individually or in combination of 2 or more types.

The content of the polymerizable liquid crystal compound is, for example, 70 to 99.5 parts by mass, preferably 80 to 99 parts by mass, more preferably 90 to 98 parts by mass relative to 100 parts by mass of solid content of the polymerizable liquid crystal composition. When the content is within the above range, the orientation of the layer tends to be high. Here, the term "solid content" refers to 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 from 50 to 98 parts by mass, more preferably from 70 to 95 parts by mass, relative to 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, since the viscosity of the composition becomes low, the thickness of the layer becomes approximately uniform, and unevenness tends to be less likely to occur in the layer. The above-mentioned solid content can be appropriately determined in consideration of the thickness of the layer to be produced.

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

By formulating a polymerization inhibitor, the polymerization reaction of the polymerizable liquid crystal compound can be controlled. Examples of polymerization inhibitors include: hydroquinone and hydroquinones having substituents such as alkyl ethers; catechols having substituents such as alkyl ethers such as butylcatechol; pyrogallols; , 2,6,6-tetramethyl-1-piperidinyloxy radical 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 to 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 0.1 to 3 parts by mass. A polymerization inhibitor can be used individually or in combination of 2 or more types.

；紅螢烯。光敏劑可單獨使用或組合2種以上使用。相對於聚合性液晶化合物100質量份，光敏劑的含量通常為0.01至10質量份，較佳為0.05至5質量份，更佳為0.1至3質量份。 Furthermore, by using a photosensitizer, the sensitivity of a photoinitiator can be made high. Photosensitizers include, for example: xanthones such as xanthone and thioxanthone; anthracenes and anthracenes with substituents such as alkyl ethers;

; rubrene. A photosensitizer can be used individually or in combination of 2 or more types. The content of the photosensitizer is usually 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound.

The so-called leveling agent is an additive that has the function of adjusting the fluidity of the curable composition and making the layer obtained by coating the composition more flat, such as polysiloxane, polyacrylate, and perfluoroalkane, such as silane coupling agents. Base leveling agent. Specifically, for example: DC3PA, SH7PA, DC11PA, SH28PA, SH29PA, SH30PA, ST80PA, ST86PA, SH8400, SH8700, FZ2123 (all of the above are manufactured by Toray.Dow Corning Co., Ltd.); 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 of the above are made by Shin-Etsu Chemical Co., Ltd.); All are manufactured by Momentive Performance Materials Japan LLC); Fluorinert (registered trademark) FC-72, Fluorinert FC-40, Fluorinert FC-43, Fluorinert FC-3283 (all above are manufactured by Sumitomo 3M Co., Ltd.); 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 (all of the above are manufactured by DIC Corporation); EFTOP (trade name) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (all of the above are manufactured by Mitsubishi Materials Corporation) ); 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 are AGC Seimi Chemical (stock) company); trade name E1830, trade name W5844 (DAIKIN Fine Chemicals Research Institute (stock) system); BM-1000, BM-1100, BYK-352, BYK-353 and BYK-361N (all trade names : manufactured by BM Chemie), etc. A leveling agent can be used individually or in combination of 2 or more types.

色素、花青色素、萘色素、偶氮色素及蒽醌色素等，其中較佳為偶氮色素。偶氮色素可舉例如單偶氮色素、雙偶氮色素、三偶氮色素、四偶氮色素及二苯乙烯偶氮色素等，較佳為雙偶氮色素及三偶氮色素。二色性色素可單獨或組合，為了在可見光全部區域得到吸收，較佳為組合3種以上的二色性色素，更佳為組合3種以上的偶氮色素。 The content of the leveling agent is preferably from 0.01 to 5 parts by mass, more preferably from 0.05 to 3 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. When the content of the leveling agent is within the above range, the obtained layer tends to be smoother, which is preferable. The so-called dichroic pigment refers to a pigment that has different absorbance in the direction of the long axis and the absorbance in the direction of the short axis of the molecule. The dichroic pigment preferably has the characteristic of absorbing visible light, and is more preferably at 380 to 680nm. The range has a maximum absorption wavelength (λMAX). Such dichroic dyes can be, for example, acridine dyes,

pigments, cyanine pigments, naphthalene pigments, azo pigments and anthraquinone pigments, among which azo pigments are preferred. Examples of azo dyes include monoazo dyes, disazo dyes, trisazo dyes, tetrazo dyes, and stilbene azo dyes, preferably disazo dyes and trisazo dyes. The dichroic dyes may be used alone or in combination, but in order to absorb in the entire range of visible light, it is preferable to combine three or more dichroic dyes, and it is more preferable to combine three or more azo dyes.

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

The optional substituents of 1,4-phenylene, naphthalene-1,4-diyl, and divalent heterocyclic groups in A ¹ , A ^2, and A ³ include, for example, methyl, ethyl, and butyl Alkyl groups with 1 to 4 carbons; alkoxy groups with 1 to 4 carbons such as methoxy, ethoxy and butoxy; fluoroalkyl groups with 1 to 4 carbons such as trifluoromethyl; cyano; Nitro; halogen atoms such as chlorine atom and fluorine atom; substituted or unsubstituted amine groups such as amine group, diethylamino group and pyrrolidinyl group (the so-called substituted amine group refers to those having 1 or 2 carbon numbers from 1 to 6 An alkyl amino group, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms. The unsubstituted amino group is -NH ₂ ). Furthermore, examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, and hexyl. The alkanediyl group with 2 to 8 carbons can be exemplified by ethylidene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1, 5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc. 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 or phenylene with no substitution or hydrogen substituted by methyl or methoxy As a divalent heterocyclic group, 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 groups, which is more preferable in terms of both the simplicity of molecular synthesis and high performance .

唑及苯並

唑中除去2個氫原子而得的基。於A²為2價雜環基的情況，較佳係分子鍵結角度實質上成為180°的結構，具體而言，更佳係2個5員環稠合而成的苯並噻唑、苯並咪唑、苯並

唑結構。 The 2-valent heterocyclic group can be exemplified from quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole,

Azole and benzo

A group obtained by removing two hydrogen atoms from an azole. When ^A2 is a divalent heterocyclic group, it is preferably a structure in which the molecular bonding angle becomes substantially 180°, and specifically, benzothiazole, benzo imidazole, benzo

azole structure.

^T1 and ^T2 are electron-absorbing groups or electron-releasing groups, preferably different structures, more preferably ^T1 is electron-absorbing groups and ^T2 is electron-releasing groups or ^T1 is electron-releasing groups and ^T2 For the relationship of attracting electron groups. Specifically, ^T1 and ^T2 are independently preferably an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, a cyano group, a nitro group, and one or two groups with 1 to 4 carbons. An amino group of an alkyl group of 6 or an amino group of an alkanediyl group having a carbon number of 2 to 8 formed by bonding two substituted alkyl groups to each other, or a trifluoromethyl group, wherein in order to be included in a height such as a smectic liquid crystal In an ordered liquid crystal structure, it must be a structure with a smaller excluded volume of the molecule, so it is preferably an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, a cyano group, and one or two An amine group of an alkyl group having 1 to 6 carbons or an amine group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbons.

Examples of such azo dyes include the following.

In formulas (2-1) to (2-6), B ¹ to B ²⁰ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, a cyano group, a nitro group , substituted or unsubstituted amino group (the definition of substituted amino group and unsubstituted amino group is the same as above), chlorine atom or trifluoromethyl group. Furthermore, from the viewpoint of obtaining high polarizing performance, B ² , B ⁶ , B ⁹ , B ¹⁴ , B ¹⁸ , and B ¹⁹ are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

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

When n1 is 2 or more, the plurality of ^B2s may be the same or different; when n2 is 2 or more, the plurality of ^B6s may be the same or different; when n3 is 2 or more In this case, the plurality of B ⁹ may be the same or different; when n4 is 2 or more, the plurality of B ¹⁴ may be the same or different.

The aforementioned anthraquinone dye is preferably a compound represented by 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.

色素較佳為式(2-8)所表示的化合物。 R ^x represents an alkyl group with 1 to 4 carbons or an aryl group with 6 to 12 carbons] as mentioned above

The pigment is preferably a compound represented by 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 with 1 to 4 carbons or an aryl group with 6 to 12 carbons]

The aforementioned acridine dye is preferably a compound represented by 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 with 1 to 4 carbons or an aryl group with 6 to 12 carbons]

The alkyl groups with 1 to 4 carbons represented by R ^x in formula (2-7), formula (2-8) and formula (2-9) can be for example methyl, ethyl, propyl, butyl, Pentyl, hexyl, etc., and the aryl group having 6 to 12 carbons include, for example, phenyl, tolyl, xylyl, and the like.

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

[In formula (2-10), D ¹ and D ² each independently represent a group represented by any one of formula (2-10a) to formula (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 formula (2-11a) to formula (2-11h).

n6 represents an integer from 1 to 3]

From the viewpoint of obtaining good light-absorbing properties, the content of the dichroic dye (or the total amount when a plurality of them are included) is usually 0.1 to 30 parts by mass, preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound. 1 to 20 parts by mass, more preferably 3 to 15 parts by mass. When the content of the dichroic dye is less than this range, light absorption becomes insufficient and sufficient polarizing performance cannot be obtained, and when it is more than this range, alignment of liquid crystal molecules may be hindered.

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

The λ/4 retardation layer 4 and the vertical alignment liquid crystal hardening layer 6 are preferably formed on the alignment layer that imparts alignment control force. More specifically, for the λ/4 retardation layer 4, the above-mentioned polymerizable liquid crystal composition can be coated on the alignment layer 5, and then the solvent is removed, and the polymerizable liquid crystal composition including the polymerizable liquid crystal compound in the alignment state is passed through Hardened by heating and/or active energy rays. For the vertical alignment liquid crystal hardening layer 6, the above-mentioned polymerizable liquid crystal composition can be coated on the vertical alignment layer 7, and then the solvent is removed, and the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound in the alignment state is heated and/or activated It is obtained by hardening the energy line.

The method of coating the polymerizable liquid crystal composition on the alignment layer 5 or the vertical alignment layer 7 can be, for example, the coating method A exemplified in the item of the reinforcing layer. The method for removing the solvent may, for example, be the solvent removal method A exemplified in the item of the reinforcing layer. The active energy ray to be irradiated is appropriately selected depending on the kind of the polymerizable liquid crystal compound, the kind of the photopolymerization initiator when the photopolymerization initiator is contained, and the amount thereof. The active energy line and its light source can use those exemplified in the item of the reinforcing layer. Furthermore, when irradiating ultraviolet rays to the polymerizable liquid crystal composition, the ultraviolet irradiation intensity, irradiation time, and cumulative light intensity can also be used within the ranges exemplified in the item of the reinforcing layer. When the accumulated light amount is below the range described above, the curing of the polymerizable liquid crystal compound becomes insufficient, and the reinforcing property may be insufficient. Conversely, when the accumulated light quantity is more than the range described above, the elliptically polarizing plate may be colored.

[Alignment layer]

The alignment layer 5 has an alignment control force for aligning the polymerizable liquid crystal compound in a predetermined direction. For example, if the alignment layer 5 can exhibit horizontal alignment control force as a material for alignment control force, the polymerizable liquid crystal compound can form horizontal alignment or mixed alignment; if it can exhibit vertical alignment control force, the polymerizable liquid crystal compound can be Form vertical alignment or oblique alignment. Moreover, since the polymerizable liquid crystal compound contained in the vertically aligned liquid crystal hardening layer 6 forms vertical alignment, the vertical alignment layer 7 is made of a material that exhibits vertical alignment control force. The alignment control force can be arbitrarily adjusted by the type of alignment layer, surface state, rubbing conditions, etc., and in the case of a photo-alignment polymer, it can be arbitrarily adjusted by polarized light irradiation conditions, etc. Moreover, liquid crystal alignment can be controlled by selecting physical properties such as surface tension and liquid crystallinity of the polymerizable liquid crystal compound.

Alignment layer 5 or alignment layer 7 preferably has solvent resistance that does not dissolve due to coating of the polymerizable liquid crystal composition, etc., and has heat resistance for solvent removal and heat treatment for alignment of the polymerizable liquid crystal compound. .

The horizontal alignment layer exhibiting the alignment control force for aligning the λ/4 retardation layer 4 in the horizontal direction may be, for example, a rubbed alignment layer, a photo alignment layer, and a groove alignment layer with a concave-convex pattern or a plurality of grooves on the surface. For example, when applied to a long roll film, a photo-alignment layer is preferable because the alignment direction can be easily controlled.

The rubbing alignment layer can usually be formed by coating a composition comprising an alignment polymer and a solvent (hereinafter also referred to as a composition for forming a rubbing alignment layer) on a substrate, removing the solvent to form a coating film, and rubbing the coating film, And give the alignment control power.

唑、聚伸乙基亞胺、聚苯乙烯、聚乙烯吡咯啶酮、聚丙烯酸及聚丙烯酸酯類。該等配向性聚合物可單獨使用或組合2種以上使用。 Alignment polymers include, for example, polyamides with amide bonds, gelatin, polyimides with amide bonds and polyamic acids of their hydrolyzates, polyvinyl alcohol, and 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 rubbed alignment layer may be within a range in which the alignment polymer is completely dissolved in the solvent. With respect to 100 parts by mass of the composition, the content of the alignment polymer is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass.

The composition for forming a frictional alignment layer is commercially available. Commercially available products include, for example, SUNEVER (registered trademark, manufactured by Nissan Chemical Industry Co., Ltd.), OPTOMER (registered trademark, manufactured by JSR Co., Ltd.), and the like.

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

As a method of rubbing treatment, for example, a method of bringing the coating film into contact with a rubbing roll wound with a rubbing cloth and rotating is mentioned. When performing the rubbing treatment, if masking is performed, a plurality of regions (patterns) having different alignment directions can be formed on the alignment film.

The photo-alignment layer is usually coated on a substrate with a composition (also called a photo-alignment layer-forming composition) containing a polymer or monomer with a photoreactive group and a solvent, and after removing the solvent, irradiates polarized light (compared to Best for polarized UV) derived. The photo-alignment layer can arbitrarily control the direction of the alignment control force by selecting the polarization direction of the irradiated polarized light.

The so-called photoreactive group refers to a group that generates alignment ability by light irradiation. Specifically, there may be mentioned photoreactive groups involved in the origin of alignment ability, such as molecular alignment-induced reaction by light irradiation, isomerization reaction, photodimerization reaction, photocrosslinking reaction, or photodecomposition reaction. The photoreactive group is preferably a group having an unsaturated bond (especially a double bond), and is particularly preferably a group selected from a carbon-carbon double bond (C=C bond), a carbon-nitrogen double bond (C=N bond), At least one group of a nitrogen-nitrogen double bond (N=N bond) and a carbon-oxygen double bond (C=O bond).

基(formazan)及具有氧偶氮苯結構的基。具有C=O鍵的光反應性基可舉例如二苯甲酮基、香豆素基、蒽醌基及馬來醯亞胺基。該等基可具有烷基、烷氧基、芳香基、烯丙氧基、氰基、烷氧基羰基、羥基、磺酸基、鹵烷基等取代基。 The photoreactive group having a C═C bond can be, for example, vinyl group, polyalkenyl group, distyryl group, stilbazole group, stilbazole group, chalcone group and cinnamyl group. As a photoreactive group which has a C=N bond, the group which has structures, such as an aromatic Schiff base and an aromatic hydrazone, is mentioned, for example. The photoreactive group with N=N bond can be for example azophenyl group, azonaphthyl group, aromatic heterocyclic azo group, disazo group, methyl

group (formazan) and a group with an oxyazobenzene structure. The photoreactive group having a C=O bond includes, for example, a benzophenone group, a coumarin group, an anthraquinone group, and a maleimide group. These groups may have a substituent such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, or a haloalkyl group.

A group that participates in a photodimerization reaction or a photocrosslinking reaction is preferable in terms of good alignment. Among them, the photoreactive group that participates in the photodimerization reaction is preferable, and in terms of the amount of polarized light irradiation required for alignment is small, and it is easy to obtain a photoalignment layer with good thermal stability and stability over time, preferably Cinnamyl and Chalcone. The polymer having a photoreactive group is particularly preferably one having a cinnamoyl group that becomes a cinnamic acid structure or a cinnamate structure at the end of the polymer side chain.

The content of polymers or monomers with photoreactive groups can be adjusted according to the type of polymers or monomers and the thickness of the intended photo-alignment layer, preferably at least It is 0.2 mass parts or more, More preferably, it is the range of 0.3-10 mass parts.

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

Irradiation with polarized light may be, for example, a form in which polarized light is directly irradiated to a composition obtained by removing the solvent from the composition for forming a photoalignment layer coated on the base material. Furthermore, the polarized light is preferably substantially parallel light. The wavelength of the polarized light to be irradiated may be in a wavelength region where the photoreactive group of the polymer or monomer having a photoreactive group can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength of 250 to 400 nm is particularly preferred. The light source for irradiating the polarized light includes, for example, a xenon lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, an ultraviolet laser such as KrF or ArF, and the like. Among them, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide lamp are preferable because they have a large luminous intensity of ultraviolet rays with a wavelength of 313 nm. By passing light from the aforementioned light source through a suitable polarizing element and irradiating it, polarized UV light can be irradiated. Examples of the polarizing element include polarizing filters, Glan-Thompson, Glan-Taylor polarizers, and wire grids. Among them, a wire grid type polarizing element is preferable from the viewpoint of increasing the area and resistance to heat.

Furthermore, when rubbing or polarized light irradiation is performed, if masking is performed, a plurality of regions (patterns) with different liquid crystal alignment directions can be formed.

Groove (groove) Alignment layer is a film with a concave-convex pattern or a plurality of grooves on the surface of the film. When a polymerizable liquid crystal compound is coated on 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 of obtaining the groove alignment layer can be, for example, a method of forming a concave-convex pattern on the surface of the photosensitive polyimide film through an exposure mask having a pattern-shaped slit, and after exposure, developing and washing are performed. ; A plate-shaped master having grooves on the surface, forming a layer of UV curable resin before hardening, moving the formed resin layer to a base material and then hardening; and UV curable resin formed on the base material before hardening A method of crimping a roller-shaped master plate having a plurality of grooves, forming concavities and convexities, and then hardening.

The vertical alignment layer exhibiting the alignment control force to align the vertically aligned liquid crystal hard layer 6 in the vertical direction is preferably a material that lowers the surface tension of the alignment layer surface. Such materials include, for example, the above-mentioned alignment polymers, such as polyimide, polyamide, its hydrolyzed polyamic acid, perfluoroalkyl and other fluorine-based polymers and silane compounds, and their Polysiloxane compound obtained by condensation reaction. The vertical alignment layer can be formed by applying a composition (hereinafter also referred to as a composition for vertical alignment layer formation) containing such a material and a solvent such as the solvent exemplified in the item of the reinforcing layer to the substrate, removing the solvent, and then applying the composition to the substrate. The coating film is obtained by heating or the like.

In the case of using a silane compound in the vertical alignment layer, it is preferable that at least the vertical alignment layer 7 is a compound containing Si element and C element among the constituent elements from the viewpoint of easily lowering the surface tension and improving the adhesion with the adjacent layer. For the layer formed, a silane compound can be suitably used. When at least the vertical alignment layer 7 is composed of a compound containing Si and C among its constituent elements, the adhesion to the adjacent layer can be improved, and the processing characteristics of the formed elliptically polarizing plate can be improved.

Silane compounds can be suitably applied to polysiloxanes such as the above-mentioned silane coupling agents, for example: vinyltrimethoxysilane, vinyltriethoxysilane, vinylparaffin (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, etc.

The silane compound can be polysiloxane monomer type or polysiloxane oligomer (polymer) type. When polysiloxane oligomers are expressed in the form of (monomer)-(monomer) copolymers, for example: 3-mercaptopropyltrimethoxysilane-tetramethoxysilane copolymer, 3-mercaptopropyl Trimethoxysilane-tetraethoxysilane copolymer, 3-mercaptopropyltriethoxysilane-tetramethoxysilane copolymer and 3-mercaptopropyltriethoxysilane-tetraethoxysilane copolymer Copolymers containing mercaptopropyl groups; mercaptomethyltrimethoxysilane-tetramethoxysilane copolymer, mercaptomethyltrimethoxysilane-tetraethoxysilane copolymer, mercaptomethyltriethoxysilane -Copolymers containing mercaptomethyl groups such as tetramethoxysilane copolymer and mercaptomethyltriethoxysilane-tetraethoxysilane copolymer; 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane Methoxysilane copolymer, 3-methacryloxypropyltrimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropyltriethoxysilane-tetramethoxy Silane copolymer, 3-methacryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetramethoxy Silane copolymer, 3-methacryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-methacryloxypropylmethyldiethoxysilane-tetramethoxysilane Oxysilane copolymers and 3-methacryloxypropyl methyldiethoxysilane-tetraethoxysilane copolymers containing methacryloxypropyl; 3-acryloxy 3-Acryloxypropyltrimethoxysilane-Tetramethoxysilane Copolymer, 3-Acryloxypropyltrimethoxysilane-Tetraethoxysilane Copolymer, 3-Acryloxypropyltriethoxysilane -Tetramethoxysilane copolymer, 3-acryloxypropyltriethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldimethoxysilane-tetramethoxysilane 3-acryloxypropylmethyldimethoxysilane-tetraethoxysilane copolymer, 3-acryloxypropylmethyldiethoxysilane-tetramethoxysilane Copolymers and 3-acryloxypropylmethyldiethoxysilane-tetraethoxysilane copolymers containing acryloxypropyl groups; vinyltrimethoxysilane-tetramethoxysilane Copolymer, vinyltrimethoxysilane-tetraethoxysilane copolymer, vinyltriethoxysilane-tetramethoxysilane copolymer, vinyltriethoxysilane-tetraethoxysilane copolymer, Vinylmethyldimethoxysilane-tetramethoxysilane copolymer, vinylmethyldimethoxysilane-tetraethoxysilane copolymer, vinylmethyldiethoxysilane-tetramethoxy Silane copolymers and vinylmethyldiethoxysilane-tetraethoxysilane copolymers and other vinyl-containing copolymers; 3-aminopropyltrimethoxysilane-tetramethoxysilane copolymers, 3- Aminopropyltrimethoxysilane-tetraethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetramethoxysilane copolymer, 3-aminopropyltriethoxysilane-tetraethoxysilane Ethoxysilane Copolymer, 3-Aminopropylmethyldimethoxysilane-Tetramethoxysilane Copolymer, 3-Aminopropylmethyldimethoxysilane-Tetraethoxysilane Copolymer , 3-aminopropylmethyldiethoxysilane-tetramethoxysilane copolymer and 3-aminopropylmethyldiethoxysilane-tetraethoxysilane copolymer containing amino group things etc. A silane compound can be used individually or in combination of 2 or more types. In addition, it may be used as a leveling agent, and a silane coupling agent or the like may also be used.

Among them, a silane compound having an alkyl group at a molecular end is preferable, and a silane compound having an alkyl group having 3 to 30 carbon atoms is more preferable.

In a preferred embodiment of the present invention, there is a vertical alignment layer 7 with a film thickness of less than 5 μm between the vertical alignment liquid crystal hardening layer 6 and the reinforcing layer 8, and the vertical alignment layer 7 is composed of Si element and C element among the constituent elements. And a layer composed of a compound of O element. From the viewpoint of improving the adhesiveness with adjacent layers and the coatability of the composition for forming the vertically aligned liquid crystal curable layer 6, the vertical alignment layer 7 is preferably composed of Si element, C element, and Composed of compounds of O elements, silane compounds can be used suitably. The substituent of the silane compound forming the vertical alignment layer 7, which includes a C atom bonded to the Si atom, is preferably an alkyl group or an alkoxy group. The number of carbon atoms is preferably 1 to 30, more preferably 2 to 25, and more preferably Preferably it is 3 to 20. That is, the ratio of Si element to C element (Si/C, molar ratio) is preferably from 0.03 to 1.00, more preferably from 0.04 to 0.50, and still more preferably from 0.05 to 0.33. When the Si/C ratio is not less than the above lower limit, the coatability of the composition for forming a vertically aligned liquid crystal curable layer 6 improves, and when the Si/C ratio is not more than the upper limit, the adhesiveness with 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 coating the composition for forming a vertical alignment layer on the substrate may be, for example, the aforementioned coating method A, and the method of removing the solvent may be, for example, the aforementioned solvent removal method A.

The composition for forming an alignment layer, that is, the composition for forming a horizontal alignment layer such as the composition for forming a rubbed alignment layer, the composition for forming a photoalignment layer, and the composition for forming a vertical alignment layer may contain, in addition to a solvent, 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 preferably 1 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less. Furthermore, the film thicknesses of the alignment layer 5 and the vertical alignment layer 7 are preferably at least 1 nm, more preferably at least 5 nm, even more preferably at least 10 nm, and most preferably at least 30 nm. 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]

The adhesive 3 can be, for example, a pressure-sensitive adhesive, a dry-curable adhesive, and a chemical reaction adhesive. The chemical reaction adhesive can be, for example, an active energy ray hardening adhesive.

Pressure-sensitive adhesives usually contain polymers, and may also contain solvents. The polymer can be, for example, acrylic polymer, polysiloxane polymer, polyester, polyurethane or polyether. Among them, acrylic adhesives containing acrylic polymers have good optical transparency, appropriate wettability, aggregation, good adhesion, and high weather resistance and heat resistance. Since floating, peeling, etc. are hard to generate|occur|produce, it is preferable.

The acrylic polymer is preferably (meth)acrylic acid ester, (meth)acrylic acid, (meth)acrylic acid hydroxyl group in which the alkyl group of the ester part is an alkyl group with 1 to 20 carbons such as methyl, ethyl or butyl. Copolymers of (meth)acrylic monomers having functional groups such as ethyl esters.

A pressure-sensitive adhesive containing such a copolymer is preferable because it has good adhesiveness and does not produce adhesive residue on the transfer object even if it is removed after being attached to the transfer object, and can be removed relatively easily. . The glass transition temperature of the acrylic polymer is preferably at most 25°C, more preferably at most 0°C. The mass average molecular weight of such an acrylic polymer is preferably 100,000 or more.

As a solvent, the solvent etc. which were mentioned as said solvent etc. are mentioned, for example. The pressure-sensitive adhesive may contain a light diffusing agent. The light-diffusing agent is an additive that imparts light-diffusing properties to the adhesive, and may be fine particles having a refractive index different from that of a polymer contained in the adhesive. As a light-diffusion agent, the fine particle which consists of an inorganic compound, and the fine particle which consists of an organic compound (polymer) are mentioned, for example. Many polymers contained in the adhesive as an active ingredient including acrylic polymers have a refractive index of about 1.4 to 1.6, so it is preferable to appropriately select from light diffusing agents with a refractive index of 1.2 to 1.8. The difference in refractive index between the polymer contained in the adhesive as an active ingredient and the light-diffusing agent is usually 0.01 or more, and is preferably from 0.01 to 0.2 from the viewpoint of brightness and display properties of the display device. The microparticles used as the light diffusing agent are preferably spherical microparticles and close to monodisperse microparticles, more preferably microparticles with an average particle diameter of 2 to 6 μm. The refractive index is measured by a general minimum declination method or an Abbe refractometer.

Microparticles composed of inorganic compounds include, for example, aluminum oxide (refractive index: 1.76) and silicon oxide (refractive index: 1.45). Microparticles composed of organic compounds (polymers) include, for example, melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), 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 polysiloxane beads (refractive index 1.46), etc. Content of a light-diffusion agent is 3-30 mass parts normally with respect to 100 mass parts of polymers.

The thickness of the pressure-sensitive adhesive is determined by its adhesive force, etc., so there is no special limitation, and it is usually 1 μm to 40 μm. From the viewpoint of processability, durability, etc., the thickness is preferably from 3 μm to 25 μm, more preferably from 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 display device can be maintained when viewing the display device from the front and when the display device is viewed from an oblique direction, and bleeding of the displayed image is less likely to occur , Vague.

The dry-curable adhesive may contain a solvent. Examples of dry-curing adhesives include polymers or urethane resins containing monomers having protonic functional groups such as hydroxyl groups, carboxyl groups, or amine groups, and ethylenically unsaturated groups as main components, and further containing polyaldehydes, epoxy resins, etc. Compounds, epoxy resins, melamine compounds, zirconia compounds, zinc compounds and other cross-linking agents or compositions of hardening compounds, etc. Polymers of monomers having protic functional groups such as hydroxyl, carboxyl, or amine groups and ethylenically unsaturated groups include, for example, ethylene-maleic acid copolymers, itaconic acid copolymers, acrylic acid copolymers, acrylamide Copolymers, saponified products of polyvinyl acetate, polyvinyl alcohol-based resins, etc.

Polyvinyl alcohol-based resins include, for example, polyvinyl alcohol, partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, methylol-modified polyvinyl alcohol, Vinyl alcohol and amino-modified polyvinyl alcohol, etc. The content of the polyvinyl alcohol-based resin in the water-based adhesive is usually 1 to 10 parts by mass, preferably 1 to 5 parts by mass, relative to 100 parts by mass of water.

The urethane resin may, for example, be a polyester-based ionomer type urethane resin or the like. Here, the polyester-based ionomer-type urethane resin refers to an urethane resin having a polyester skeleton, and a resin into which a small amount of an ionic component (hydrophilic component) is introduced. Such an ionomer type urethane resin does not use an emulsifier, and is emulsified into latex in water, so it can be used as a water-based adhesive. When using a polyester-based ionomer-type urethane resin, it is effective to mix a water-soluble epoxy compound as a crosslinking agent.

Examples of epoxy resins include polyamide polyamines obtained by reacting polyalkylene polyamines such as diethylenetriamine or triethylenetetramine with dicarboxylic acids such as adipic acid, and epoxy resins. Polyamide epoxy resin obtained by reaction of chloropropane, etc. Commercially available products of such polyamide epoxy resins include, for example, "Sumirez resin (registered trademark) 650" and "Sumirez resin 675" (manufactured by Sumika Chemtex Co., Ltd.), "WS-525" (manufactured by Japan PMC Co., Ltd. )wait. When compounding an epoxy resin, the addition amount of an epoxy resin is 1-100 mass parts normally with respect to 100 mass parts of polyvinyl alcohol-type resins, Preferably it is 1-50 mass parts.

The thickness of the adhesive layer formed by the dry-curable adhesive is usually 0.001 to 5 μm, preferably 0.01 to 2 μm, more preferably 0.01 to 0.5 μm. When the thickness of the adhesive layer formed by the dry-curable adhesive is too thick, it is easy to cause poor appearance.

The active energy ray-curable adhesive may contain a solvent. The active energy ray-curable adhesive refers to an adhesive that is cured by irradiation with active energy rays. Examples of active energy ray-curable adhesives include cationically polymerizable adhesives containing epoxy compounds and cationic polymerization initiators, radically polymerizable adhesives containing acrylic curing components and radical polymerization initiators, epoxy compound-containing An adhesive that contains both a cationically polymerizable hardening component and a radically polymerizable hardening component such as an acrylic compound, and further contains a cationic polymerization initiator and a radical polymerization initiator, and an adhesive that does not contain these polymerization initiators and is irradiated with an electron beam And hardened adhesive, etc.

Among them, a radically polymerizable active energy ray-curable adhesive containing an acrylic curing component and a photoradical polymerization initiator, and a cationically polymerizable active energy ray-curable adhesive containing an epoxy compound and a photocationic polymerization initiator are preferable. 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 active energy ray-curable adhesive containing an epoxy compound may further contain compounds other than the epoxy compound. Compounds other than epoxy compounds include, for example, oxetane compounds, acrylic compounds, and the like.

As a photoradical polymerization initiator and a photocationic polymerization initiator, the photoradical polymerization initiator and photocationic polymerization initiator mentioned above are mentioned, for example. The content of the radical polymerization initiator and the cationic polymerization initiator is usually 0.5 to 20 parts by mass, preferably 1 to 15 parts by mass relative to 100 parts by mass of the active energy ray-curable adhesive.

The active energy ray hardening adhesive may further contain ion scavengers, antioxidants, chain transfer agents, tackifiers, thermoplastic resins, fillers, flow regulators, plasticizers, and defoamers.

In this specification, the so-called active energy ray is defined as an energy ray that can decompose a compound that generates active species to generate active species. Examples of such active energy rays include visible light, ultraviolet rays, infrared rays, X-rays, alpha rays, beta rays, gamma rays, electron beams, etc., preferably ultraviolet rays and electron beams. Preferable conditions for irradiation of ultraviolet rays are the same as those for the above-mentioned polymerization of the polymerizable liquid crystal compound.

[Elliptical polarizer]

The ellipsoidal polarizers 1, 10 and 100 of the present invention have a distance between the vertically aligned liquid crystal hardened layer 6 and the reinforcing layer 8 of 5 μm or less, so the vertically aligned liquid crystal hardened layer 6 of the film can be fully reinforced to suppress or prevent the gap between the cut end faces. 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 still more preferably 30 to 100 μm. When the film thickness of the elliptically polarizing plate is not less than the aforementioned lower limit, it is advantageous from the viewpoint of processing characteristics, and when the film thickness of the elliptically polarizing plate is not more than the aforementioned upper limit, it is advantageous from the viewpoint of thinning.

In the elliptically polarizing plates 1, 10, and 100 of the present invention, the difference in the in-plane average refractive index at a wavelength of 550 nm in adjacent layers is preferably 0.20 or less. When the difference in in-plane average refractive index is not more than the above-mentioned upper limit, the reflection at the interface between the layers becomes small. In addition, the in-plane average refractive index can be measured according to the method described in an Example.

[Manufacturing method of elliptically polarizing plate]

The elliptically 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 vertical alignment liquid crystal hardening layer 6, a vertical alignment layer 7, and a reinforcing layer. 8 laminated body B, through the adhesive 3 bonded. For example, a laminate A with an alignment layer 5 and a λ/4 retardation layer 4 sequentially laminated on the substrate, and a reinforcing layer 8, a vertical alignment layer 7, and a vertical alignment liquid crystal hardening layer are formed on the substrate in sequence 6 laminate B, the polarizing layer 2 and the λ/4 retardation layer 4 side of the laminate A are separated by an adhesive 3 so that the absorption axis of the polarizing layer 2 is aligned with the slow axis of the λ/4 retardation layer 4 They were bonded so that the formed angle was 45°, and only the base material was peeled off to produce a laminate C. Then, the alignment layer 5 side of the laminate C and the vertically aligned liquid crystal cured layer 6 side of the laminate B are bonded through the adhesive 3, and only the base material is peeled off, whereby the elliptically polarizing plate 1 can be produced.

The elliptically polarizing plate 10 shown in FIG. 2 can be made by separately manufacturing the polarizing layer 2, the above-mentioned laminate A and the above-mentioned laminate B, and the polarizing layer 2 and the vertically aligned liquid crystal hardened layer 6 side of the laminate B are separated by an adhesive. 3 Bonding, only the base material is peeled off, and the laminate D is produced. Then, the reinforcing layer 8 side of the laminate D and the λ/4 retardation layer 4 side of the laminate A can be interposed with the adhesive 3 so that the absorption axis of the polarizing layer 2 is relative to the λ/4 retardation layer 4 The slow axis (optical axis) is bonded so that it becomes substantially 45°, and only the base material is peeled off.

The elliptically polarizing plate 100 shown in FIG. 3 can separate the λ/4 retardation layer 4 side of the laminate A from the vertically aligned liquid crystal of the laminate B by fabricating the polarizing layer 2, the laminate A, and the laminate B respectively. The hardened layer 6 side is bonded via the adhesive 3 , and the base materials of both are peeled off to produce a laminate E. Then, the reinforcing layer 8 side of the laminate E and the polarizing layer 2 are interposed with the adhesive 3 so that the absorption axis of the polarizing layer 2 is substantially equal to the slow axis (optical axis) of the λ/4 retardation layer 4 . It can be made by bonding in a 45° way.

(Substrate)

Examples of the substrate include glass substrates and film substrates, and film substrates are preferred from the viewpoint of processability, and elongate roll films are more preferred because continuous production is possible. Examples of the resin constituting the film substrate include polyolefins such as polyethylene, polypropylene, and norcamphene-based polymers; cyclic olefin-based resins; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate ; Polyacrylate; Cellulose esters such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Polyethylene; Polyether cellulose ; Polyether ketone; polyphenylene sulfide and polyphenylene ether and other plastics. A release treatment such as silicone treatment can be implemented on the bonding surface of the base material and the adhesive layer. Examples of 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 film by conventional methods such as solvent casting method and melt extrusion method to become a substrate.

Commercially available cyclic olefin-based resins include, for example, "Topas" (registered trademark) (manufactured by Ticona Co., Ltd.), "ARTON" (registered trademark) (manufactured by JSR Co., Ltd.), "ZEONOR" (registered trademark), " ZEONEX" (registered trademark) (manufactured by ZEON Co., Ltd. above) and "APEL" (registered trademark) (manufactured by Mitsui Chemicals Co., Ltd.). Commercially available cyclic olefin-based resin substrates can be used. Commercially available cyclic olefin-based resin substrates include, for example, "Escena" (registered trademark), "SCA40" (registered trademark) (manufactured by Sekisui Chemical Co., Ltd.), "ZEONOR FILM" (registered trademark) (OPTES Co., Ltd. system) and "ARTON FILM" (registered trademark) (JSR Co., Ltd.).

The base material is preferably thick enough to easily laminate each layer and to be easily peeled off. The thickness of such a substrate is usually 5 to 300 μm, preferably 10 to 150 μm.

[Other forms 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 at least includes a polarizing layer, a λ/4 retardation layer, The vertical alignment liquid crystal hardening layer and the reinforcing layer are sufficient, and other layers such as other alignment liquid crystal hardening layers, protective layers, etc. may be included.

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

In a preferred aspect, the other aligned liquid crystal cured layer has the optical properties represented by formula (6), preferably has the optical properties represented by formula (6-1). The in-plane retardation value Re(550) can be adjusted by the same method as the method for adjusting the in-plane retardation value of the λ/4 retardation layer described above.

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

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

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

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

The protective layer is preferably formed of the following protective layer-forming composition, which generally contains polyfunctional acrylate (methacrylate), urethane acrylate, polyester acrylate, cyclic Acrylic oligomers or polymers composed of oxyacrylates, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyvinylpyrrolidone, starches, methylcellulose, carboxymethylcellulose, alginic acid Sodium and other water-soluble polymers and solvents.

The solvent contained in the composition for forming a protective layer may be, for example, the same solvents as those exemplified in the item of the polymerizable liquid crystal composition, wherein at least one solvent selected from the group consisting of water, alcohol solvents, and ether solvents, It is preferable in terms of not dissolving the layer forming the protective layer. Alcohol solvents include, for example, methanol, ethanol, butanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether. The ether solvent may, for example, be ethylene glycol monomethyl ether acetate or 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, more preferably 0.3 μm to 5.0 μm.

In the elliptically polarizing plate of the present invention, as in the elliptically polarizing plate shown in Figs. 1 to 3, each layer may be laminated through an adhesive after forming each layer, or each layer may be directly laminated without an adhesive or the like. The method of attaching each layer may be, for example, a method of laminating each layer on a substrate, bonding the layers through an adhesive, and then peeling off the substrate; or a method of bonding the layers through an adhesive after peeling off the substrate. . In addition, the method of directly laminating each layer or the method of lamination|stacking on a base material can use the method similar to the above-mentioned method of forming each layer on a base material. Furthermore, surface treatment such as corona treatment, plasma treatment, etc. may be performed on the surface of the substrate or the surface of each layer before laminating the layers on the substrate and before bonding each layer through an adhesive.

[display device]

The elliptically polarizing plate of the present invention can be used in a display device. The so-called 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. Display devices include, for example, liquid crystal display devices, organic electroluminescence (EL) display devices, inorganic electroluminescence (EL) display devices, touch panel display devices, electron emission display devices (field emission display devices (FED, etc.), surface Electric field emission display device (SED)), electronic paper (display device using electronic ink, electrophoretic element), plasma display device, projection display device (grating light valve (GLV) display device, digital micromirror device ( DMD) display devices, etc.) and piezoelectric ceramic displays, etc. The liquid crystal display device includes any of a transmissive liquid crystal display device, a semi-transmissive liquid crystal display device, a reflective liquid crystal display device, a direct-view liquid crystal display device, and a projection type liquid crystal display device. These display devices may be display devices that display 2D images, or may be stereoscopic display devices that display 3D images. In particular, the display device including the elliptically polarizing plate of the present invention is preferably an organic EL display device and a touch panel display device, and is 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 can be, for example, a device in which the reinforcing layer 8 side of the elliptical polarizing plate shown in FIG. 1 is bonded to the organic EL panel through an adhesive agent. Or a device in which the alignment layer 5 of the elliptically polarizing plate shown in FIG. 3 is bonded to the organic EL panel through an adhesive.

[Example]

Hereinafter, the present invention will be described more specifically by means of examples. In addition, "%" and "part" in an example mean mass % and a mass part unless otherwise specified. In addition, the polymer films, devices, and measurement methods used in the following examples are as follows.

‧AGF-B10 manufactured by Kasuga Electric Co., Ltd. was used as the corona treatment device.

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

‧Ushio Electric Co., Ltd. SPOT CURE SP-9 with polarizer unit was used as the polarized UV irradiation device.

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

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

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

(Example 1)

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

[Manufacture of polarizing layer 2]

After immersing a polyvinyl alcohol film with an average degree of polymerization of about 2400, a saponification degree of 99.9 mol% or more, and a thickness of 75 μm in pure water at 30°C, it is immersed in iodine/potassium iodide/water at a mass ratio of 0.02/2/100 at 30°C aqueous solution, 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 boric acid treatment (boric acid treatment step). The polyvinyl alcohol film subjected to the boric acid treatment step was washed with pure water at 8° C., and then dried at 65° C. to obtain a polarizer (27 μm in thickness after stretching) in which iodine was adsorbed and aligned to the polyvinyl alcohol. At this time, extension is performed in the iodine staining step and the boric acid treatment step. The total elongation ratio of such elongation was 5.3 times. The obtained polarizer and a saponified triacetylcellulose film (KC4UYTAC 40 μm manufactured by Konica Minolta Corporation) were bonded together with a nip roller through a water-based adhesive. It dried at 60 degreeC for 2 minutes, maintaining the tension|tensile_strength of the obtained bonded product at 430 N/cm, and obtained the polarizing layer which has a triacetyl cellulose film as a protective film on one surface. Furthermore, the aforementioned water-based adhesive was prepared by adding 3 parts of carboxyl-modified polyvinyl alcohol (manufactured by Kuraray, "Kuraray Poval KL318") and water-soluble polyamide epoxy resin (manufactured by Sumika Chemtex Co., Ltd., "Sumirez KL318") to 100 parts of water. resin 650", an aqueous solution with a solid content concentration of 30%) was prepared by 1.5 parts.

Optical characteristics were measured about the obtained polarizing layer 2 . The measurement was carried out using a spectrophotometer ("V7100", manufactured by JASCO Corporation) using the polarizer surface of the polarizing layer obtained above as the incident surface. The absorption axis of the polarizing layer is consistent with the extension direction of polyvinyl alcohol. The sensitivity-corrected monomer transmittance of the obtained polarizing layer is 42.1%, the sensitivity-corrected polarization degree is 99.996%, and the monomer hue a is -1.1. Hue b is 3.7.

[Modulation of composition (a) for forming alignment layer 5 for forming λ/4 retardation layer 4]

5 parts of photo-alignment material (weight average molecular weight: 30000) with the following structure and 95 parts of cyclopentanone (solvent) were mixed as components, and the resulting mixture was stirred at 80°C for 1 hour to obtain a λ/4 phase Composition (a) for forming alignment layer 5 for forming difference layer 4 .

[Preparation of the composition for forming the λ/4 retardation layer 4 and the composition for forming the vertically aligned liquid crystal hardened layer 6]

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

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

The polymerizable liquid crystal compound A was produced using the method described in JP-A-2010-31223. In addition, the polymerizable liquid crystal compound B was produced according to the method described in JP-A-2009-173893. Each molecular structure is shown below.

[Polymerizable Liquid Crystal Compound A]

[Polymerizable Liquid Crystal Compound B]

[Manufacture of laminate A composed of base material, alignment layer 5 and λ/4 retardation layer 4]

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

Next, the composition for forming the λ/4 retardation layer 4 was applied to the alignment layer 5 using a bar coater, dried at 120°C for 1 minute, and then dried using a high-pressure mercury lamp ("Unicure VB-15201BY-A", Ushio Electric Co., Ltd. ) to irradiate ultraviolet light (accumulated light intensity at a wavelength of 365nm: 500mJ/cm ² under a nitrogen atmosphere), thereby forming a λ/4 retardation layer 4, and obtaining the substrate, the alignment layer 5, and the λ/4 retardation layer 4 The formed laminate A. The film thickness of the λ/4 retardation layer 4 of the laminate A was 2.3 μm when measured using an ellipsometer.

[Preparation of Vertical Alignment Layer Forming Composition (b) for Formation of Vertical Alignment Liquid Crystal Cured Layer]

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

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

Prepare 50 parts of diperythritol hexaacrylate (ARONIX M-403, polyfunctional acrylate manufactured by Toagosei Co., Ltd.), 50 parts of acrylate resin (EBECRYL 4858, manufactured by DAICEL UCB Co., Ltd.), 2-methyl - 3 parts of 1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Irgacure 907; manufactured by Ciba Specialty Chemicals) dissolved in 250 parts of isopropanol, prepared A composition for forming a reinforcing layer comprising an acrylic resin.

[Manufacture of laminate B composed of substrate, reinforcing layer 8, alignment layer 7, and vertically aligned liquid crystal hardening layer 6]

On a release-treated polyethylene terephthalate film manufactured by ZEON Co., Ltd. (Lintec Co., Ltd., SP-PLR382050, hereinafter referred to as "separator"), a bar coater containing 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 (at a wavelength of 365 nm in a nitrogen atmosphere) using a high-pressure mercury lamp (“Unicure VB-15201BY-A”, manufactured by Ushio Electric Co. Cumulative light quantity: 500 mJ/cm ² ), thereby forming the reinforcing layer 8 made of acrylic resin. The film thickness of the obtained reinforcing layer 8 was 10 μm when measured using a contact film thickness gauge. Then, the composition (b) for forming a vertical alignment layer was coated 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, on the vertical alignment layer 7, the composition for forming the vertical alignment liquid crystal cured layer 6 was coated with a bar coater, dried at 120° C. for 1 minute, and then sprayed with a high-pressure mercury lamp ("Unicure VB-15201BY-A", Ushio Electric Co., Ltd. Manufactured by the company) to irradiate ultraviolet rays (accumulated light intensity at a wavelength of 365nm in a nitrogen atmosphere: 500mJ/cm ² ), thereby forming a vertically aligned liquid crystal hardened layer 6, and obtaining a hardened layer composed of a base material, a reinforcing layer 8, an alignment layer 7, and a vertically aligned liquid crystal Laminate B composed of layer 6. The film thickness of the vertically aligned liquid crystal cured layer 6 of the laminate B was 1.2 μm when measured using an ellipsometer. Moreover, the interlayer distance between the reinforcing layer 8 and the vertically aligned liquid crystal cured layer 6 is 50 nm. Furthermore, 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 vertically aligned liquid crystal hardening layer 6 manufactured by the above method are after confirming that the COP film belonging to the substrate has no retardation , and measured with a measuring machine (“KOBRA-WPR”, manufactured by Oji Scientific Instruments Co., Ltd.). As a result of measuring the retardation value ReQ(λ) at each wavelength, ReQ(450)=119nm, ReQ(550)=140nm, ReQ(650)=146nm, ReQ(450)/ReQ(550)=0.85.

[Rth Measurement of Vertically Aligned Liquid Crystal Curing Layer 6]

The retardation value (RthV(λ)) in the thickness direction of the vertically aligned liquid crystal hardened layer 6 manufactured by the above method is that the vertically aligned liquid crystal hardened layer 6 is bonded to glass via an adhesive (15 μm pressure-sensitive adhesive manufactured by Lintec Corporation). Then, the separator belonging to the base material was peeled off, and the measurement sample was prepared. After confirming that there was no phase difference between the alignment layer 7 and the reinforcement layer 8, the measurement was performed by changing the incident angle of light on the sample with an ellipsometer. In addition, the average refractive index of the wavelength λ of 450 nm and 550 nm was measured using the refractometer (made by Atago Co., Ltd., "multi-wavelength Abbe refractometer DR-M4"). The RthV calculated from the obtained film thickness, average refractive index and ellipsometer measurement results are RthV(450)=-60nm, RthV(550)=-70nm, RthV(450)/RthV(550)=0.85.

[Manufacture of elliptically polarizing plate 1]

After corona treatment was performed on the polymerizable liquid crystal composition-coated surface of the λ/4 retardation layer 4 of the laminate A, the polarizing layer 2 produced above was adhered to the λ/4 retardation layer 4 of the laminate A through the Agent 3 (pressure-sensitive adhesive 15 μm manufactured by Lintec Co., Ltd.) was attached 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 was 45°, and only the substrate was peeled off. Laminate C is produced. Then, after performing corona treatment on the vertically aligned liquid crystal hardened layer 6 of the laminate B, the alignment layer 5 of the laminated body C and the vertically aligned liquid crystal hardened layer 6 of the laminated body B were separated by an adhesive 3 (pressure sensitive type made by Lintec Co., Ltd.). Adhesive (15 μm) was bonded, and only the substrate was peeled off to produce an elliptically polarizing plate 1 .

[Difference in in-plane average refractive index of each layer]

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

[Observation of cut end face]

Place the obtained elliptical polarizer on a cutting mat, cut out a 3cm×3cm square with a cutter, and then visually observe the end surface with a 10x magnifying glass to confirm whether there are defects such as waviness and cracks. The same operation was carried out three times, and the case where a defect was observed even in one of them was made X, and the case where a defect was not observed was made ○, and the results are shown in Table 1.

(Example 2 and 3)

Except having changed the film thickness of the reinforcing layer 8 to what is described in Table 1, an elliptically polarizing plate was produced in the same manner as in Example 1, and observation of the cut end surface was implemented.

(Example 4)

In addition to mixing 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.) were used to prepare the composition (b) for forming a vertical alignment layer, and the composition (b) for forming a vertical alignment layer was used and Except that the film thickness of the reinforcing layer 8 was 5 μm, an elliptically polarizing plate was produced in the same manner as in Example 1, and the cut end face was observed. The results are shown in Table 1. In addition, the film 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 cured layer 6 is 0.5 μm.

(Example 5)

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

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

Mix 80 parts of 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 20 parts of 2-ethylhexyl glycidyl ether, 2.25 parts of CPI-100P manufactured by SAN-APRO, 2.25 parts of propylene carbonate was used to prepare a composition for forming the reinforcing layer 8 including an epoxy resin.

[Manufacture of laminate B composed of base material, reinforcing layer 8, alignment layer 7, and vertically aligned liquid crystal cured layer 6 (only the manufacturing part of reinforcing layer 8)]

On the release-treated separator, apply a composition for forming the reinforcing layer 8 including epoxy resin using a bar coater, dry at 50°C for 1 minute, and then use a high-pressure mercury lamp ("Unicure VB-15201BY-A ", manufactured by Ushio Electric Co., Ltd.) was irradiated with ultraviolet light (accumulated light intensity at a wavelength of 365 nm: 400 mJ/cm ² in a nitrogen atmosphere), thereby forming the reinforcing layer 8 made of epoxy resin. When the film thickness of the obtained reinforcing layer 8 was measured using a contact film thickness meter, it was 5 micrometers.

(Example 6)

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

[Preparation of composition for forming reinforcing layer 8 including urethane resin]

Prepare 100 parts of acrylate resin (EBECRYL 4858, manufactured by DAICEL UCB Co., Ltd.), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (Irgacure 907 ; Ciba Specialty Chemicals Co., Ltd.) was dissolved in 250 parts of isopropanol to obtain a composition for forming the reinforcing layer 8 comprising urethane resin.

[Manufacture of laminate B composed of base material, reinforcing layer 8, alignment layer 7, and vertically aligned liquid crystal cured layer 6 (only the manufacturing part of reinforcing layer 8)]

On the release-treated separator sheet, apply a composition for forming the reinforcement layer 8 including urethane resin using a bar coater, dry at 50°C for 1 minute, and then use a high-pressure mercury lamp ("Unicure VB-15201BY-A ", manufactured by Ushio Electric Co., Ltd.) by irradiating ultraviolet rays (accumulated light intensity at a wavelength of 365 nm: 400 mJ/cm ² in a nitrogen atmosphere) to form the reinforcing layer 8 made of urethane resin. When the film thickness of the obtained reinforcing layer 8 was measured using a contact film thickness meter, it was 5 micrometers.

(Examples 7 to 9)

Except for changing the film thickness of the reinforcing layer 8 and changing the manufacturing method of the elliptically polarizing plate as described below, the elliptically polarizing plate 10 having the layer configuration shown in FIG. 2 was produced in the same manner as in Example 1, and the cut end surface was observed.

[Manufacturing method of elliptically polarizing plate 10]

First, after performing corona treatment on the vertically aligned liquid crystal hardened layer 6 of the laminate B, the vertically aligned liquid crystal hardened layer 6 side of the laminated body B is separated from the polarizing layer 2 obtained above through an adhesive 3 (pressure sensitive type made by Lintec Co., Ltd. Adhesive (15 μm) was bonded, and the base material was peeled off to produce a laminate D. Then, after performing corona treatment on the polymerizable liquid crystal composition-coated surface of the λ/4 retardation layer 4 of the laminate A, the reinforcing layer 8 of the laminate D and the λ/4 retardation layer 4 of the laminate A, Adhesive 3 (pressure-sensitive adhesive 15 μm manufactured by Lintec Co., Ltd.) is interposed 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 substrates are bonded together, and the substrates are peeled off to produce the elliptical polarizing plate 10 .

(Examples 10 to 12)

Except for changing the film thickness of the reinforcing layer 8 and changing the manufacturing method of the elliptically polarizing plate as described below, an elliptically polarizing plate 100 having the layered structure shown in FIG. 3 was produced in the same manner as in Example 1, and the cut end faces were observed.

[Manufacturing method of elliptically polarizing plate 100]

First, after performing corona treatment on the λ/4 retardation layer 4 of the laminate A and the vertical alignment liquid crystal hardened layer 6 of the laminate B, the λ/4 retardation layer 4 of the laminate A and the vertical alignment layer 6 of the laminate B The liquid crystal cured layer 6 was bonded via the adhesive 3 (15 μm pressure-sensitive adhesive manufactured by Lintec Co., Ltd.), and the base material of the laminate B was peeled off to prepare a laminate E. Then, the reinforcing layer 8 and the polarizing layer 2 of the laminate E were interposed between the adhesive 3 (pressure-sensitive adhesive manufactured by Lintec Co., Ltd., 15 μm), so that the absorption axis of the polarizing layer 2 was relative to that of the λ/4 retardation layer 4. After bonding so that the slow axis (optical axis) becomes substantially 45°, the base material contained in the laminate A is peeled off to produce the elliptically polarizing plate 100 .

(comparative example 1)

Except for omitting the step of producing the reinforcing layer, an elliptically polarizing plate was produced in the same manner as in Example 1, and the cut end face was observed.

(comparative example 2)

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

Hereinafter, the results of observing the cut end faces are shown for Examples and Comparative Examples. Furthermore, in Table 1, the interlayer distance refers to the interlayer distance between the vertically aligned liquid crystal cured layer 6 and the reinforcing layer 8 .

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

1‧‧‧elliptical polarizer

2‧‧‧Polarizing layer

3‧‧‧adhesive layer

4‧‧‧λ/4 retardation layer

5‧‧‧Alignment layer

6‧‧‧Vertically aligned liquid crystal hardening layer

7‧‧‧Vertical alignment layer

8‧‧‧reinforcing layer

Claims (9)

An elliptical polarizing plate, which has a polarizing layer, a λ/4 retardation layer, a vertically aligned liquid crystal hardened layer, a vertically aligned layer, and a reinforcing layer in sequence, or has a polarizing layer, a reinforcing layer, a vertically aligned layer, and a vertically aligned liquid crystal in sequence The cured layer and the λ/4 retardation layer, wherein the vertically aligned liquid crystal cured layer is a polymer made of a polymerizable liquid crystal composition including a polymerizable liquid crystal compound aligned in a vertical direction relative to the plane of the liquid crystal cured layer. In this configuration, the film thickness of the vertically aligned liquid crystal hardening layer is 3 μm or less, and the film thickness of the reinforcing layer is 1 to 5 μm. The elliptically polarizing plate as described in item 1 of the patent claims, 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 described in item 1 or item 2 of the scope of the patent application, wherein the λ/4 retardation layer is a horizontally aligned liquid crystal hardened layer, and the horizontally aligned liquid crystal hardened layer is contained relative to the plane of the liquid crystal hardened layer The polymerizable liquid crystal composition of the polymerizable liquid crystal compound in the state aligned in the horizontal direction is composed of polymers. The elliptical polarizing plate as described in item 1 or item 2 of the scope of the patent application, wherein the reinforcing layer is composed of acrylic resin, epoxy resin, oxetane resin, urethane resin and melamine resin. At least 1 of those formed. The elliptically polarizing plate described in item 1 or item 2 of the scope of the patent application has an alignment layer with a film thickness of 5 μm or less between the vertically aligned liquid crystal hardening layer and the reinforcing layer, and the alignment layer is composed of Si contained in the constituent elements A layer composed of compounds of elements, C elements, and O elements. The elliptically polarizing plate according to claim 1 or 2, wherein the difference in the average refractive index in the plane at a wavelength of 550 nm is 0.20 or less in each adjacent layer. The elliptically polarizing plate as described in item 1 or item 2 of the scope of the patent application, wherein, with regard to the λ/4 retardation layer, in the refractive index ellipsoid formed by the λ/4 retardation layer, at wavelengths λ=400 to The range of 700nm has the relationship of the following formula, nxQ(λ)>nyQ(λ)≒nzQ(λ) In the formula, nxQ(λ) means that in the refractive index ellipsoid formed by the λ/4 retardation layer, for The main refractive index of the light with wavelength λ (nm) in the direction parallel to the phase difference layer plane; nyQ(λ) means that in the refractive index ellipsoid formed by the λ/4 phase difference layer, relative The plane is parallel and relative to the direction of nxQ(λ) which is orthogonal to the refractive index of light with wavelength λ(nm); nzQ(λ) means the refractive index ellipse formed in the λ/4 retardation layer In the body, the refractive index of the light of wavelength λ (nm) in the direction perpendicular to the plane of the phase difference layer; and satisfy 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 λ/4 phase of light with wavelength λ=450nm The in-plane retardation value of the difference layer, ReQ(550) represents the in-plane retardation value of the λ/4 retardation layer for light with wavelength λ=550nm, and ReQ(650) represents the in-plane retardation value for The in-plane retardation value of the λ/4 retardation layer of light with wavelength λ=650nm, the in-plane retardation value ReQ(λ) of the λ/4 retardation layer of light with wavelength λ(nm) is expressed by ReQ(λ )=(nxQ(λ)-nyQ(λ))×dQ, where dQ represents the thickness of the λ/4 retardation layer. The elliptically polarizing plate as described in item 1 or item 2 of the scope of the patent application, wherein, regarding the vertically aligned liquid crystal hardened layer, in the refractive index ellipsoid formed by the vertically aligned liquid crystal hardened layer, at wavelength λ=400 to 700nm The range has the relationship of the following formula, nzV(λ)>nxV(λ)≒nyV(λ) In the formula, nzV(λ) means that in the refractive index ellipsoid formed by the liquid crystal hardening layer, the wavelength λ(nm) The refractive index of the light in the direction perpendicular to the plane of the liquid crystal hardening layer; nxV(λ) means that in the refractive index ellipsoid formed by the liquid crystal hardening layer, the light of wavelength λ (nm) is relative to the liquid crystal hardening layer The maximum refractive index in the direction parallel to the plane, nyV(λ) means that in the refractive index ellipsoid formed by the liquid crystal hardening layer, it is parallel to the plane of the liquid crystal hardening layer and is perpendicular to the direction nxV. To the refractive index of the light of wavelength λ (nm); But in the case of nxV (λ)=nyV (λ), nxV (λ) represents the refractive index of any direction parallel to the plane of the liquid crystal hardening layer; and satisfies the following The relationship between 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 hardening layer for light with wavelength λ=450nm, and RthV(550) represents the retardation value in the thickness direction of the liquid crystal hardening layer for light with wavelength λ=550nm , RthV(650) represents the retardation value in the thickness direction of the liquid crystal hardening layer for light with wavelength λ=650nm, and the retardation value RthV(λ) for the thickness direction of the liquid crystal hardening layer for light with wavelength 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 hardening layer, nzV(λ) represents The principal refractive index in the direction perpendicular to the plane of the liquid crystal hardened layer at the wavelength λ (nm), "(nxV(λ)+nyV(λ))/2" represents the plane of the liquid crystal hardened layer at the wavelength λ (nm) The average refractive index; dV represents the thickness of the liquid crystal hardened layer. An organic EL display device is provided with the elliptically polarizing plate described in any one of the first to eighth items of the scope of the patent application.

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