KR102059695B1 - Circular polarizing plate and display device - Google Patents

Abstract

[PROBLEMS] To provide a thin, broadband broadband polarizing plate and a display device having the circular polarizing plate.
[Resolution] The birefringence Δn (λ) with respect to the light having the wavelength λnm of the retardation layer having the base material, the retardation layer and the polarization layer satisfies the formulas (1) and (2), and the retardation layer and the polarizing layer Together, it is a coating layer, the sum total of the thickness of a phase difference layer and a polarizing layer is 10 micrometers or less, and the said polarizing layer contains a dichroic dye, The circular polarizing plate characterized by the above-mentioned.
Δn (450) / Δn (550) ≤1.00 (1)
1.00≤Δn (650) / Δn (550) (2)

Description

Circular polarizer and display device {CIRCULAR POLARIZING PLATE AND DISPLAY DEVICE}

The present invention relates to a circular polarizing plate and a display device.

BACKGROUND ART A liquid crystal display device comprising a polarizing film made of polyvinyl alcohol dyed with iodine and a broadband circular polarizing plate in which a half wave plate and a quarter wave plate are laminated is known. In such a broadband circular polarizer, the angle formed by the slow axis of the half wave plate and the absorption axis of the polarizing film and the angle formed by the slow axis of the quarter wave plate and the absorption axis of the polarizing film are shifted by 15 ° or 75 °, respectively. Since it is necessary to laminate, it is difficult to produce the circular polarizing plate by roll-to-roll bonding. On the other hand, the thinning of the display device is also strongly demanded, and therefore, the circularly polarizing plate is also required to be thinned.

Patent Document 1 describes a circularly polarizing plate having a thickness of 130 to 370 µm in which a polarizer obtained by coating a reverse wavelength dispersible film and a dichroic dye is laminated on a phase difference layer. Patent Document 2 describes a circularly polarizing plate having a thickness of 36 to 205 µm in which a polarizer containing a thermotropic liquid crystalline or lyotropic liquid crystalline substance is laminated on a phase difference layer.

Patent Document 1: Japanese Patent Application Laid-Open No. 2006-337892 Patent Document 2: Japanese Patent Application Laid-Open No. 2009-251288

However, since the circularly polarizing plate of patent document 1 has laminated | stacked two films through an adhesive or an adhesive agent, it was not able to fully be satisfied from a viewpoint of the simplicity of a manufacturing process, and the thickness of a circularly polarizing plate. In the circular polarizing plate described in Patent Literature 2, since the retardation layer showed the constant wavelength dispersion, the performance as a broadband circular polarizing plate was insufficient.

The present invention includes the following inventions.

[1] The birefringence Δn (λ) with respect to the light having a wavelength λnm of the retardation layer having the base material, the retardation layer, and the polarization layer satisfies Equations (1) and (2), and the retardation layer and the polarization layer are together. It is a coating layer, The sum total of the thickness of a phase difference layer and a polarizing layer is 10 micrometers or less, and the said polarizing layer contains a dichroic dye, The circular polarizing plate characterized by the above-mentioned.

Δn (450) / Δn (550) ≤1.00 (1)

1.00≤Δn (650) / Δn (550) (2)

[2] The circularly polarizing plate according to [1], wherein the retardation layer is formed by polymerizing one or more polymerizable liquid crystals.

[3] The circularly polarizing plate according to [1] or [2], wherein the polarizing layer is formed by polymerizing one or more polymerizable liquid crystals.

[4] The circularly polarizing plate described in [2] or [3], wherein the polymerizable liquid crystal is polymerized by light irradiation.

[5] The circularly polarizing plate according to any one of [1] to [4], wherein the polarizing layer is a polarizing layer capable of obtaining Bragg peaks in X-ray diffraction measurement.

[6] The circularly polarizing plate according to any one of [1] to [5], wherein the thickness of the retardation layer and the polarizing layer is 5 µm or less, respectively.

[7] The circularly polarizing plate according to any one of [1] to [6], wherein the retardation layer, the polarizing layer, or both thereof are formed on the alignment film.

[8] The circularly polarizing plate described in [7], wherein the alignment film is an alignment film in which an alignment regulating force is caused by light irradiation.

[9] The circularly polarizing plate according to [7] or [8], wherein the thickness of the alignment film is 500 nm or less.

[10] The circularly polarizing plate according to any one of [1] to [9], wherein a phase difference layer is formed on or without the alignment film on the substrate, and a polarization layer is formed on or without the alignment film on the phase difference layer. .

[11] The circularly polarizing plate described in any one of [1] to [9], wherein a polarizing layer is formed on or without the alignment film on the substrate, and a phase difference layer is formed on or without the alignment film on the polarizing layer. .

[12] The circularly polarizing plate described in [10] or [11], which has a protective layer between the polarizing layer and the retardation layer.

[13] In any of [1] to [9], wherein a polarizing layer is formed on one side of the substrate with or without the alignment film, and a phase difference layer is formed on the other side of the substrate with or without the alignment layer. Circular polarizing plate described.

[14] The circularly polarizing plate according to any one of [1] to [13], further comprising an adhesive layer on the surface of the phase difference layer or the polarizing layer.

[15] The circularly polarizing plate according to [14], which has a base material, a first alignment film, a polarizing layer, a second alignment film, a retardation layer, and an adhesive layer in this order.

[16] The peeling strength (F1) of the substrate and the first alignment layer includes the peeling strength (F2) of the first alignment layer and the polarizing layer, the peeling strength (F3) of the second alignment layer and the retardation layer, and the retardation layer and the adhesive layer. The circularly polarizing plate as described in [15] lower than peeling strength (F4) of the.

[17] A display device comprising the circularly polarizing plate according to any one of [1] to [16] and a display element.

[18] A display device having a circularly polarized film in which a circularly polarized film whose substrate is removed from the circularly polarizing plate according to any one of [14] to [16] is bonded to a display surface of a display element through an adhesive layer of the circularly polarized film. .

[19] The display device according to [18], wherein the circularly polarizing film has a thickness of 5 µm or more and 15 µm or less.

[20] The display device according to any one of [17] to [19], wherein the display element is a liquid crystal cell, an organic electroluminescent element, or a touch panel.

[21] A display device having a circularly polarizing film, wherein the circularly polarizing plate according to any one of [14] to [16] is bonded to the display surface of the display element via an adhesive layer of the circularly polarizing plate, and the substrate is removed from the circularly polarizing plate. Method of preparation.

According to the present invention, it is possible to provide a thin and broadband circular polarizing plate and a display device having the circular polarizing plate.

1 is a schematic cross-sectional view of a circular polarizing plate of the present invention.
2 is a schematic view of a liquid crystal display device including the circular polarizing plate of the present invention.
3 is a schematic view of an organic EL display device including the circular polarizing plate of the present invention.

The substrate is usually a transparent substrate. On the other hand, when the substrate of the circularly polarizing plate of the present invention (hereinafter sometimes referred to as the circularly polarizing plate) is not provided on the display surface of the display element, for example, the circularly polarizing film from which the substrate is removed from the circularly polarizing plate is displayed on the display element. In the case of installing on the surface, the substrate may not be transparent. A transparent base material means the base material which has transparency which can transmit light, especially visible light, and transparency means the characteristic that the transmittance | permeability with respect to the light ray over wavelength 380-780 nm becomes 80% or more. A transparent resin base material is mentioned as a specific transparent base material. As resin which comprises a translucent resin base material, Polyolefin, such as polyethylene and a polypropylene; Cyclic olefin resins such as norbornene-based polymers; Polyvinyl alcohol; Polyethylene terephthalate; Polymethacrylic acid ester; Polyacrylic acid ester; Cellulose esters such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Polysulfones; Polyether sulfone; Polyether ketones; Polyphenylene sulfide and polyphenylene oxide. From the viewpoint of availability and transparency, polyethylene terephthalate, polymethacrylic acid ester, cellulose ester, cyclic olefin resin or polycarbonate is preferable.

The cellulose ester is obtained by esterifying some or all of the hydroxyl groups contained in the cellulose in the market. Moreover, a cellulose ester base material can also be obtained easily in a market. As a commercially available cellulose ester base material, it is "Fuji tag film" (Fuji Shashin Film Co., Ltd.); "KC8UX2M", "KC8UY", "KC4UY" (Konica Minolta Opt Co., Ltd.), etc. are mentioned.

Cyclic olefin resin is easily available on the market. Commercially available cyclic olefin resins include "Topas" [Ticona Corporation (Germany)], "Aton" [JSR Corporation], "ZEONOR" [Nippon Xeon Corporation], "ZEONEX" [Nippon Xeon Corporation] and "Apel" (made by Mitsui Chemical Co., Ltd.) are mentioned. Such cyclic olefin resin can be formed into a film by well-known means, such as a solvent casting method and a melt extrusion method, for example. In addition, a commercially available cyclic olefin resin substrate can also be used. Commercially available cyclic olefin resin base materials include "Esshina" [Sekisuga Chemical Co., Ltd.], "SCA40" [Sekisuga Chemical Co., Ltd.], "Zenooa Film" [Optes Co., Ltd.], and "Aton Film" [JSR Corporation] is mentioned.

When the cyclic olefin resin is a copolymer of a cyclic olefin with an aromatic compound having a chain olefin or a vinyl group, the content ratio of the structural unit derived from the cyclic olefin is usually 50 mol% or less with respect to all the structural units of the copolymer, preferably It is the range of 15-50 mol%. Examples of the chain olefins include ethylene and propylene, and examples of the aromatic compound having a vinyl group include styrene, α-methylstyrene, and alkyl substituted styrene. When the cyclic olefin resin is a ternary copolymer of a cyclic olefin, a chain olefin, and an aromatic compound having a vinyl group, the content ratio of the structural units derived from the chain olefins is usually 5 to 80 mol% based on the total structural units of the copolymer. And the content rate of the structural unit derived from the aromatic compound which has a vinyl group is 5-80 mol% normally with respect to the whole structural unit of a copolymer. This terpolymer has the advantage that the amount of expensive cyclic olefins can be relatively low in its production.

Although the characteristic required for a base material changes with the structure of a circularly polarizing plate, the base material which is as small as possible with retardation normally is preferable. As a base material as small as possible with retardation, the cellulose ester film which does not have retardation, such as zero tag (Konica Minolta Opt Co., Ltd.) and Z tag (FUJIFILM Corporation), is mentioned. Moreover, unstretched cyclic olefin resin base material is also preferable.

In the case of the circularly polarizing plate on which the polarizing layer is formed on or without the alignment film on the substrate and the retardation layer is formed on or on the polarizing layer, on the surface of the substrate on which the polarizing layer is not formed, A heart coat treatment, an antireflection treatment, an antistatic treatment or the like may be performed. Moreover, the hard coat layer may contain additives, such as a ultraviolet absorber, in the range which does not affect performance.

When the thickness of the base material is too thin, the strength is lowered and the workability tends to be inferior. Therefore, it is usually 5 to 300 m, and preferably 20 to 200 m.

The retardation layer is a coating layer in which the birefringence Δn (λ) with respect to light having a wavelength λnm satisfies the formulas (1) and (2). A coating layer means the layer formed by application | coating.

Δn (450) / Δn (550) ≤1.00 (1)

1.00≤Δn (650) / Δn (550) (2)

The birefringence Δn (λ) is obtained by measuring the retardation and dividing by the thickness of the phase difference layer. Although the specific measuring method is shown in the Example, the characteristic of a substantial retardation layer can be measured by measuring what film-formed on the base material which does not have retardation in the base material itself like a glass substrate.

The retardation layer is preferably formed by polymerizing one or more polymerizable liquid crystals (hereinafter sometimes referred to as polymerizable liquid crystals (A)).

A polymerizable liquid crystal is a compound which has a polymeric group and has liquid crystallinity. A polymerizable group means group which participates in a polymerization reaction, and it is preferable that it is a photopolymerizable group. Here, a photopolymerizable group means group which can participate in a polymerization reaction by active radical, acid, etc. which generate | occur | produced from the photoinitiator mentioned later. Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group and oxetanyl group. Especially, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group, and oxetanyl group are preferable, and acryloyloxy group is more preferable. The liquid crystal may be either a thermotropic liquid crystal or a lyotropic liquid crystal. If the thermotropic liquid crystal is classified in order, the nematic liquid crystal or the smectic liquid crystal may be used.

Especially, a thermotropic nematic liquid crystal is preferable from a viewpoint of film forming ease, and is represented by a following formula (A) from a viewpoint of providing the phase difference represented by the said Formula (1) and said Formula (2). Compounds (hereinafter sometimes referred to as compound (A)) are preferred. The polymerizable liquid crystals may be used alone or in combination.

[In formula (A), X <^1> represents an oxygen atom, a sulfur atom, or NR <^1> -. R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

Y <^1> represents the C6-C12 monovalent aromatic heterocyclic group which may have a substituent, or may have a C6-C12 monovalent aromatic hydrocarbon group.

Q ³ and Q ⁴ each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a 6 to 20 carbon atoms which may have a substituent. A monovalent aromatic hydrocarbon group, a halogen atom, a cyano group, a nitro group, -NR ² R ³ or -SR ² , or Q ³ and Q ⁴ are bonded to each other to form an aromatic ring or aromatic compound together with the carbon atom to which they are bonded Form a summon. R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

D ¹ and D ² are each independently a single bond, -C (= O) -O-, -C (= S) -O-, -CR 4 R 5 -, -CR 4 R 5 -CR 6 R 7 - , -O-CR ⁴ R ^5- , -CR ⁴ R ⁵ -O-CR ⁶ R ^7- , -CO-O-CR ⁴ R ^5- , -O-CO-CR ⁴ R ^5- , -CR ⁴ R ⁵ -O-CO-CR ⁶ R ^7- , -CR ⁴ R ⁵ -CO-O-CR ⁶ R ⁷ -or NR ⁴ -CR ⁵ R ⁶ -or CO-NR ^4- .

R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and the methylene group constituting the alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom or NH-, and the alicyclic hydrocarbon group described above. The methine group which it comprises may be substituted by the tertiary nitrogen atom.

L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² has a polymerizable group]

L ¹ in the compound (A) is preferably a group represented by formula (A1), and L ² is preferably a group represented by formula (A2).

P ¹ -F ^1- (B ¹ -A ¹ ) _k -E ^1- (A1)

P ² -F ^2- (B ² -A ² ) _l -E ^2- (A2)

[In Formula (A1) and Formula (A2), B ¹ , B ² , E ¹ and E ² are each independently —CR ⁴ R ⁵ —, —CH ₂ —CH ₂ —, —O—, —S—, -CO-O-, -O-CO-O-, -CS-O-, -O-CS-O-, -CO-NR ^1- , -O-CH _2- , -S-CH ₂ -or Indicates binding.

A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and the methylene group constituting the alicyclic hydrocarbon group is an oxygen atom, a sulfur atom or NH-; The methine group constituting the alicyclic hydrocarbon group may be substituted with a tertiary nitrogen atom.

k and 1 respectively independently represent the integer of 0-3.

F ¹ and F ² represent a divalent aliphatic hydrocarbon group having 1 to 12 carbon atoms.

P ¹ represents a polymerizable group.

P ² represents a hydrogen atom or a polymerizable group.

R ⁴ and R ⁵ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms]

As a preferable compound (A), the compound of Unexamined-Japanese-Patent No. 2011-207765 is mentioned.

As a specific example of a polymerizable liquid crystal, "3.8.6 network (complete crosslinking type)" of the liquid crystal handbook (Liquid Crystal Handbook Editing Committee edition, issued March 30, 2000), "6.5.1 liquid crystal material b. And a compound having a polymerizable group in the compound described in "Polymerizable nematic liquid crystal material".

A retardation layer is normally formed by apply | coating the composition containing 1 or more polymerizable liquid crystal (A) on a base material, an orientation film, or a polarizing layer, and polymerizing the said polymerizable liquid crystal (A) in the obtained coating film.

The alignment film in the present invention has an alignment regulating force for aligning the polymerizable liquid crystal in a desired direction.

It is preferable that the alignment film has solvent resistance that does not dissolve by application of a composition containing a polymerizable liquid crystal, and has heat resistance in heat treatment for removal of the solvent and alignment of the polymerizable liquid crystal. Examples of such an alignment film include an alignment film and an optical alignment film containing an alignment polymer.

Examples of the oriented polymer include polyamides and gelatin having amide bonds in the molecule, polyimides having imide bonds in the molecule and polyamic acid, polyvinyl alcohol, alkyl modified polyvinyl alcohol, polyacrylamide, polyoxazole, Polyethylenimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid, and polyacrylic acid ester are mentioned. Especially, polyvinyl alcohol is preferable. You may use combining 2 or more types of oriented polymers.

Orientation film containing an orientation polymer usually apply | coats the composition in which an orientation polymer was melt | dissolved in the solvent (henceforth an orientation polymer composition) to a base material, removes a solvent, or applies an orientation polymer composition to a base material, and removes a solvent It is obtained by rubbing (rubbing method).

Examples of the solvent include alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether, ethyl acetate, butyl acetate, and ethylene glycol methyl ether acetate. ester solvents such as γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate, ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone, and methyl isobutyl ketone, pentane, hexane And aliphatic hydrocarbon solvents such as heptane, aromatic hydrocarbon solvents such as toluene and xylene, nitrile solvents such as acetonitrile, ether solvents such as tetrahydrofuran and dimethoxyethane, and chlorinated hydrocarbon solvents such as chloroform and chlorobenzene. These solvents may be used alone or in combination of two or more thereof.

The concentration of the orientation polymer in the orientation polymer composition may be in a range in which the orientation polymer material can be completely dissolved in the solvent. The concentration is preferably 0.1 to 20%, more preferably about 0.1 to 10%, in terms of solids with respect to the solution.

As the oriented polymer composition, a commercially available alignment film material may be used as it is. Examples of commercially available alignment film materials include San Eva (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), Optoma (registered trademark, manufactured by JSR Corporation), and the like.

As a method of apply | coating an orientation polymer composition to a base material, well-known methods, such as the spin coating method, the extrusion method, the gravure coating method, the die coating method, the coating method, such as an applicator method, the printing method, such as a flexographic method, Can be mentioned. When this circularly polarizing plate is manufactured by the roll-to-roll type continuous manufacturing method mentioned later, the said coating method is employ | adopted the printing method, such as the gravure coating method, the die-coating method, or the flexographic method normally.

As a method of removing the solvent contained in an oriented polymer composition, natural drying method, ventilation drying method, heat drying, pressure reduction drying method, etc. are mentioned.

In order to provide an orientation regulation force to an alignment film, rubbing can be performed as needed (rubbing method).

As a method of imparting the orientation regulating force by the rubbing method, a method of contacting a film of the orientation polymer formed on the surface of the substrate by applying the annealing polymer composition to the substrate and annealing the rubbing roll wound around the rotating roll is applied.

A photo-alignment film is apply | coated to the base material by apply | coating the composition (henceforth "the composition for forming a photo-alignment film") containing a polymer or a monomer and a solvent which have a photoreactive group normally, and irradiating polarized light (preferably polarized UV). Obtained. The photo-alignment film is more preferable at the point which can arbitrarily control the direction of the orientation regulation force by selecting the polarization direction of the polarized light to irradiate.

A photoreactive group means the group which raises liquid crystal aligning ability by irradiating light. Specifically, the group which participates in the optical reaction used as the origin of liquid crystal aligning ability, such as the orientation organic or isomerization reaction of a molecule | numerator produced by light irradiation, a dimerization reaction, a photocrosslinking reaction, or a photolysis reaction, is mentioned. Especially, the group which participates in a dimerization reaction or a photocrosslinking reaction is preferable at the point which is excellent in orientation. As the photoreactive group, unsaturated bonds, in particular, groups having double bonds are preferable, carbon-carbon double bonds (C = C bonds), carbon-nitrogen double bonds (C = N bonds), nitrogen-nitrogen double bonds (N = N And groups having at least one selected from the group consisting of a bond) and a carbon-oxygen double bond (C═O bond).

Examples of the photoreactive group having a C = C bond include vinyl group, polyene group, stilbene group, stilazole group, stilbazolium group, chalcone group and cinnamoyl group. Examples of the photoreactive group having a C═N bond include groups having structures such as aromatic sieve bases and aromatic hydrazones. As a photoreactive group which has N = N bond, the group which has an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bis azo group, a formazan group, and an azoxybenzene structure is mentioned. Examples of the photoreactive group having a C═O bond include a benzophenone group, coumarin group, anthraquinone group and maleimide group. These groups may have substituents, such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, and a halogenated alkyl group.

Especially, the photoreactive group which participates in a photodimerization reaction is preferable, Cinnamoyl group and a chalcone group are preferable at the point that the amount of polarization irradiation required for photo-alignment is comparatively small, and it is easy to obtain the optical alignment film excellent in thermal stability and time-lapse stability. Do. As a polymer which has a photoreactive group, what has a cinnamoyl group in which the terminal part of the polymer side chain becomes a cinnamic acid structure is especially preferable.

The photo-alignment organic layer can be formed on a base material by apply | coating the composition for photo-alignment film formation on a base material. As a solvent contained in the said composition, the same thing as the solvent contained in the orientation polymer composition mentioned above can be mentioned, It can select suitably according to the solubility of the polymer or monomer which has a photoreactive group.

The content of the polymer or monomer having a photoreactive group in the composition for forming a photo-alignment film can be appropriately adjusted according to the type of polymer or monomer and the thickness of the photo-alignment film for the purpose, but it is preferably at least 0.2 mass%, preferably 0.3 to 10 The range of mass% is more preferable. As long as the properties of the photoalignment film are not significantly impaired, the composition for forming the photoalignment film may contain a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer.

As a method of apply | coating the composition for photo-alignment film formation to a base material, the method similar to the method of apply | coating an orientation polymer composition to a base material is mentioned. As a method of removing a solvent from the apply | coated photo-alignment film formation composition, the method similar to the method of removing a solvent from an orientation polymer composition is mentioned, for example.

In order to irradiate polarized light, the form which irradiates the polarization UV directly to the thing which removed the solvent from the composition for photo-alignment film formation apply | coated on the board | substrate, or the form which irradiates a polarized light and transmits the polarized light from the base material side may be sufficient. Moreover, it is especially preferable if the said polarization is substantially parallel light. The wavelength of the polarized light to be irradiated is preferably in the wavelength range where the photoreactive group of the polymer or monomer having the photoreactive group can absorb light energy. Specifically, UV (ultraviolet) in the wavelength range of 250 to 400 nm is particularly preferable. As a light source used for the said polarization irradiation, ultraviolet light lasers, such as a xenon lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, KrF, ArF, etc. are mentioned, A high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a metal halide lamp are more preferable. Do. These lamps are preferable because the luminous intensity of ultraviolet rays having a wavelength of 313 nm is large. Polarized UV can be irradiated by irradiating light from the light source through an appropriate polarizer. As such a polarizer, polarizing filters, such as a polarizing filter, a Glen Thompson, and a Gran Taylor, and a polarizer of a wire grid type can be used.

On the other hand, when masking at the time of rubbing or polarizing irradiation, you may form some area | region (pattern) from which the direction of liquid crystal orientation differs.

The thickness of the alignment film (alignment film containing an alignment polymer and photoalignment film) is usually in the range of 10 nm to 10000 nm, preferably in the range of 10 nm to 1000 nm, more preferably 500 nm or less, and even more preferably It is the range of 10 nm-100 nm.

A composition (hereinafter sometimes referred to as composition A) containing at least one polymerizable liquid crystal (A) used in the formation of the retardation layer usually contains a solvent, and as a solvent, the same solvent as that contained in the above-described alignment polymer composition These can be mentioned, According to the solubility of a polymeric liquid crystal (A), it can select suitably.

The coating of the composition A is usually performed by a known method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method, or a printing method such as a flexographic method. After application | coating, a dry film is formed by removing a solvent normally on the conditions which the polymerizable liquid crystal (A) contained in the obtained coating film does not superpose | polymerize. As a drying method, a natural drying method, a ventilation drying method, heat drying, and a vacuum drying method are mentioned.

Polymerization of the polymerizable liquid crystal (A) can be performed by a known method for polymerizing a compound having a polymerizable functional group. Specific examples include thermal polymerization and photopolymerization, and photopolymerization is preferred from the viewpoint of ease of polymerization. In the case of polymerizing the polymerizable liquid crystal (A) by photopolymerization, after the polymerizable liquid crystal (A) in the dry film obtained by applying and drying the composition A containing the photopolymerization initiator, the liquid crystal state is maintained. It is preferable to carry out photopolymerization.

Photopolymerization is normally performed by irradiating light to a dry film. The light to be irradiated is suitably selected according to the kind of photoinitiator contained in a dry film, the kind of polymerizable liquid crystal (A) (especially the kind of photopolymerization group which a polymerizable liquid crystal (A) has), and the quantity, specifically, Examples thereof include light and active electron beams selected from the group consisting of visible light, ultraviolet light and laser light. Among them, ultraviolet light is preferred in that it is easy to control the progress of the polymerization reaction and that it can be used widely in the art as a photopolymerization apparatus, and the polymerizable liquid crystal (A) is capable of photopolymerization by ultraviolet light. ) And a type of photopolymerization initiator are preferable. In addition, at the time of superposition | polymerization, superposition | polymerization temperature can also be controlled by irradiating light, cooling a dry film with appropriate cooling means. By employ | adopting such a cooling means, when superposing | polymerizing a polymeric liquid crystal (A) at low temperature, even if the base material used the thing with comparatively low heat resistance, a phase difference layer can be formed suitably. At the time of photopolymerization, a patterned retardation layer can also be obtained by masking, developing, or the like.

The sum total of the thickness of the phase difference layer and polarizing layer in this circular polarizing plate is 10 micrometers or less. 0.5 micrometer or more and 9.5 micrometers or less are preferable, and, as for the thickness of a phase difference layer, 1 micrometer or more and 5 micrometers or less are more preferable. 0.5 micrometer or more and 9.5 micrometers or less are preferable, and, as for the thickness of a polarizing layer, 1 micrometer or more and 5 micrometers or less are more preferable. The thickness of the retardation layer and the polarizing layer can usually be obtained by measurement by an interference film thickness meter, a laser microscope or a stylus film thickness meter.

The polarizing layer contains a dichroic dye. "Dichroic dye" means the pigment | dye which has the property which the absorbance in the long axis direction of a molecule | numerator differs from the absorbance in a short axis direction. As long as it has such a property, a dichroic dye is not restrict | limited, A dye may be sufficient and a pigment may be sufficient. Two or more types of dyes may be used in combination, two or more types of pigments may be used in combination, or dyes and pigments may be used in combination.

It is preferable that a dichroic dye has maximum absorption wavelength ((lambda) MAX) in the range of 300-700 nm. Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes and anthraquinone dyes, and among these, azo dyes are preferable. As an azo dye, a mono azo dye, a bis azo dye, a tris azo dye, a tetrakis azo dye, and a stilbena dye are mentioned, A bis azo dye and a tris azo dye are preferable.

As an azo dye, the compound (henceforth called "compound (1)") represented by Formula (1) is mentioned.

A ¹ (-N = NA ² ) _p -N = NA ³ (1)

[In formula (1), A <^1> and A <^3> represent the monovalent heterocyclic group which may independently have a phenyl group which may have a substituent, the naphthyl group which may have a substituent, or may have a substituent. A ² represents a p-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent heterocyclic group which may have a substituent. p represents the integer of 1-4. when p is an integer of 2 or more, a plurality of A ² may be the same as or different from each other]

Examples of the monovalent heterocyclic group include groups in which heterocyclic compounds such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzoimidazole, oxazole, and benzoxazole are excluded from one hydrogen atom. As a bivalent heterocyclic group, the group remove | excluding two hydrogen atoms from the said heterocyclic compound is mentioned.

A ¹ and A ³ phenyl group, a naphthyl group and a monovalent heterocyclic group, and A ² p- phenylene group, a naphthalene-1,4-Examples of the substituent group and having a carbon number of 1 to 2. The divalent heterocyclic group optionally in the in An alkyl group of 4; C1-C4 alkoxy groups, such as a methoxy group, an ethoxy group, butoxy group; C1-C4 alkyl fluoride groups, such as a trifluoromethyl group; Cyano group; Nitro group; Halogen atom; Substituted or unsubstituted amino groups such as amino groups, diethylamino groups and pyrrolidino groups (substituted amino groups are those having 2 to 8 carbon atoms by combining amino or two substituted alkyl groups having one or two alkyl groups of 1 to 6 carbon atoms with each other; An amino group forming a candiyl group, and an unsubstituted amino group is -NH ₂ ).

Among the compounds (1), compounds represented by any of the following formulas (1-1) to (1-6) are preferable.

In formulas (1-1) to (1-6), B ^{1 to} B ²⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, and a substitution. Or an unsubstituted amino group (a definition of the substituted amino group and an unsubstituted amino group is as described above), a chlorine atom or a trifluoromethyl group.

n1-n4 represent the integer of 0-3 each independently.

If more than n1 is 2, a plurality of B ² may be different even though the same or different,

When n2 is 2 or more, a plurality of B ⁶ may be the same as or different from each other,

When n3 is 2 or more, the plurality of B ⁹ may be the same as or different from each other,

when n4 is 2 or more, a plurality of B ¹⁴ may be the same as or different from each other]

As said anthraquinone pigment | dye, the compound represented by Formula (1-7) is preferable.

Equation (1-7) in a, R ¹ ~R ⁸ are independently a hydrogen _{^{atom, -R x, -NH 2, -NHR}} x, -NR x 2, ^x represents an -SR or a halogen atom.

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

As said oxazone pigment | dye, the compound represented by Formula (1-8) is preferable.

Wherein in (1-8), R ⁹ ~R ¹⁵ independently represent a hydrogen _{^{atom, -R x, -NH 2, -NHR}} x, -NR x 2, ^x represents an -SR or a halogen atom.

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

As said acridine pigment, the compound represented by Formula (1-9) is preferable.

Equation (1-9) in, R ¹⁶ ~R ²³ independently represents a hydrogen _{^{atom, -R x, -NH 2, -NHR}} x, -NR x 2, ^x represents an -SR or a halogen atom.

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

In formula (1-7), formula (1-8) and formula (1-9), a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are mentioned as a C1-C6 alkyl group of R <^x> . Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, toluyl group, xylyl group and naphthyl group.

As said cyanine pigment | dye, the compound represented by Formula (1-10) and the compound represented by Formula (1-11) are preferable.

[In Formula (1-10), D ¹ and D ² independently represent a group represented by any of Formulas (1-10a) to (1-10d).

n5 represents an integer of 1 to 3]

[In formula (2-11), D <^3> and D <^4> represent group represented by either of formula (1-11a)-formula (1-11h) independently of each other.

n6 represents an integer of 1 to 3]

The polarizing layer is a coating layer. In addition, the polarizing layer contains a composition (hereinafter sometimes referred to as composition B) containing one or more polymerizable liquid crystals (hereinafter, sometimes referred to as polymerizable liquid crystals (B)) serving as host compounds in addition to the dichroic dye. It is preferable to apply | coat and form by superposing | polymerizing the polymerizable liquid crystal (B) in the obtained coating film.

It is preferable that the liquid crystal state which a polymeric liquid crystal (B) shows is a smectic phase, and it is more preferable that it is a higher order smectic phase from the point that a polarizing layer with a higher degree of orientation order can be manufactured. "Higher Smectic" means Smectic B, Smectic D, Smectic E, Smectic F, Smectic G, Smectic H, Smectic I, Smectic J, Smectic K Phase and Smectic L phase, and among them, Smectic B phase, Smectic F phase and Smectic I phase are more preferable. In the polarization layer having a high degree of orientation, a Bragg peak derived from a higher order structure such as a hexatic phase or a crystal phase is obtained in X-ray diffraction measurement. The "bragg peak" means the peak derived from the surface periodic structure of molecular orientation, and the polarizing layer whose period interval is 3.0-5.0 microseconds is preferable.

The polymerizable liquid crystal (B) having a smectic phase is called a polymerizable smectic liquid crystal compound. As a polymerizable smectic liquid crystal compound, the compound (henceforth a compound (B) may be mentioned) represented by Formula (B) is mentioned.

U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (B)

[In formula (B), X <^1> , X <^2> and X <^3> represent the ¹ , 4- phenylene group which may have a substituent independently of each other, or the cyclohexane-1, 4- diyl group which may have a substituent. Provided that at least one of X ¹ , X ² and X ³ is a 1,4-phenylene group which may have a substituent. -CH ₂ -constituting the cyclohexane-1,4-diyl group may be substituted with -O-, -S-, or -NR-. R represents a C1-C6 alkyl group or a phenyl group.

Y ¹ and Y ² independently of one another are -CH ₂ CH _2- , -CH ₂ O-, -COO-, -OCOO-, single bond, -N = N-, -CR ^a = CR ^b- , -C≡ C- or CR ^a = N-. R ^a and R ^b independently of one another represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

U ¹ represents a hydrogen atom or a polymerizable group.

U ² represents a polymerizable group.

W ¹ and W ² independently represent a single bond, -O-, -S-, -COO- or OCOO-.

V ¹ and V ² each independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -constituting the alkanediyl group is substituted with -O-, -S- or NH-. May be]

It is preferable that it is a ¹ , 4-phenylene group in which at least 2 of X <^1> , X <^2> and X <^3> may have a substituent.

It is preferable that the 1, 4-phenylene group which may have a substituent is unsubstituted. The cyclohexane-1,4-diyl group which may have a substituent is preferably a trans-cyclohexane-1,4-diyl group which may have a substituent, and the trans-cyclohexane-1,4- which may have a substituent It is preferable that a diyl group is unsubstituted.

As a substituent which the 1, 4- phenylene group which may have a substituent, or the cyclohexane-1, 4-diyl group which may have a substituent optionally has a C1-C4 alkyl group, such as a methyl group, an ethyl group, and a butyl group, a cyano group, and a halogen Atoms are mentioned.

Y ¹ is preferably -CH ₂ CH _2- , -COO- or a single bond, and Y ² is preferably -CH ₂ CH ₂ -or CH ₂ O-.

U ² is a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, and preferably a polymerizable group. It is preferable that U <^1> and U <^2> are a polymerizable group together, and it is preferable that together, it is a photopolymerizable group. The "photopolymerizable group" means a group which can be involved in the polymerization reaction by an active radical or an acid generated from a photopolymerization initiator described later.

Although the photopolymerizable group represented by U <^1> and the polymeric group represented by U <^2> may differ from each other, it is preferable that they are the same kind of group. Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group and oxetanyl group. Especially, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group, and oxetanyl group are preferable, and acryloyloxy group is more preferable.

Examples of the alkanediyl groups represented by V ¹ and V ² are methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group and pentane-1,5 -Diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl group and An icosane-1,20-diyl group is mentioned. V ¹ and V ² are preferably alkanediyl groups having ² to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.

Examples of the substituent which the alkanediyl group optionally has include a cyano group and a halogen atom. The alkanediyl group is preferably unsubstituted, and more preferably an unsubstituted or linear alkanediyl group.

W ¹ and W ² are independently of each other preferably a single bond or O-.

As a compound (B), the compound represented by Formula (B-1)-a formula (B-25) is mentioned. When compound (B) has a cyclohexane-1, 4-diyl group, it is preferable that this cyclohexane-1, 4-diyl group is a trans body.

Among them, formula (B-2), formula (B-3), formula (B-4), formula (B-5), formula (B-6), formula (B-7), formula (B-8) At least 1 sort (s) chosen from the group which consists of a compound represented by Formula (B-13), Formula (B-14), Formula (B-15), Formula (B-16), and Formula (B-17) is preferable. .

The illustrated polymeric liquid crystal (B) can be used individually or in combination. Moreover, when combining 2 or more types of polymerizable liquid crystals, at least 1 type is preferable if it is a polymerizable liquid crystal (B), and it is more preferable if 2 or more types are polymerizable liquid crystals (B). By combining, liquid crystallinity may be temporarily maintained even at the temperature below liquid crystal-crystal phase transition temperature. The mixing ratio in the case of combining two types of polymeric liquid crystal compounds is 1: 99-50: 50 normally, Preferably it is 5: 95-50: 50, More preferably, it is 10: 90-50: 50.

The polymerizable liquid crystal (B) is, for example, Lub et al. Recl. Trav. Chim. It is produced by a known method described in Pays-Bas, 115, 321-328 (1996) or Japanese Patent No. 4719156 and the like.

70-99.9 mass% is preferable with respect to solid content of a composition, and, as for the content rate of the polymeric liquid crystal (B) in the composition B, 80-99.9 mass% is more preferable. When the content ratio of the polymerizable liquid crystal (B) is within the above range, the orientation of the polymerizable liquid crystal (B) tends to be increased. Here, "solid content" means the total amount of the component except the volatile components, such as a solvent, in the composition B.

Although content of the dichroic dye in composition B can be suitably adjusted according to the kind etc. of a dichroic dye, 0.1 mass part or more and 50 mass parts or less are preferable with respect to 100 mass parts of polymeric liquid crystals (B), and 0.1 mass part 20 mass parts or more are more preferable, and 0.1 mass part or more and 10 mass parts or less are further more preferable. If content of a dichroic dye exists in this range, it can superpose | polymerize without disturbing the orientation of a polymeric liquid crystal (B). When there is too much content of a dichroic dye, there exists a possibility that the orientation of a polymeric liquid crystal (B) may be inhibited.

It is preferable that composition B contains a solvent. In general, since the smectic liquid crystal compound has a high viscosity, the composition containing the solvent is easy to apply, and as a result, the polarizing film is often formed easily. As a solvent, the same thing as the solvent contained in the orientation polymer composition mentioned above can be mentioned, According to the solubility of a polymeric liquid crystal (B) and a dichroic dye, it can select suitably.

As for content of a solvent, 50-98 mass% is preferable with respect to the total amount of the composition B. In other words, 2-50 mass% of solid content in the composition B is preferable.

Composition A and / or Composition B preferably contain one or more leveling agents. The leveling agent adjusts the fluidity of the composition B, has a function of making the coating film obtained by applying the composition B more flat, and specifically includes a surfactant. As a leveling agent, at least 1 sort (s) chosen from the group which consists of a leveling agent which has a polyacrylate compound as a main component, and a leveling agent which has a fluorine atom containing compound as a main component is preferable.

Leveling agents mainly composed of polyacrylate compounds include "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK-355", "BYK-358N", and "BYK-358". 361N "," BYK-380 "," BYK-381 ", and" BYK-392 "[BYK Chemie Corporation].

Leveling agents mainly composed of fluorine atom-containing compounds include "Mega Park® R-08", copper "R-30", copper "R-90", copper "F-410" and copper "F-411". , "F-443", "F-445", "F-470", "F-471", "F-477", "F-479", "F-482" and "F-483" [DIC Corporation]; "Suplon® S-381", "S-382", "S-383", "S-393", "SC-101", "SC-105", "KH- 40 "and" SA-100 "[AGC Seiko Chemical Co., Ltd.]; "E1830", "E5844" [Daikin Fine Chemicals Gensho Co., Ltd.]; "F-top EF301", "F-top EF303", "F-top EF351", and "F-top EF352" [Mizubishimateri Alden Shigasei Co., Ltd.] is mentioned.

When composition A and / or composition B contain a leveling agent, 0.05 mass part or more and 5 mass parts or less are preferable, and, as for the content, with respect to 100 mass parts of polymeric liquid crystals, 0.05 mass part or more and 3 mass parts or less are more preferable. . If content of a leveling agent exists in the said range, it will be easy to horizontally align a polymeric liquid crystal, and there exists a tendency for the polarizing layer obtained to become more smooth. If content of the leveling agent with respect to a polymeric liquid crystal exists in the said range, there exists a tendency for a stain to not arise easily to the polarizing layer obtained.

Composition A and / or Composition B preferably contains one or more polymerization initiators. The polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal (B), and the photopolymerization initiator is preferable in that the polymerization reaction can be initiated under lower temperature conditions. Specifically, the photoinitiator which can generate | occur | produce an active radical or an acid by the action of light is mentioned, Especially the photoinitiator which generate | occur | produces a radical by the action of light is preferable.

Examples of the polymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts and sulfonium salts.

As a benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether are mentioned.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl ) Benzophenone and 2,4,6-trimethylbenzophenone.

As the alkylphenone compound, diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholin) Nophenyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethan-1-one, 2-hydroxy -2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1- [4- ( And oligomers of 1-methylvinyl) phenyl] propan-1-one.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide.

As the triazine compound, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2 -(Furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl ] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine Can be.

A commercially available thing can be used for a polymerization initiator. Commercially available polymerization initiators include "Irgacure (registered trademark) 907", "Irgacure (registered trademark) 184", "Irgacure (registered trademark) 651", "Irgacure (registered trademark) 819" "," Irgacure (registered trademark) 250 "," Irgacure (registered trademark) 369 "(Chiba Japan Co., Ltd.); "Sakeol® BZ", "Sakeol® Z", "Sakeol® BEE" (Seikogagaku Co., Ltd.); "Kayakure® BP100" (Nippon Kayaku Co., Ltd.); "Kayacure® UVI-6992" (manufactured by Dowsa); "ADECA OPTOMA SP-152", "ADEKA OPTOMA SP-170" (ADEKA); "TAZ-A" and "TAZ-PP" (Nippon Siberheg Screw); And "TAZ-104" (Sanwa Chemical Co., Ltd.).

When composition A and / or composition B contain a polymerization initiator, the content can be suitably adjusted according to the kind and quantity of polymeric liquid crystal contained in the composition, but 0.1-30 to 100 mass parts of polymeric liquid crystals A mass part is preferable, 0.5-10 mass parts is more preferable, 0.5-8 mass parts is further more preferable. If content of a polymeric initiator is in this range, it can superpose | polymerize without disturbing the orientation of a polymeric liquid crystal (B).

When composition A and / or composition B contain a photoinitiator, the said composition may further contain a photosensitizer. As a photosensitizer, Xanthone compounds, such as xanthone and thioxanthone (for example, 2, 4- diethyl thioxanthone, 2-isopropyl thioxanthone, etc.); Anthracene compounds such as anthracene and an alkoxy group-containing anthracene (eg, dibutoxyanthracene); Phenothiazine and rubrene.

When composition A and / or composition B contain a photoinitiator and a photosensitizer, the polymerization reaction of the polymeric liquid crystal contained in the composition can be promoted more. Although the usage-amount of a photosensitizer can be suitably adjusted according to the kind and quantity of a photoinitiator and a polymeric liquid crystal, 0.1-30 mass parts is preferable with respect to 100 mass parts of polymeric liquid crystals, 0.5-10 mass parts is more preferable, 0.5-8 mass parts is more preferable.

In order to make the polymerization reaction of the polymerizable liquid crystal proceed more stably, the composition A and / or the composition B may contain an appropriate amount of polymerization inhibitor, thereby making it easy to control the progress of the polymerization reaction of the polymerizable liquid crystal.

Examples of the polymerization inhibitor include radical supplements such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (eg, butylcatechol, etc.), pyrogallol, and 2,2,6,6-tetramethyl-1-piperidinyloxy radicals. ; Thiophenols; (beta) -naphthylamine and (beta) -naphthol are mentioned.

When composition A and / or composition B contain a polymerization inhibitor, the content can be suitably adjusted according to the kind and quantity of a polymeric liquid crystal, the usage-amount of a photosensitizer, etc., with respect to 100 mass parts of polymeric liquid crystals 0.1-30 mass parts is preferable, 0.5-10 mass parts is more preferable, 0.5-8 mass parts is further more preferable. If content of a polymerization inhibitor is in this range, it can superpose | polymerize without disturbing the orientation of a polymeric liquid crystal.

A polarizing layer is normally formed by apply | coating composition B on a base material, an orientation film, or a retardation layer, and superposing | polymerizing the polymerizable liquid crystal (B) in the obtained coating film. The method of apply | coating the said composition is not limited. Examples of the alignment film include those mentioned above.

A dry film is formed by apply | coating composition B and drying-drying a solvent on the conditions which the polymerizable liquid crystal (B) contained in the obtained coating film does not superpose | polymerize. As a drying method, a natural drying method, a ventilation drying method, heat drying, and a vacuum drying method are mentioned. In the case where the polymerizable liquid crystal (B) is a polymerizable smectic liquid crystal compound, it is preferable to make the liquid crystal state of the polymerizable smectic liquid crystal compound included in the dry film into a nematic phase (nematic liquid crystal state), and then transfer the smectic phase. Do. In order to form a smectic phase via the nematic phase, for example, the polymerizable smectic liquid crystal compound contained in the dry coat is heated to a temperature above the temperature at which the nematic phase phase transitions to the liquid crystal state of the nematic phase. The method of cooling to the temperature which shows a meticulous liquid crystal state is employ | adopted.

Next, after making the liquid crystal state of the polymeric liquid crystal (B) in a dry film into a smectic phase, the method of photopolymerizing a polymeric liquid crystal (B) while maintaining the liquid crystal state of a smectic phase is demonstrated. In photopolymerization, the light irradiated to a dry film is a kind of photoinitiator contained in the said dry film, a kind of polymerizable liquid crystal (B) (especially a kind of photopolymerizer which the said polymerizable liquid crystal (B) has), and its quantity It selects suitably according to the specific example, The light and active electron beam chosen from the group which consists of visible light, an ultraviolet light, and a laser light are mentioned as the specific example. Among these, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction, and in that one widely used in the art can be used as the photopolymerization apparatus. Therefore, it is preferable to select the kind of polymerizable liquid crystal (B) and photoinitiator contained in the said composition B so that photopolymerization by ultraviolet light may be carried out. In addition, at the time of superposition | polymerization, superposition | polymerization temperature can also be controlled by irradiating light, cooling a dry film with appropriate cooling means. By employ | adopting such a cooling means, when superposing | polymerizing a polymeric liquid crystal (B) at low temperature, even if the base material used the thing with comparatively low heat resistance, a polarizing layer can be formed suitably. When photopolymerizing, it is also possible to obtain the patterned polarizing layer by masking, developing, or the like.

By performing photopolymerization, the polymerizable liquid crystal (B) is polymerized while maintaining a liquid crystal state of a smectic phase, preferably a higher order smectic phase, thereby forming a polarizing layer. The polarizing layer obtained by superposing | polymerizing with a polymeric liquid crystal (B) maintaining the liquid crystal state of a smectic phase is also the polarization which consists of a conventional host guest type polarizing film, ie, a nematic liquid crystal state, according to the action of the said dichroic dye. Compared with the film, there is an advantage that the polarization performance is high. In addition, there is an advantage that the strength is excellent as compared with the application of only a dichroic dye or a lyotropic liquid crystal.

In this circular polarizing plate, the slow axis of the retardation layer and the absorption axis of the polarizing layer are neither parallel nor direct. In order to express the favorable function as a circularly polarizing plate, it is preferable that the angle which the slow axis of a retardation layer and the absorption axis of a polarizing layer make is substantially 45 degrees.

When manufacturing this circular polarizing plate, the order of forming a phase difference layer and a polarizing layer is arbitrary. After forming a retardation layer in a base material, you may form a polarizing layer on a retardation layer. After forming a polarizing layer in a base material, you may form a retardation layer on a polarizing layer. The polarizing layer may be formed on one side of the substrate and the retardation layer may be formed on the other side of the substrate. The alignment film may be formed between the substrate and the retardation layer, the substrate and the polarizing layer, and / or the retardation layer and the polarizing layer.

After forming a retardation layer in a base material, when forming a polarizing layer on a retardation layer, you may form a protective layer on a retardation layer as needed, and may form a polarizing layer on a protective layer. An alignment film may be formed on the protective layer, and a polarizing layer may be formed thereon. In addition, after forming a polarizing layer in a base material, you may form a protective layer on a polarizing layer, and may form a phase difference layer on it. An alignment film may be formed on the protective layer, and a retardation layer may be formed thereon.

The protective layer is usually an acrylic oligomer or polymer composed of polyfunctional acrylate (methacrylate), urethane acrylate, polyester acrylate, epoxy acrylate, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylpyrrolidone It is preferable that it is formed from the composition for protective layer formation containing water-soluble polymers, such as starch, methylcellulose, carboxymethylcellulose, and sodium alginate, and a solvent.

Solvents contained in the composition for forming a protective layer include the same solvents as described above, and among these, at least one solvent selected from the group consisting of water, an alcohol solvent and an ether solvent dissolves the layer forming the protective layer. This is preferable in that there is no. Examples of the alcohol solvent include methanol, ethanol, butanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether. Ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate are mentioned as an ether solvent. Especially, ethanol, isopropyl alcohol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are preferable.

The thickness of a protective layer is 20 micrometers or less normally. 0.5 micrometer or more and 9.5 micrometers or less are preferable, and, as for the thickness of a protective layer, 1 micrometer or more and 5 micrometers or less are more preferable. The thickness of a protective layer can be normally calculated | required by the measurement by an interference film thickness meter, a laser microscope, or a stylus film thickness meter.

The circular polarizing plate may further have an adhesive layer on the surface of the retardation layer or the polarizing layer formed on the surface of the circular polarizing plate. Moreover, you may have a primer layer between retardation layer or a polarizing layer, and an adhesive layer.

The pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive, the pressure-sensitive adhesive usually contains a polymer, and may contain a solvent.

Examples of the polymers include acrylic polymers, silicone polymers, polyesters, polyurethanes, and polyethers. Among them, acrylic pressure sensitive adhesives containing acrylic polymers are excellent in optical transparency, maintain proper wettability and cohesive force, have excellent adhesiveness, and also have high weather resistance and heat resistance, and thus they may float or peel off under conditions of heating or humidification. It is preferable because a peeling problem such as this is unlikely to occur.

Examples of the acrylic polymer include (meth) acrylates (hereinafter, acrylates and methacrylates) in which the alkyl group of the ester moiety is an alkyl group having 20 or less carbon atoms such as methyl group, ethyl group or butyl group. Methacrylic acid may be named generically (meth) acrylic acid), and the copolymer of the (meth) acrylic-type monomer which has functional groups, such as (meth) acrylic acid and hydroxyethyl (meth) acrylate, is preferable.

Since the adhesive containing such a copolymer is excellent in adhesiveness and can be peeled relatively easily without causing debris or the like on the display device even when peeling after bonding to the display device, it is preferable. 25 degrees C or less is preferable, and, as for the glass transition temperature of the said acrylic polymer, 0 degrees C or less is more preferable. It is preferable that the weight average molecular weight of such an acrylic polymer is 100,000 or more.

As said solvent, the solvent etc. which were mentioned as an example of the solvent of the said oriented polymer composition are mentioned, for example.

In addition, the pressure-sensitive adhesive may contain a light diffusing agent. The light diffusing agent is for imparting light diffusivity to the pressure-sensitive adhesive layer, and may be a fine particle having a refractive index different from that of the polymer included in the pressure-sensitive adhesive layer, and the light diffusing agent may be fine particles made of an inorganic compound or fine particles made of an organic compound (polymer). Can be mentioned. Since the base polymer including the acryl-based polymer constituting the pressure-sensitive adhesive layer exhibits a refractive index of about 1.4, the light diffusing agent may be appropriately selected from those having a refractive index of about 1-2. The refractive index difference of the polymer which an adhesive contains as an active component and a light-diffusion agent is 0.01 or more normally, and it is suitable to set it as 0.01 or more and 0.5 or less from a viewpoint of the brightness and visibility of a liquid crystal display device. It is preferable that the microparticles | fine-particles used as a light-diffusion agent are spherical and it is also close to monodispersion, For example, the microparticles | fine-particles in which the average particle diameter is about 2-6 micrometers are used suitably.

Refractive index is measured by a general minimum polarization method or Abbe refractometer.

Examples of the fine particles made of the inorganic compound include aluminum oxide (refractive index 1.76), silicon oxide (refractive index 1.45), and the like.

Moreover, as microparticles | fine-particles which consist of an organic compound (polymer), for example, melamine beads (refractive index 1.57), polymethyl methacrylate beads (refractive index 1.49), methyl methacrylate / styrene copolymer resin beads (refractive index 1.50-1.59), 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), silicone resin beads (refractive index 1.46), and the like.

The compounding amount of the light diffusing agent can be appropriately determined in consideration of the haze value required for the pressure-sensitive adhesive layer to which it is dispersed, the brightness of the liquid crystal display device to which it is applied, and the like. Generally, 3 to 100 parts by weight of the resin constituting the pressure-sensitive adhesive layer is used. It is about 30 weight part.

The haze value of the pressure-sensitive adhesive layer in which the light diffusing agent is dispersed is preferably in the range of 20 to 80% from the viewpoint of ensuring the brightness of the liquid crystal display device to which the circularly polarizing plate having the pressure-sensitive adhesive layer is applied and making it difficult to cause bleeding or blur on the display. Do. The haze value is a value expressed by (diffusion transmittance / total light transmittance) × 100 (%), and is measured according to JIS K 7105.

The thickness of the pressure-sensitive adhesive layer is determined depending on the adhesion and the like, and is not particularly limited, but is usually about 1 to 40 μm. In order to obtain a circularly polarizing plate provided with a thin pressure-sensitive adhesive layer without impairing properties such as workability or durability, the thickness of the pressure-sensitive adhesive layer is preferably about 3 to 25 µm. Moreover, when the thickness of an adhesive layer is about 3-25 micrometers, the brightness | luminance in the case where the liquid crystal display device is seen from the front view or obliquely can be maintained, and the blur and blur on a display can become difficult to produce.

The primer layer usually contains a transparent resin and is formed of a transparent resin solution. When forming an adhesive layer, a primer layer can suppress the defect of a retardation layer or a polarizing layer. As transparent resin, what is excellent in coatability and excellent in transparency and adhesiveness after primer layer formation is preferable.

Examples of the solvent for the transparent resin solution include aromatic hydrocarbon solvents such as benzene, toluene, and xylene depending on the transparency of the transparency; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Ester solvents such as ethyl acetate and isobutyl acetate; Chlorinated hydrocarbon solvents such as methylene chloride, trichloroethylene and chloroform; Although general organic solvents, such as alcohol solvents, such as ethanol, 1-propanol, 2-propanol, and 1-butanol, can be used, if a primer layer is formed using the transparent resin solution containing an organic solvent, Since it may affect, it is preferable to form a primer layer using the solution which uses water as a solvent.

An epoxy resin is mentioned as said transparent resin. The epoxy resin may be a one-liquid curing type or may be a two-liquid curing type. Water-soluble epoxy resins are particularly preferred. As a water-soluble epoxy resin, the polyamide epoxy resin obtained by making epichlorohydrin react with the polyamide polyamine obtained by reaction of polyalkylene polyamine like diethylene triamine and triethylene tetramine, and dicarboxylic acid like adipic acid Can be mentioned. Commercially available products of such polyamide epoxy resins include "Sumireze Resin (registered trademark) 650 (30)" and "Semireze Resin (registered trademark) 675" (registered trademark) sold by Smica Chemicals Co., Ltd. Can be.

When using a water-soluble epoxy resin as said transparent resin, in order to improve applicability | paintability further, it is preferable to use together other water-soluble resins, such as a polyvinyl alcohol-type resin. The polyvinyl alcohol-based resin is modified polyvinyl alcohol such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, acetacetyl group-modified polyvinyl alcohol, methylol group-modified polyvinyl alcohol, amino group-modified polyvinyl alcohol Alcoholic water may be sufficient. As a commercially available product of suitable polyvinyl alcohol-type resin, "KL-318" (brand name) etc. which are polyvinyl alcohol containing the anionic group sold by Kuraray Co., Ltd. are mentioned.

When forming a primer layer from the solution containing water-soluble epoxy resin, it is preferable to make an epoxy resin into the range of about 0.2-1.5 weight part with respect to 100 weight part of water. Moreover, when mix | blending polyvinyl alcohol-type resin with this solution, it is preferable to make the quantity into about 1-6 weight part with respect to 100 weight part of water. It is preferable to make the thickness of a primer layer into the range of about 0.1-10 micrometers.

The formation method of a primer layer is not restrict | limited, Well-known various coating methods, such as the direct gravure method, the reverse gravure method, the die coat method, the comma coat method, the bar coat method, can be used.

The pressure-sensitive adhesive layer can be formed by applying the pressure-sensitive adhesive to the surface of the retardation layer, the polarizing layer or the primer layer, and drying the coating, and applying the pressure-sensitive adhesive to the release-treated surface of the film subjected to the release treatment and drying the adhesive. After forming an adhesive layer, the film which has this adhesive layer can also be formed by the method of bonding to the surface of a phase difference layer, a polarizing layer, or a primer layer so that an adhesive layer side may become a bonding surface. It is preferable to perform a corona discharge process on the surface of the primer layer in which an adhesive layer is formed previously. Thereby, adhesiveness of a primer layer and an adhesive layer can be improved further.

As a method of apply | coating an adhesive, the method similar to what was illustrated as a method of apply | coating an orientation polymer composition to a base material is mentioned, for example. As a method of removing a solvent from the apply | coated adhesive, the method similar to the method of removing a solvent from an orientation polymer composition is mentioned, for example.

The peeling strength of this circularly polarizing plate which has an adhesive layer on the surface is measured by the following formula.

After cutting a test piece having a width of 25 mm x a length of about 200 mm from the circularly polarizing plate having the pressure-sensitive adhesive layer on the surface, and bonding the pressure-sensitive adhesive surface to a glass plate, one end of the test piece in the longitudinal direction (a width of 25 mm) was used using a tensile tester. Side), at a crosshead speed of 200 mm / min in a temperature of 23 ° C. and a relative humidity of 60%, JIS K 6854-1: 1999 "Adhesive-peel adhesion strength test method-Part 1: 90 degree peeling test in conformity with "90 degree peeling".

In the circularly polarizing plate which has a base material, a 1st alignment film, a polarizing layer, a 2nd alignment film, a retardation layer, and an adhesive layer in this order, the peeling strength (F1) of a base material and a 1st alignment film of a 1st alignment film and a polarizing layer It is preferable that it is lower than peeling strength (F2), peeling strength (F3) of a 2nd orientation film and a phase difference layer, and peeling strength (F4) of a phase difference layer and an adhesive layer. Peeling strength F1 can be adjusted with a base material and a 1st orientation film.

For example, the base material which has a functional group which forms a chemical bond with an alignment film on the surface tends to increase the peeling strength (F1) of a base material and a 1st alignment film. Therefore, as a base material for making peeling strength (F1) low, the base material with few functional groups on the surface is preferable, and the base material which did not perform the surface treatment which forms a functional group on the surface is preferable.

Moreover, the alignment film which has a functional group which forms a chemical bond with a base material tends to increase the peeling strength (F1) of a base material and a 1st alignment film. Therefore, as an oriented film for making peeling strength F1 low, the oriented film with few functional groups which form a chemical bond with a base material is preferable. In addition, in order to make (F1) low, it is preferable that the reagent which crosslinks a base material and an orientation film is not contained in an orientation polymer composition or the composition for photo-alignment film formation, and it is preferable that components, such as a solvent which melt | dissolves a base material, are not included. Do. There exists a tendency for peeling strength (F1) of a base material and a 1st oriented film to become large by melt | dissolving the surface of a base material with an orientation polymer composition or the composition for photo-alignment film formation.

In order to raise peeling strength (F2), (F3), and (F4), what is necessary is just to form a chemical bond between a 1st orientation film, a polarizing layer, a 2nd orientation film, a retardation layer, and a retardation layer and an adhesive layer.

The circularly polarizing film which has an adhesive layer can be obtained by removing a base material from the circularly polarizing plate which has an adhesive layer on the surface. Arbitrary methods are mentioned as a method of removing a base material.

The thickness of the circularly polarizing film which has an adhesive layer is 5 micrometers or more and 15 micrometers or less normally, Preferably they are 5 micrometers or more and 10 micrometers or less. The thickness of the circularly polarizing film having the pressure-sensitive adhesive layer can usually be determined by measurement by an interference film thickness meter, a laser microscope, or a stylus film thickness meter.

Next, the method of manufacturing this circularly polarizing plate continuously is demonstrated. As a suitable method of manufacturing such a circularly polarizing plate continuously, the method by the roll-to-roll form is mentioned.

Specifically, (1) the process of preparing the roll by which the base material is wound up to the core,

(2) a step of continuously sending out the substrate from the roll,

(3) forming an alignment film on the substrate continuously;

(4) Process of apply | coating composition A on the said oriented film and forming retardation layer continuously,

(5) process of continuously forming a protective layer on the retardation layer of the roll obtained by said (4),

(6) Process of apply | coating an oriented film on the protective layer obtained by said (5), and forming continuously,

(7) Process of apply | coating composition B on the orientation film obtained by said (6), and continuously forming a polarizing layer,

(8) a step of bonding the film with the pressure-sensitive adhesive layer on the polarizing layer obtained in the above (7) so that the pressure-sensitive adhesive layer side becomes the bonding surface;

(9) The method of winding up the circularly obtained polarizing plate continuously to the 2nd core and obtaining a 2nd roll is mentioned one by one. In addition, process (5) and (8) may be omitted as needed.

Moreover, the process of preparing the roll by which the base material is wound up to the core,

(2a) a step of continuously sending out the substrate from the roll,

(3a) a step of continuously forming an alignment film on the substrate;

(4a) Process of apply | coating composition B on the said oriented film, and forming a polarizing layer continuously,

(5a) Process of continuously forming a protective layer on the polarizing layer of the roll obtained by said (4a),

(6a) Process of apply | coating an oriented film on the protective layer obtained by said (5a), and forming continuously,

(7a) Process of apply | coating composition A on the oriented film obtained by said (6a), and forming retardation layer continuously,

(8a) The process of bonding the film which has an adhesive layer on the phase difference layer obtained by said (7a) so that an adhesive layer side may become a bonding surface,

(9a) The method of winding the circularly polarizing plate obtained continuously in the 2nd core and obtaining a 2nd roll is also performed sequentially. In addition, process (5a) and (8a) may be omitted as needed.

Moreover, (1b) process of preparing the roll by which the base material is wound up to the core,

(2b) a step of continuously sending out the substrate from the roll,

(3b) a step of continuously forming an alignment film on the substrate;

(4b) process of apply | coating composition A on the said oriented film, and forming retardation layer continuously,

(5b) Process of apply | coating an oriented film to the surface opposite to the retardation layer of the roll obtained by said (4b), and forming continuously,

(6b) Process of apply | coating composition B on the orientation film obtained by said (5b), and continuously forming a polarizing film,

(7b) The method of winding up the circularly obtained polarizing plate continuously in the 2nd core and obtaining a 2nd roll is also mentioned sequentially.

Moreover, (1c) process of preparing the roll by which the transparent base material is wound up to the core,

(2c) process of sending out the said transparent base material continuously from the said roll,

(3c) a step of continuously forming an alignment film on the transparent substrate,

(4c) Process of apply | coating the composition containing composition B on the said oriented film, and continuously forming a polarizing layer,

(5c) Process of continuously forming an oriented film in the surface opposite to the polarizing layer of the roll obtained by said (4c),

(6c) Process of apply | coating composition A on the oriented film obtained by said (5c), and forming retardation layer continuously,

(7c) The method of winding up the circularly polarizing plate obtained continuously to the 2nd core and obtaining a 2nd roll is also mentioned one by one.

A schematic diagram of the circular polarizing plate seen in FIG. 1 is shown. Fig. 1A is a circular polarizing plate in which a base material, a phase difference layer, and a polarizing layer are laminated in this order. Fig. 1B is a circular polarizing plate in which a substrate, a polarizing layer, and a retardation layer are laminated in this order.

The circular polarizing plate can be used for various display devices. In addition, the circularly polarizing plate which has an adhesive layer on the surface can be used for manufacture of various display apparatuses. Specifically, by bonding the circularly polarizing plate having the pressure-sensitive adhesive layer on the surface to the display surface of the display device via the pressure-sensitive adhesive layer, the display device having the circularly polarizing plate can be obtained, and the circularly polarized light of the present invention is removed by removing the substrate. A display device having a circularly polarized film provided with a film can be obtained.

The display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. As the display device, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, a touch panel display device, an electron emission display device (for example, an electric field emission display device (FED), a surface electric field) Emission display device (SED), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device (eg grating light valve (GLV) display device, display with digital micromirror device (DMD)) Device) and a piezoelectric ceramic display, etc. The liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device and a projection type liquid crystal display device. These display devices may be display devices for displaying two-dimensional images, or stereoscopic display devices for displaying three-dimensional images. Hi it can be effectively used in an organic electroluminescence (EL) display device or an inorganic electroluminescence (EL) display device of the display device.

2 is a schematic view showing a liquid crystal display device 10 that is one of the display devices of the present invention. The liquid crystal layer 15 is placed between two substrates 12a and 12b. The color filter 13 is arrange | positioned at the liquid crystal layer 15 side of the board | substrate 12a. The color filter 13 is disposed at a position facing the pixel electrode 20 with the liquid crystal layer 15 interposed therebetween, and the black matrix 18 is disposed at a position facing the boundary between the pixel electrodes. The transparent electrode 14 covers these. An overcoat layer may be provided between the color filter 13 and the transparent electrode 14.

The thin film transistor 19 and the pixel electrode 20 are regularly arranged on the liquid crystal layer 15 side of the substrate 12b. The pixel electrode 20 is disposed at a position facing the color filter 13 with the liquid crystal layer 15 therebetween. An interlayer insulating film 16 having a connection hole (not shown) is disposed between the thin film transistor 19 and the pixel electrode 20.

As the board | substrate 12a and the board | substrate 12b, a glass substrate and a plastic substrate are mentioned. When manufacturing the color filter 13 and thin film transistor 19 formed on these board | substrates, when heating to high temperature is necessary, it is preferable that the board | substrate 12a and the board | substrate 12b are glass substrates.

As the thin film transistor 19, there may be mentioned a high temperature polysilicon transistor formed on a quartz substrate, a low temperature polysilicon transistor formed on a glass substrate, and an amorphous silicon transistor formed on a glass substrate or a plastic substrate. For miniaturization of the liquid crystal display device, a driver IC may be formed on the substrate 12b.

The liquid crystal layer 15 is disposed between the transparent electrode 14 and the pixel electrode 20. The spacer 21 is formed in the liquid crystal layer 15 so as to keep the distance between the substrate 12a and the substrate 12b constant. An alignment film for orienting the liquid crystal compound included in the liquid crystal layer 15 in a desired direction may be disposed on the surface of the layers formed on the substrate 12a and the substrate 12b in contact with the liquid crystal layer 15.

Each member includes a substrate 12a, a color filter 13 and a black matrix 18, a transparent electrode 14, a liquid crystal layer 15, a pixel electrode 20, an interlayer insulating film 16 and a thin film transistor 19, And the substrate 12b in this order.

The circularly polarizing plate 11a and the circularly polarizing plate 11b are laminated on the outer side of the substrate 12a and the substrate 12b sandwiching the liquid crystal layer 15. The backlight unit 17 which is a light emitting source is arrange | positioned outside this circular polarizing plate 11b. The backlight unit 17 includes a light source, a light guide, a reflector, a diffusion sheet, and a viewing angle adjustment sheet. As a light source, various light sources, such as an electroluminescence (EL), a cold cathode tube, a hot cathode tube, a light emitting diode (LED), a laser light source, a mercury lamp, can be used.

3 is a schematic diagram showing an organic EL display device 30 that is one of the display devices of the present invention. The organic EL display device 30 of the present invention shown in Fig. 3A includes the circular polarizing plate 31, and is formed on a substrate 32 on which a pixel electrode 34 is formed through an interlayer insulating film 33. The light emitting layer 35 and the cathode electrode 36 are laminated. The circularly polarizing plate 31 is disposed on the opposite side to the light emitting layer 35 with the substrate 32 therebetween. The light emitting layer 35 emits light by applying a positive voltage to the pixel electrode 34 and a negative voltage to the cathode electrode 36, and applying a direct current between the pixel electrode 34 and the cathode electrode 36. The light emitting layer 35 includes an electron transporting layer, a light emitting layer, a hole transporting layer, and the like. Light emitted from the light emitting layer 35 passes through the pixel electrode 34, the interlayer insulating film 33, the substrate 32, and the circular polarizing plate 31.

In order to manufacture the organic EL display device 30, first, a thin film transistor 38 is formed on a substrate 32 in a desired shape. The interlayer insulating film 33 is formed, and then the pixel electrode 34 is formed by the sputtering method and patterned. Thereafter, the light emitting layer 35 is laminated.

Subsequently, the circular polarizing plate 31 is provided on the surface opposite to the surface on which the thin film transistor 38 of the substrate 32 is provided. In that case, the quarter wavelength layer of the circular polarizing plate 31 is disposed so as to be on the substrate 32 side.

Examples of the substrate 32 include ceramic substrates such as sapphire glass substrates, quartz glass substrates, soda glass substrates, and alumina; Metal substrates such as copper; Plastic substrates; Although not shown, a thermally conductive film may be formed on the substrate 32. Examples of the thermal conductive film include diamond thin films (DLC and the like). When the pixel electrode 34 is a reflective type, light is emitted in a direction opposite to the substrate 32. Therefore, not only a transparent material but also a non-transmissive material, such as stainless steel, can be used. The substrate may be formed singly or may be formed as a laminated substrate by joining a plurality of substrates with an adhesive. In addition, these board | substrates are not limited to what is plate-shaped, A film may be sufficient.

As the thin film transistor 38, for example, a polycrystalline silicon transistor or the like may be used. The thin film transistor 38 is provided at the end of the pixel electrode 34, and its size is about 10 to 30 μm. On the other hand, the size of the pixel electrode 34 is about 20 µm x 20 µm to 300 µm x 300 µm.

Wiring electrodes of the thin film transistors 38 are provided on the substrate 32. The wiring electrode has a low resistance and has a function of electrically connecting with the pixel electrode 34 to suppress the resistance value. Generally, the wiring electrode has Al, Al, and transition metals (except Ti), Ti, or nitride. Any one or two or more kinds of titanium (TiN) are used.

An interlayer insulating film 33 is provided between the thin film transistor 38 and the pixel electrode 34. The interlayer insulating film 33 is formed by sputtering or vacuum vapor deposition of inorganic materials such as silicon oxide and silicon nitride such as SiO ₂ , and silicon oxide layer formed of SOG (spin-on-glass), photoresist, polyimide and acrylic. As long as it has insulation, such as a coating film of resin materials, such as resin, any may be sufficient.

Ribs 39 are formed on the interlayer insulating film 33. The rib 39 is disposed at the periphery (between adjacent pixels) of the pixel electrode 34. Examples of the material for the ribs 39 include acrylic resins and polyimide resins. The thickness of the ribs 39 is preferably 1.0 µm or more and 3.5 µm, more preferably 1.5 µm or more and 2.5 µm or less.

Next, an EL element composed of the pixel electrode 34, the light emitting layer 35, and the cathode electrode 36 will be described. The light emitting layer 35 has at least one hole transporting layer and a light emitting layer, respectively, and has, for example, an electron injection transporting layer, a light emitting layer, a hole transporting layer and a hole injection layer sequentially.

Examples of the pixel electrode 34 include ITO (tin doped indium oxide), IZO (zinc doped indium oxide), IGZO, ZnO, SnO ₂ , In ₂ O ₃ , and the like, and ITO and IZO are particularly preferable. The thickness of the pixel electrode 35 should just have a thickness more than a fixed enough to perform hole injection, and it is preferable to set it as about 10-500 nm.

The pixel electrode 34 can be formed by vapor deposition (preferably sputtering). The sputtering gas is not particularly limited, and an inert gas such as Ar, He, Ne, Kr, and Xe or a mixed gas thereof may be used.

As the constituent material of the cathode electrode 36, metal elements such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn and Zr may be used. In order to improve the operational stability, it is preferable to use a two- or three-component alloy system selected from the illustrated metal elements. Examples of the alloy system include Ag.Mg (Ag: 1 to 20 at%), Al.Li (Li: 0.3 to 14 at%), In.Mg (Mg: 50 to 80 at%), and Al.Ca (Ca: 5 -20 at%), etc. are preferable.

The cathode electrode 36 is formed by a vapor deposition method, a sputtering method, or the like. The thickness of the cathode electrode 37 is preferably 0.1 nm or more, preferably 1 to 500 nm or more.

The hole injection layer has a function of easily injecting holes from the pixel electrode 34, and the hole transport layer has a function of transporting holes and a function of interrupting electrons, and is also called a charge injection layer or a charge transport layer.

The thickness of the light emitting layer, the thickness of the hole injecting layer and the hole transporting layer, and the thickness of the electron injecting transporting layer are not particularly limited and may vary depending on the formation method, but are preferably about 5 to 100 nm. Various organic compounds can be used for the hole injection layer and the hole transport layer. The vacuum evaporation method can be used in that a homogeneous thin film can be formed for formation of a hole injection transport layer, a light emitting layer, and an electron injection transport layer.

As the light emitting layer 35, light emission from singlet excitons (fluorescence), light emission from triplet excitons (phosphorescence), light emission from singlet excitons (fluorescence) and light emission from triplet excitons ( Phosphorescent), including those formed by organic matter, those formed by organic matter and those formed by inorganic matter, materials of polymers, materials of low molecules, materials of polymers and materials of low molecules, and the like. It is available. However, the present invention is not limited thereto, and the light emitting layer 35 using various kinds of materials known for EL elements can be used for the organic EL display device 30.

A desiccant (not shown) is disposed in the space between the cathode electrode 36 and the sealing layer 37. This is because the light emitting layer 35 is weak in humidity. Moisture is absorbed by the desiccant to prevent deterioration of the light emitting layer 35.

The organic EL display device 30 of the present invention shown in Fig. 3B has the circular polarizing plate 31, and is formed on the substrate 32 on which the pixel electrode 34 is formed through the interlayer insulating film 33. The light emitting layer 35 and the cathode electrode 36 are stacked. The sealing layer 37 is formed on the cathode electrode, and the circularly polarizing plate 31 seen on the opposite side to the substrate 32 is disposed. Light emitted from the light emitting layer 35 passes through the cathode electrode 36, the sealing layer 37, and the circular polarizing plate 31.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, "%" and "parts" are% by mass and parts by mass unless otherwise specified.

Example 1

[Preparation of composition for phase difference layer formation]

The following components were mixed and the mixture obtained was stirred at 80 degreeC for 1 hour, and the composition for retardation layer formation was obtained.

Compound A1 and Compound A2 were synthesized by the method described in JP 2010-31223 A.

Compound A1 (80 parts):

Compound A2 (20 parts):

Polymerization initiator (6 parts): 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (irgacure 369; manufactured by Chivas Specialty Chemicals)

Leveling agent (0.1 parts): polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)

Solvent: Mixed solvent of o-xylene (300 parts) and cyclopentanone (130 parts)

[Preparation of Composition for Forming Photoalignment Film]

The following component was mixed, and the obtained mixture was stirred at 80 degreeC for 1 hour, and the composition for photoalignment film formation was obtained.

Photo-Oriented Materials (Part 5):

Solvent (95 parts): Cyclopentanone

[Preparation of Composition for Polarizing Layer Formation]

The following component was mixed, and the obtained mixture was stirred at 80 degreeC for 1 hour, and the composition for polarizing layer formation was obtained. Compound B1 and Compound B2 were synthesized by the method described in Japanese Patent No. 4719156.

Compound B1 (Compound (B-6); 75 parts)

Compound B2 (Compound (B-7); 25 parts)

Dichroic dyes;

2.5 parts of bis azo compound (1-1-1)

2.5 parts of bis azo compound (1-1-2)

Bis azo compound (1-4-1) 2.5 parts

Polymerization initiator; 6 parts of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (irgacure 369; manufactured by Chivas Specialty Chemicals)

Leveling agents; 1.5 parts of polyacrylate compounds (BYK-361N; manufactured by BYK-Chemie)

solvent; 250 parts cyclopentanone

[Measurement of Phase Transition Temperature]

The obtained composition for polarizing layer formation was apply | coated on glass, and it dried, and produced the sample for a measurement. When the phase transition temperature was confirmed by texture observation by a polarization microscope, after temperature rising to 140 degreeC, the phase transition from 108 degreeC to a nematic phase at the time of temperature-fall, the phase transition from a 101 degreeC to a smectic A phase at 76 degreeC Phase transition to Smectic B phase was confirmed, respectively.

[Preparation of Composition for Adhesive Formation]

The following components were mixed at 55 degreeC under nitrogen atmosphere, and the acrylic resin was obtained.

Butyl acrylate 70 parts

20 parts methyl acrylate

1.0 parts acrylic acid

Initiator: 0.2 parts of azobisisobutyronitrile

Solvent (80 parts): ethyl acetate

In addition, 0.5 parts of collonate L (75% ethyl acetate solution of the trimethylolpropane addition product of tolylene diisocyanate, the number of isocyanate groups in 1 molecule: 3, the Nippon Urethane Co., Ltd. product), a silane coupling agent X-12-981 ( 0.5 parts of Shin-Etsu Silicone Co., Ltd.) were mixed, and ethyl acetate was added so that total solid content concentration might be 10%, and it was set as the composition for adhesive formation. The obtained pressure-sensitive adhesive forming composition was applied to a release treated surface of a release-treated polyethylene terephthalate film (manufactured by Lintech Co., Ltd.) using an applicator so as to have a thickness of 10 μm after drying, and dried at 100 ° C. for 1 minute to carry an adhesive. The film (1) was obtained.

[Production of Circular Polarizer Plate]

1. Formation of alignment layer for polarizing layer

KC4UY (TAC film, manufactured by Konica Minolta Co., Ltd.), which is a cellulose film, was used as the transparent base film. The said photo-alignment film formation composition was apply | coated on this film by the bar coat method, and it heat-dried for 1 minute in 60 degreeC drying oven. The obtained dry film was subjected to polarization UV irradiation treatment to form a first alignment film. The polarization UV treatment was performed under a condition that the intensity measured at a wavelength of 365 nm was 100 mJ using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.). In addition, the polarization direction of polarization UV was made to be 0 degrees with respect to the slow axis of a retardation layer.

2. Formation of Polarizing Layer

The composition for polarizing layer formation was apply | coated by the bar coat method on the formed 1st orientation film, and it heat-dried for 1 minute in 120 degreeC drying oven, and cooled to room temperature. Using a UV irradiation apparatus (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.), a polarizing layer was formed by irradiating a dry film with ultraviolet light at an exposure dose of 1200 mJ / cm 2 (365 nm standard). It was 1.8 micrometers when the thickness of the obtained polarizing layer was measured with the laser microscope (OLS3000 by Olympus Corporation).

3. Formation of protective layer

50 parts of dipentaerythritol hexaacrylate (manufactured by Aronix M-403 Toagosei Co., Ltd.), 50 parts of acrylate resin (manufactured by Evercryl 4858 Daicel UBC Co., Ltd.) and 2-methyl-1 [4 on the formed polarizing layer. A solution (composition for forming a protective layer) prepared by dissolving 3 parts of-(methylthio) phenyl] -2-moripolynopropan-1-one (irgacure 907; manufactured by Chivas Specialty Chemicals) in 250 parts of isopropanol It applied by the coating method and heat-dried for 1 minute in 50 degreeC drying oven. The protective layer was formed on the said polarizing layer by irradiating an ultraviolet-ray with an exposure amount of 400 mJ / cm <2> (365 nm standard) using the UV irradiation apparatus (SPOT CURE SP-7; Ushio Denki Corporation make) to the obtained dry film.

4. Formation of alignment film for retardation layer

The photo-alignment film-forming composition was applied on the formed protective layer by a bar coat method and dried by heating for 1 minute in a drying oven at 60 ° C. The polarizing UV irradiation process was performed to the obtained dry film, and the 2nd alignment film was formed. The polarization UV treatment was performed under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.). In addition, the polarization direction of polarization UV was performed so that it might become 45 degrees with respect to the absorption axis of a polarizing layer.

5. Formation of Retardation Layer

The composition for phase difference layer forming was apply | coated by the bar coat method on the formed 2nd orientation film, and it heat-dried for 1 minute in 120 degreeC drying oven, and cooled to room temperature. The retardation layer was formed by irradiating the obtained dry film with the ultraviolet-ray of 1000 mJ / cm <2> (365 nm reference | standard) of exposure amount using UV irradiation apparatus (SPOT CURE SP-7; Ushio Denki Co., Ltd. product). It was 2.0 micrometers when the thickness of the obtained retardation layer was measured with the laser microscope (OLS3000 by Olympus Corporation).

In this way, a broadband circular polarizing plate could be produced. It was 45 micrometers when the total thickness of this circularly polarizing plate was measured with the contact film thickness meter.

[Evaluation of Circular Polarizer Plate]

1. X-ray diffraction measurement

About the obtained polarizing layer, X-ray-diffraction measurement was performed with the X-ray-diffraction apparatus X 'Pert PRO MPD (made by SPECTLESS Corporation). Using Cu as a target, X-rays generated under conditions of X-ray tube current of 40 mA and X-ray tube voltage of 45 kV are subjected to a rubbing direction (preliminarily, the rubbing direction of the alignment layer under the polarizing layer is determined) through a fixed divergence slit 1/2 °. It was made to enter and measured at 2θ = 0.01671 ° steps in the range of scanning range 2θ = 4.0 to 40.0 °. As a result, a sharp diffraction peak of peak half width (FWHM) = about 0.29 ° was obtained near 2θ = 20.12 °. In addition, the same result was obtained even when X-rays were incident on the rubbing vertical direction. The order period (d) found at the peak position was about 4.4 Hz, indicating that a structure reflecting the higher order smectic phase was formed.

2. Measurement of reflectance

In order to confirm the usefulness of a circularly polarizing plate, reflectance was measured as follows. The phase difference layer and the reflecting plate (mirror surface aluminum plate) of the produced circular polarizing plate were bonded together using the adhesive, and the measurement sample was prepared.

Using a spectrophotometer (UV-3150 manufactured by Shimadzu Seisakusho Co., Ltd.), light having a wavelength of 400 to 700 nm in 2 nm steps was incident on the measurement sample at 12 ° in the normal direction, and the reflectance of the reflected light was measured. did. When reflectance is calculated by measuring the reflectance as 100% when only the reflecting plate is measured without arranging the circularly polarizing plate, the reflectance of light in the wavelength range of 400 to 700 nm is about 1 to 10%. It was found that to get.

Example 2

In the same manner as in Example 1, a first alignment film (the polarization direction of polarized light UV was 45 ° with respect to the long side of the base film) was formed on one surface of the transparent base film, and a phase difference layer was formed on the photoalignment film. After forming a protective layer on the retardation layer, a second alignment film (the polarization direction of the polarization UV is 0 ° with respect to the long side of the base film) is formed, and a polarizing layer is further formed on the photoalignment film to produce a circularly polarizing plate. did.

In the same manner as in Example 1, the transparent base film and the reflecting plate of the prepared circularly polarizing plate were bonded together using an adhesive to measure reflectance. The reflectance of light having a wavelength in the range of 400 to 700 nm was about 1 to 10% over the entire visible light. It was found that sufficient antireflection properties could be obtained.

Example 3

Example 1 except that compound (B-14) was used instead of compound (B-6) as the polymerizable liquid crystal compound B1 and compound (B-17) was used instead of the compound (B-7) as the polymerizable liquid crystal compound B2, respectively. A circularly polarizing plate was produced in the same manner as described above.

In the same manner as in Example 1, the retardation layer and the reflecting plate of the manufactured circularly polarizing plate were bonded together using an adhesive to measure reflectance. The reflectance of light in the wavelength range of 400 to 700 nm was about 1 to 10%, which was sufficient over the entire visible light. It was found that antireflection characteristics could be obtained.

Comparative Example 1

As the retardation film, a quarter wave plate (Zenoa film, Nippon Xeon Co., In-plane retardation value Ro: 138 nm), which is a uniaxially stretched film of cyclic olefin resin, was used in the same manner as in Example 1 to obtain a retardation film. On one surface, the 1st alignment film (polarization direction of polarization UV was 45 degrees with respect to the slow axis of retardation film) was formed, the polarizing layer was further formed on this 1st alignment film, and the circular polarizing plate was produced.

In the same manner as in Example 1, the prepared circularly polarizing plate was bonded to the reflecting plate using an adhesive to measure the reflectance. The reflectance of light having a wavelength of 500 to 600 nm is a good reflectance of about 1 to 10%, but a 400 to 500 nm wavelength. The reflectance of the light and the reflectance of the light having a wavelength of 600 to 700 nm are 10% or more, indicating that the reflected light is bluish purple and a sufficient antireflection function cannot be obtained.

Comparative Example 2

As a polarizing plate, an iodine-PVA polarizing plate (105 micrometers in thickness of Sumikaran Sumitomo Chemical Co., Ltd. product) was cut out into small pieces of 100x100 mm so that an absorption axis might be 0 degrees. The 1/2 wave plate used in Example 1 was cut into small pieces of 100 × 100 mm so that the slow axis was 15 °. The quarter wave plate used in Comparative Example 1 was cut into small pieces of 100 × 100 mm so that the slow axis was 15 °. Each film cut out was bonded together using the acrylic adhesive (film thickness of 25 micrometers) so that it might become a polarizing plate +1/4 wavelength plate +1/2 wavelength plate, and the circular polarizing plate was produced.

In the same manner as in Example 1, the prepared circularly polarizing plate was bonded to the reflecting plate using an adhesive to measure reflectance. The reflectance of light in the wavelength range of 400 to 700 nm was about 1 to 10%. Although it was found that the total thickness of the circularly polarizing plate was measured by a contact film thickness meter, the total thickness of the circularly polarizing plate of Example 1 was 240 µm, which was about 5 times.

Example 4

A circularly polarizing plate was produced in the same manner as in Example 1 except that a polyethylene terephthalate film was used instead of KC4UY (TAC film, manufactured by Konica Minolta Co., Ltd.) as a substrate. The film 1 with an adhesive was bonded together on the phase difference layer of this circularly polarizing plate, and the circularly polarizing plate which has an adhesive layer was obtained. The sample was cut to a size of 40 mm x 40 mm, the film of the film with the bonded adhesive was peeled off, pressed onto a reflecting plate (mirror aluminum plate), and the substrate was slowly removed to obtain a reflecting plate with a circularly polarized film. . The thickness of the said circularly-polarizing film which consists of a 1st alignment film, a polarizing layer, a protective layer, a 2nd alignment film, a retardation layer, and an adhesive layer was 14.7 micrometers.

The peeling strength (F1) of the base material and the first alignment film is the peeling strength (F2) of the first alignment film and the polarizing layer, the peeling strength (F3) of the second alignment film and the retardation layer, and the peeling strength of the phase difference layer and the pressure-sensitive adhesive layer. Since it was lower than (F4), peeling occurred between the base material and the 1st alignment film, and the base material could be removed.

As a result of measuring the reflectance in the same manner as in Example 1, it was found that the reflectance of the light in the wavelength range of 400 to 700 nm was about 1 to 10%, so that sufficient antireflection characteristics could be obtained over the entire visible light. Since this antireflection principle is the same principle as reflection of external light in the metal electrode of the organic EL display, it is similarly suitably used for the organic EL display.

The circular polarizing plate of the present invention has sufficient performance as a broadband circular polarizing plate, the thickness thereof can satisfy the thinning of the display device, and the manufacturing process thereof is also simple. In addition, the display device provided with the circularly polarizing plate of the present invention can achieve thinning.

1: this circular polarizing plate 2: substrate
3: retardation layer 4: polarization layer
5: dichroic dye 10: liquid crystal display device
11a and 11b: present circularly polarizing plates 12a and 12b: substrate
13: color filter 14: transparent electrode
15: liquid crystal layer 16: interlayer insulating film
17: backlight unit 18: black matrix
19 thin film transistor 20 pixel electrode
21: spacer 30: organic EL display device
31: present circular polarizing plate 32: substrate
33: interlayer insulating film 34: pixel electrode
35: light emitting layer 36: cathode electrode
37: sealing layer 38: thin film transistor
39: Rib

Claims (21)

Having a substrate, a retardation layer, and a polarizing layer, the birefringence Δn (λ) for light having a wavelength of λnm of the retardation layer satisfies Equations (1) and (2), and the retardation layer and the polarizing layer are coated layers together. A total polarizing plate having a total thickness of the retardation layer and the polarizing layer is 10 μm or less, and the polarizing layer contains two or more dichroic dyes having a maximum absorption wavelength in a range of 300 to 700 nm, wherein the polarizing plate is 400 to 700 nm. Circularly polarized plates with a reflectivity of light in the range wavelength of 10% or less.
Δn (450) / Δn (550) ≤1.00 (1)
1.00≤Δn (650) / Δn (550) (2) The circularly polarizing plate according to claim 1, wherein the retardation layer is formed by polymerizing one or more polymerizable liquid crystals. The circularly polarizing plate according to claim 1 or 2, wherein the polarizing layer is formed by polymerizing one or more polymerizable liquid crystals. The circularly polarizing plate of Claim 2 which superposes | polymerizes a polymeric liquid crystal by light irradiation. The circularly polarizing plate of Claim 1 or 2 whose polarizing layer is a polarizing layer which can obtain a Bragg peak in X-ray diffraction measurement. The circularly polarizing plate of Claim 1 or 2 whose thickness of a retardation layer and a polarizing layer is 5 micrometers or less, respectively. The circularly polarizing plate of Claim 1 or 2 in which a retardation layer, a polarizing layer, or both are formed on an oriented film. The circularly polarizing plate according to claim 7, wherein the alignment film is an alignment film which generates an alignment regulating force by light irradiation. The circularly polarizing plate according to claim 7, wherein the alignment film has a thickness of 500 nm or less. The circularly polarizing plate of Claim 1 or 2 in which the retardation layer is formed on the base material with or without the alignment film, and the polarizing layer is formed on the retardation layer with or without the alignment film. The circularly polarizing plate of Claim 1 or 2 in which the polarizing layer is formed on the base material with or without the oriented film, and the phase difference layer is formed on the polarizing layer with or without the oriented film. The circularly polarizing plate of Claim 1 or 2 which has a protective layer between a polarizing layer and a retardation layer. The circularly polarizing plate according to claim 1 or 2, wherein a polarizing layer is formed on one side of the substrate with or without the alignment film, and a phase difference layer is formed on the other side of the substrate with or without the alignment layer. The circularly polarizing plate of Claim 1 or 2 which further has an adhesive layer on the surface of a retardation layer or a polarizing layer. The circularly polarizing plate of Claim 14 which has a base material, a 1st alignment film, a polarizing layer, a 2nd alignment film, a retardation layer, and an adhesive layer in this order. The peeling strength (F1) of a base material and a 1st alignment film is a peeling strength (F2) of a 1st alignment film and a polarizing layer, a peeling strength (F3) of a 2nd alignment film and a phase difference layer, and a phase difference layer of Claim 15. Circular polarizing plate lower than peeling strength (F4) with an adhesive layer. The display device provided with the circularly-polarizing plate of Claim 1, or a display element. The display device which has a circularly polarizing film by which the circularly polarizing film from which the base material was removed from the circularly polarizing plate of Claim 14 was bonded to the display surface of a display element via the adhesive layer of the said circularly polarizing film. The display device according to claim 18, wherein the circularly polarizing film has a thickness of 5 μm or more and 15 μm or less. 18. The display device according to claim 17, wherein the display element is a liquid crystal cell, an organic electroluminescent element or a touch panel. The manufacturing method of the display apparatus which has a circularly polarizing film which bonds the circularly polarizing plate of Claim 14 to the display surface of a display element via the adhesive layer of the said circularly polarizing plate, and removes a base material from the said circularly polarizing plate.

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