KR20130055527A - Polarizing film, circular polarizing plate and organic el image display device using the same - Google Patents

Abstract

PURPOSE: A polarization film, a circular polarization plate, and an organic EL image display device using the same are provided to offer a circular polarization plate reducing optical absorption from an organic EL light-emitting device, specifically optical absorption around 450 nm wavelength. CONSTITUTION: An organic EL image display device installs a proper rotation unit in a winding core(210A) of a first roll and unwinds a transparent material from the first roll(210) by rotating the first roll. The surface of the transparent material unwound from the first roll is coated with an orientation film formation composition while passing through a coating apparatus(211A). The transparent material is returned to a dry furnace, and is heated by the dry furnace and is transformed into a first laminate consisting of the transparent material and a first dry film. The first dry film side surface or the transparent member side surface of the first laminate is irradiated by polarized UV by a polarization UV irradiation apparatus, and the first dry film is transformed into an optical polarization film. The polarization film formation composition of the first laminate is coated on the optical orientation film of the first laminate by passing through a coating apparatus(211B). Afterward, the first laminate is a laminate forming a liquid crystalline state by passing through a dry furnace(212B). A solvent included in the polarization film formation composition of the film passing through the dry furnace is sufficiently removed and the film is returned to an optical irradiation apparatus(213B). The polarization film is wound to a second winding core(220A) in a laminate shape including the transparent material and the orientation film and is to be a second roll(220) shape.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polarizing film, a circular polarizer, and an organic EL image display device using the polarizing film,

The present invention relates to a polarizing film, a circularly polarizing plate, and an organic EL image display apparatus using the same.

In the organic EL image display apparatus, a circularly polarizing plate is used for preventing reflection of external light in a bright place. As such a circularly polarizing plate, for example, a polarizing film (iodine-PVA polarizing film) in which PVA (polyvinyl alcohol) is dyed with iodine is known (see, for example, Patent Document 1).

Patent Document 1: JP-A-7-142170

However, in the organic EL image display apparatus provided with the circularly polarizing plate including the conventional polarizing film, there is a problem that the polarizing film absorbs about half of the amount of light from the organic EL light emitting element. Therefore, the light emission intensity of the organic EL light emitting element must be increased, resulting in a short life of the organic EL image display apparatus. Particularly, blue light having a short lifetime (light emitting element near a wavelength of 450 nm) deteriorated with time. However, the circular polarizer and the polarizing film that can solve the above problems have not been realized at all.

The present invention includes the following inventions.

[1] A composition comprising two or more dichroic dyes different in maximum absorption wavelength (hereinafter referred to as " composition for polarizing film formation " in some cases)

Directional orientation direction,

The following formulas (I) to (V)

0.3? A450 / A550 <0.8 (I)

0.3? A450 / A650 < 1.0 (II)

0.5? A450? 2 (III)

1? A550? 3 (IV)

1? A? 650? 3 (V)

(Wherein,

A450 is the absorbance of the polarized light parallel to the alignment direction at a wavelength of 450 nm,

A550 is the absorbance of the polarized light parallel to the alignment direction at a wavelength of 550 nm,

A650 represents absorbance of polarized light parallel to the alignment direction at a wavelength of 650 nm, respectively.

(Hereinafter occasionally referred to as &quot; main polarizing film &quot;) having an absorption spectrum satisfying all of the relationships shown in Figs.

[2] The polarizing film according to the above [1], wherein the composition further comprises a polymerizable smectic liquid crystal compound.

[3] The polarizing film according to the above [1] or [2], wherein the two or more dichroic dyes are all polyazo dyes represented by the following formula (1).

[In the formula (1)

n is 1 or 2;

Ar ₁ and Ar ₃ each independently represent any one of the following groups.

Ar ₂ represents any one of the following groups.

A ₁ and A ₂ each independently represent any one of the following groups.

m is an integer of 0 to 10, and when two m are present in the same group, these two m are the same or different.]

[4] The polarizing film according to any one of [1] to [3], wherein the visual sensitivity-corrected single transmission (Ty) is 43% or more and the visual sensitivity-adjusted individual polarization degree Py is 90% or more.

[5] A polarizing plate having a polarizing film and a? / 4 layer according to any one of [1] to [4]

(Hereinafter referred to as &quot; original circular polarizer &quot; in some cases) satisfying the following requirements (A1) and (A2).

(A1) an angle formed between the absorption axis of the polarizing film and the slow axis of the? / 4 layer is approximately 45 占;

(A2) the front retardation of the? / 4 layer measured by light having a wavelength of 550 nm is in the range of 100 nm to 150 nm

[6] The circularly polarizing plate according to [5], wherein a front retardation value of the? / 4 layer with respect to visible light is reduced as the wavelength becomes shorter.

[7] A polarizing plate as described in any one of [1] to [4], wherein the polarizing film, the? / 2 layer and the? / 4 layer are provided in this order,

The circular polarizer satisfies the following requirements (B1) to (B4).

(B1) the angle formed by the absorption axis of the polarizing film and the slow axis of the? / 2 layer is approximately 15 占;

(B2) an angle formed by the slow axis of the? / 2 layer and the slow axis of the? / 4 layer is about 60 degrees;

(B3) the? / 2 layer has a value of the front retardation of the? / 4 layer measured with light having a wavelength of 550 nm in the range of 200 nm to 300 nm;

(B4) the? / 4 layer has a front retardation value of the? / 4 layer measured with light having a wavelength of 550 nm in a range of 100 nm to 150 nm

[8] An organic EL display device (hereinafter occasionally referred to as &quot; present organic EL display device &quot;) comprising the circularly polarizing plate and the organic EL element described in any one of [5] to [7] above.

[9] When the intensity of the light of 450 nm in the light emitted from the light emitting layer is I450, the intensity of the light in the wavelength of 550 nm is I550, and the intensity of the light in the wavelength of 650 nm is I650,

1 < / = I450 / I550 &lt; 2 (X)

1 < / = I450 / I650 &lt; 2 (XI)

Of the organic EL display device according to the above [8].

According to the present polarizing film, when used in an organic EL image display apparatus, it is possible to provide a circularly polarizing plate (original circularly polarizing plate) with reduced absorption of light from the organic EL light emitting element, particularly absorption of light in the vicinity of 450 nm.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing one embodiment of a continuous production method of the present polarizing film.
Fig. 2 is a schematic diagram schematically showing an angle formed by the absorption axis of the present polarizing film and the slow axis of the? / 4 layer in one embodiment of the present circular polarizer. Fig.
3 is a cross-sectional view schematically showing one embodiment of a continuous production method of the present polarizing film.
4 is a cross-sectional view schematically showing the structure of the present organic EL display device.
5 is a cross-sectional view schematically showing a layer sequence of the C portion of the organic EL display device 30. Fig.
6 is a cross-sectional view schematically showing a configuration of the present organic EL display device.

The present polarizing film can be realized in a high number of main organic EL display devices by using a circular polarizing plate including a main polarizing film to be described later.

A450 / A550 in the formula (I) is more preferable if the relation of 0.5? A450 / A550 <0.8 is satisfied.

A450 / A650 in the formula (II) is more preferable when the relation of 0.5? A450 / A650 <0.8 is satisfied.

A450 in the formula (III) is more preferably satisfies the relationship of 0.5? A450? 1.6 and more preferably satisfies the relationship of 1.0? A550? 2.0 in the formula (IV) A650 is more preferable when the relationship of 1.0? A650? 2.0 is satisfied.

The drawings attached to this specification are arbitrarily made for easy viewing.

<Dichromatic dye>

The composition for forming a polarizing film contains two or more dichroic dyes different in maximum absorption wavelength. The dichroic dye refers to a dye having a property that the absorbance in the major axis direction of the molecule is different from the absorbance in the minor axis direction. The dichroic dye may be a dye or a pigment. A plurality of dyes may be used, a plurality of dyes may be used, or a combination of dyes and pigments may be used.

The dichroic dye preferably has a maximum absorption wavelength (λMAX) in the range of 300 nm to 700 nm. Examples of such a dichroic dye include an acridine dye, an oxazine dye, a cyanine dye, a naphthalene dye, an azo dye, and an anthraquinone dye. Among them, the dichroic dye is preferably an azo dye. Examples of the azo dyes include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes and stilbenazo dyes, and preferred are bisazo dyes and trisazo dyes.

The dichroic dye is particularly preferably a dye represented by the formula (1) (hereinafter referred to as "azo dye (1)" in some cases). It is more preferable that the azo dye 1 exhibits a maximum absorption wavelength (? MAX) in a wavelength range of 300 nm to 700 nm.

It is preferable that the azobenzene moiety of the azo dye (1) is trans.

Examples of the azo dye (1) include compounds represented by the formulas (1-1) to (1-28), respectively.

Among the specific examples of the azo dye (1), the following formulas (1-2), (1-5), (1-6), (1-8), (1-10) ), Expression (1-13), Expression (1-15), Expression (1-16), Expression (1-19), Expression (1-20), Expression (1-21) (1-2), (1-5), (1-8), (1-24), , (1-10), (1-15), (1-21), (1-22) and (1-26)

The anthraquinone dye is preferably a compound represented by the formula (1-28).

[In the formula (1-28)

R ¹ to R ⁸ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x, or a halogen atom.

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

As the acridine dye, a compound represented by the formula (1-29) is preferable.

[In the formula (1-29)

R ⁹ to R ¹⁵ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x, or a halogen atom.

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

As the oxazone dye, a compound represented by the formula (1-30) is preferable.

[In the formula (1-30)

R ¹⁶ to R ²³ independently represent a hydrogen atom, -R ^x , -NH ₂ , -NHR ^x , -NR ^x ₂ , -SR ^x, or a halogen atom.

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

In the above formulas (1-28), (1-29) and (1-30), the alkyl group having 1 to 6 carbon atoms represented by R ^x means a methyl group, an ethyl group, And examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a toluyl group, a xylyl group and a naphthyl group.

As the cyanine dye, a compound represented by the formula (1-31) and a compound represented by the formula (1-32) are preferable.

[In the formula (1-31)

D ¹ and D ² independently represent a group represented by any one of formulas (1-31a) to (1-31d).

and n5 represents an integer of 1 to 3.]

[In the formula (1-32)

D ³ and D ⁴ independently represent a group represented by any one of formulas (1-32a) to (1-32h).

n6 represents an integer of 1 to 3.]

The composition for forming a polarizing film contains two or more dichroic dyes, more preferably two to three dichroic dyes, and even more preferably two or three kinds of azo dyes (1) Do. Is represented by the combination of two or three kinds of azo dyes (1) (referred to as "first dyes", "second dyes" and "third dyes").

[Table 1]

[Table 2]

According to the composition for forming a polarizing film containing a combination of the azo dye (1) shown in the above-mentioned table, it is possible to obtain an absorption satisfying all the relations expressed by the formulas (I) to (V) The present polarizing film having a spectrum is easily obtained.

The notation in the table corresponds to the sign of a specific example of the azo dye (1), and for example, "1-5" means "azo dye (1) represented by the formula (1-5)".

The content of the dichroic dye in the composition for forming a polarizing film is preferably 1 part by mass or more and 90 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the total amount of the composition for forming a polarizing film More preferably 3 parts by mass or more and 10 parts by mass or less.

The content of the dichroic dye in the composition for forming a polarizing film is preferably 0.1 part by mass or more and 50 parts by mass or less, more preferably 0.1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total amount of the polymerizable liquid crystal compound described below More preferably 0.1 part by mass or more and 10 parts by mass or less. When the content of the dichroic dye is within this range, the polymerizable liquid crystal compound can be polymerized without disturbing the orientation of the polymerizable liquid crystal compound.

&Lt; Polymerizable liquid crystal compound &

The composition for forming a polarizing film preferably contains a polymerizable liquid crystal compound since a polarizing film having practical strength can be obtained. The polymerizable liquid crystal compound is a compound having a polymerizable group and exhibiting a liquid crystal state. The polymerizable group means a group involved in the polymerization reaction of the polymerizable liquid crystal compound.

Examples of the polymerizable liquid crystal compound include a polymerizable nematic liquid crystal compound and a polymerizable smectic liquid crystal compound, and from the viewpoint of polarization performance, a polymerizable smectic liquid crystal compound is preferable.

The liquid crystal state exhibited by the polymerizable smectic liquid crystal compound is more preferably a high-order smectic phase. The higher order smectic phases referred to herein are the Smectic B phase, Smectic D phase, Smectic E phase, Smectic F phase, Smectic G phase, Smectic H phase, Smectic I phase, Smectic J phase, Mectic K phase and Smectic L phase. Among them, Smectic B phase, Smectic F phase and Smectic I phase are more preferable.

The main polarizing film having a high degree of alignment can be obtained by the liquid crystal state exhibited by the polymerizable Smectic liquid crystal compound. Further, the main polarizing film having such a high degree of alignment order can obtain a black peak in X-ray reflection measurement.

The black peak is a peak derived from the planar periodic structure of the molecular orientation, and according to the composition for forming a polarizing film, the main polarizing film having a periodic interval of 3.0 Å to 5.0 Å can be obtained.

A preferred polymerizable smectic liquid crystal compound is, for example, a compound represented by formula (2) (hereinafter sometimes referred to as "compound (2)").

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

[In the formula (2)

X ¹ , X ² and X ³ independently represent a p-phenylene group which may have a substituent or a 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 p-phenylene group which may have a substituent.

Y ¹ and Y ² independently represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a single bond, -N═N-, -CR ^a = CR ^b -, - C? C- or -CR ^a = N-. R ^a and R ^b independently 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 independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent and -CH ₂ - which constitutes an alkanediyl group may be replaced by -O-, -S- or -NH- May be substituted.

At least one of X ¹ , X ² and X ³ is a 1,4-phenylene group which may have a substituent, but two or more of them are preferably a p-phenylene group which may have a substituent.

The p-phenylene group is preferably an amorphous group. The cyclohexane-1,4-diyl group is preferably a trans-cyclohexane-1,4-diyl group, and the trans-cyclohexane-1,4-diyl group is more preferably an indefinite group.

Examples of the substituent optionally having a p-phenylene group or a cyclohexane-1,4-diyl group include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a butyl group; Cyano; Halogen atoms and the like. Further, -CH ₂ - constituting the cyclohexane-1,4-diyl group may be substituted with -O-, -S- or -NR-. R is an alkyl group having 1 to 6 carbon atoms or a phenyl group.

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, preferably a polymerizable group. That is, all of U ¹ and U ² are preferably a polymerizable group, and all of them are preferably a photopolymerizable group. The photopolymerizable group means a group capable of participating in the polymerization reaction by an active radical or an acid generated from a photopolymerization initiator described later. Use of the polymerizable Smectic liquid crystal compound having a photopolymerizable group is also advantageous in that the polymerizable Smectic liquid crystal compound can be polymerized at a lower temperature.

The polymerizable groups of U ¹ and U ² may be different from each other, but are preferably groups of the same kind. Examples of the polymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloyloxy group, a methacryloyloxy group, an oxiranyl group and an oxetanyl group. Among them, an acryloyloxy group, a methacryloyloxy group, a vinyloxy group, an oxiranyl group and an oxetanyl group are preferable, and an acryloyloxy group is more preferable. U ¹ and U ² are polymeric groups of the same kind, for example, when U ¹ and U ² are both acryloyloxy groups.

Examples of the alkanediyl group of V ¹ and V ² include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane- A heptane-1,7-diyl group, an octane-1,8-diyl group, a decane-1,10-diyl group, a tetradecane-1,14-diyl group, An acid-1,20-diyl group and the like. V ¹ and V ² are preferably an alkanediyl group having ² to 12 carbon atoms, more preferably an alkanediyl group having 6 to 12 carbon atoms.

Examples of the substituent optionally having an alkanediyl group include a cyano group and a halogen atom, and the alkanediyl group is preferably an amorphous group, more preferably an unsubstituted straight-chain alkanediyl group.

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

Examples of the compound (2) include compounds represented by the formulas (2-1) to (2-24), respectively. When the specific example of the compound (2) has a cyclohexane-1,4-diyl group, it is preferable that the cyclohexane-1,4-diyl group is a trans.

The polymerizable smectic liquid crystal compounds may be used alone or in combination of two or more thereof in a composition for forming a polarizing film. Further, two or more polymerizable Smectic liquid crystal compounds may be used, and at least one of the two or more polymerizable Smectic liquid crystal compounds may be Compound (2).

When the polymerizable smectic liquid crystal compound is used in a composition for forming a polarizing film, the phase transition temperature of the polymerizable smectic liquid crystal compound is determined in advance and the polymerizable smectic liquid crystal compound is polymerized under a temperature condition below the phase transition temperature, Components other than the polymerizable Smectic liquid crystal compound of the film-forming composition are adjusted. Examples of the component capable of controlling the polymerization temperature include a photopolymerization initiator, a photosensitizer and a polymerization inhibitor which will be described later. The polymerization temperature of the polymerizable smectic liquid crystal compound can be controlled by suitably controlling these kinds and amounts. Also in the case of using a mixture of two or more polymerizable smectic liquid crystal compounds in a composition for forming a polarizing film, the phase transition temperature of a mixture of two or more polymerizable smectic liquid crystal compounds is determined, Lt; / RTI &gt;

Among the compounds (2), the compounds represented by formulas (2-2), (2-3), (2-4), (2-6), (2-7), (2-8) (2-13), (2-14), (2-15) and (2-24), respectively.

The polymerizable smectic liquid crystal compound can be obtained by mixing two or more kinds of the polymerizable smectic liquid crystal compounds, or by interacting with a polymerization initiator used together, the polymerizable smectic liquid crystal compound is easily maintained under temperature conditions below the phase transition temperature, Can be polymerized. More specifically, the polymerizable smectic liquid crystal compound is polymerized while maintaining a high-order smectic phase liquid crystal state under a temperature condition of 70 ° C or lower, preferably 60 ° C or lower, by interaction with a polymerization initiator Is preferred.

The polymerizable smectic liquid crystal compound contained in the composition for forming a polarizing film may be a single species or a plurality of species (two or more species), but preferably a plurality of species.

When a composition for forming a polarizing film containing a polymerizable smectic liquid crystal compound is used, the content of the polymerizable smectic liquid crystal compound is preferably from 70% by mass to 99.9% by mass based on the solid content of the composition for polarizing film formation, And more preferably 90% by mass to 99.9% by mass. When the content of the polymerizable smectic liquid crystal compound is within the above range, the alignment property of the polymerizable smectic liquid crystal compound tends to be high. Here, the solid content refers to the total amount of components excluding a volatile component such as a solvent from the composition for forming a polarizing film. When plural kinds of polymerizable smectic liquid crystal compounds are contained in the composition for forming a polarizing film, the total content ratio may be within the above-mentioned range.

<Solvent>

The composition for forming a polarizing film may contain a solvent. In general, since the polymeric smectic liquid crystal compound has a high viscosity, the application is facilitated by the inclusion of a solvent, and as a result, the formation of the polarizing film is often easy. As the solvent, a polymerizable smectic liquid crystal compound and a solvent capable of dissolving a dichroic dye are preferable. It is also preferable that the solvent is inert to the polymerization reaction of the composition for forming a polarizing film.

Examples of the solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate,? -Butyrolactone or propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Aromatic hydrocarbons such as toluene and xylene (xylene may be any of o-form, m-form and p-form, or a mixture of two or more selected from them); nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-containing solvents such as chloroform and chlorobenzene, and the like. These solvents may be used as a single species or a combination of plural species.

The content of the solvent is preferably 50% by mass to 98% by mass with respect to the total amount of the composition for forming a polarizing film. In other words, the solid content in the composition for forming a polarizing film is preferably 2% by mass to 50% by mass. When the solid content is 2% by mass or more, a thin polarizing film tends to be easily obtained. On the other hand, when the solid content is 50% by mass or less, the viscosity of the composition for forming a polarizing film is lowered, so that the thickness of the polarizing film tends to become substantially uniform, and the polarizing film tends to become unlikely to be uneven. Such a solid content can be determined by forming a desired thickness of a polarizing film described later.

<Preparation of Polymerization Reaction>

The composition for forming a polarizing film preferably contains a polymerization initiator. The polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable smectic liquid crystal compound and is preferably a photopolymerization initiator in that polymerization reaction can be initiated at a lower temperature. Specifically, a compound capable of generating an active radical or an acid by the action of light is used as a photopolymerization initiator. Among photopolymerization initiators, it is more preferable to generate radicals by the action of light.

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

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- Oxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- 2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2 Hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2- And oligomers of 4- (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.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis - [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) ) Ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-tri Azine, and the like.

As the polymerization initiator, those readily available on the market can be used. Examples of commercially available photopolymerization initiators include Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369, (Chiba Japan Co., Ltd.); "SEQUOOL BZ", "SEQUOOL Z", "SEQUOOL BEE" (Seiko Chemical Co., Ltd.); "Kayacure BP100" (Nippon Kayaku Co., Ltd.); "Kayacure-UVI-6992" (manufactured by Dow Chemical Company); "Adeka Optoma SP-152", "Adeka Optoma SP-170" (ADEKA Corporation); "TAZ-A "," TAZ-PP "(Nippon Shibel Hegner); And "TAZ-104" (manufactured by Sanwa Chemical Co., Ltd.).

When the composition for forming a polarizing film contains a polymerization initiator, the content thereof can be appropriately adjusted depending on the kind and amount of the polymerizable liquid crystal compound (polymerizable smectic liquid crystal compound) contained in the composition for forming a polarizing film, For example, the content of the polymerization initiator in the total amount of 100 parts by mass of the polymerizable liquid crystal compound (polymerizable smectic liquid crystal compound) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, further preferably 0.5 to 10 parts by mass Do. If the content of the polymerizable initiator is within this range, the alignment of the polymerizable smectic liquid crystal compound can be polymerized without clogging, so that the polymerizable smectic liquid crystal compound is polymerized while maintaining the liquid phase state of the higher order smectic phase .

When the composition for forming a polarizing film contains a polymerization initiator, the composition for forming a polarizing film may contain a sensitizer. As the sensitizer, a photosensitizer is preferred. Examples of sensitizers include xanthone compounds such as xanthone and thioxanthone (e.g., 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); Anthracene compounds such as anthracene and alkoxy group-containing anthracene (e.g., dibutoxyanthracene); Phenothiazine, rubrene, and the like.

When the composition for polarizing film formation contains a polymerization initiator and a sensitizer, the polymerization reaction of the polymerizable liquid crystal compound (polymerizable smectic liquid crystal compound) contained in the composition for forming a polarizing film can be further promoted. The amount of the sensitizer used can be appropriately adjusted depending on the type and amount of the polymerization initiator and the polymerizable smectic liquid crystal compound used in combination. For example, the amount of the sensitizer is preferably 0.1 to 30 parts by mass More preferably 0.5 to 10 parts by mass, still more preferably 0.5 to 8 parts by mass.

It has been described that the polymerization reaction of the polymerizable liquid crystal compound (polymerizable smectic liquid crystal compound) can be promoted by adding a sensitizer to the composition for forming a polarizing film. However, in order to stably proceed the polymerization reaction, A polymerization inhibitor may be appropriately contained in the composition. By containing a polymerization inhibitor, it is possible to control the progress of the polymerization reaction of the polymerizable liquid crystal compound (polymerizable smectic liquid crystal compound).

Examples of the polymerization inhibitor include radicals such as hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (such as butyl catechol), pyrogallol, 2,2,6,6-tetramethyl-1-piperidinyloxy radical Supplements; Thiophenols; β-naphthyl amines, β-naphthols, and the like.

When a polymerization inhibitor is contained in the composition for forming a polarizing film, its content can be appropriately adjusted depending on the type and amount of the polymerizable smectic liquid crystal compound to be used, the amount of the sensitizer used, and the like. Polymerizable smectic liquid crystal compound) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, still more preferably 0.5 to 8 parts by mass. When the content of the polymerization inhibitor is within the above range, the alignment of the polymerizable liquid crystal compound (polymerizable smectic liquid crystal compound) contained in the composition for forming a polarizing film can be polymerized without cluttering, (Smectic liquid crystal compound) can be further polymerized while maintaining a liquid crystal state of a higher order Smectic phase.

<Leveling agent>

The composition for forming a polarizing film preferably contains a leveling agent. The leveling agent has a function of adjusting the fluidity of the composition for forming a polarizing film and further making the coating film obtained by applying the composition for forming a polarizing film more flattened, and examples thereof include a surfactant and the like. The leveling agent is more preferably at least one selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component.

As a leveling agent containing a polyacrylate compound as a main component, there may be mentioned "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK- 381 ", " BYK-381 ", and "BYK-392 " [BYK Chemie Co., Ltd.].

Examples of the leveling agent containing a fluorine atom-containing compound as a main component include "Megapak R-08", "R-30", "R-90", "F-410" F-443 "," F-475 "," F-470 "," F-471 " -483 "[DIC (note)]; S-383, S-393, S-101, S-105, S-382, S- SA-100 "[AGC Seiyam Chemical Co., Ltd.]; "E1830 "," E5844 "[Daikin Chemical Research Institute, Ltd.]; EF301 "," EF303 "," EF351 "and" EF352 "manufactured by Mitsubishi Materials Corporation.

When the leveling agent is contained in the composition for forming a polarizing film, the content thereof is preferably 0.3 parts by mass or more and 5 parts by mass or less, more preferably 0.5 parts by mass or less, per 100 parts by mass of the polymerizable liquid crystal compound (polymerizable smectic liquid crystal compound) More preferably not less than 3 parts by mass. When the content of the leveling agent is within the above-mentioned range, it is easy to horizontally align the polymerizable liquid crystal compound (polymerizable smectic liquid crystal compound), and the obtained polarizing film tends to become smoother. If the content of the leveling agent in the polymerizable smectic liquid crystal compound exceeds the above range, unevenness tends to occur in the resulting polarizing film. The composition for forming a polarizing film may contain two or more kinds of leveling agents.

&Lt; Method of forming polarizer film >

Next, a method of forming the polarizing film from the composition for forming a polarizing film will be described. In this method, it is preferable that the present polarizing film is formed by applying a composition for forming a polarizing film on a substrate, preferably on a transparent substrate.

<Transparent substrate>

The transparent base material is a base material having transparency enough to transmit light, particularly visible light. Transparency refers to a characteristic in which the transmittance for a light beam having a wavelength ranging from 380 nm to 780 nm is 80% or more. Specifically, examples of the transparent substrate include a glass substrate, a translucent sheet made of plastic, and a translucent film. Examples of the plastic constituting the light transmitting sheet and the light transmitting film include polyolefins such as polyethylene, polypropylene and norbornene polymer; Cyclic olefin based resins; Polyvinyl alcohol; Polyethylene terephthalate; Polymethacrylic acid esters; Polyacrylic acid esters; Cellulose esters such as triacetylcellulose, diacetylcellulose and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Polysulfone; Polyethersulfone; Polyether ketones; Polyphenylene sulfide, and polyphenylene oxide. Among the specific examples of the transparent substrate, a transparent translucent film made of plastic or a polymer film is preferable in view of a preferable translucent sheet made of plastic and a translucent film. Among the polymer films, a polymer film composed of a cellulose ester, a cyclic olefin resin, polyethylene terephthalate or polymethacrylic acid ester is particularly preferable because it is easily available on the market or has excellent transparency. A supporting substrate or the like may be adhered to the transparent substrate in that the polarizing film can be easily handled without causing breakage such as tearing when the transparent substrate is transported or stored in manufacturing the polarizing film using the transparent substrate . Further, as will be described later, when producing a circularly polarizing plate from the present polarizing film, there is a case where the transparent substrate is given a phase difference. In this case, a polymer film may be prepared as a transparent material, and the polymer film may be subjected to stretching treatment or the like to impart a retardation to the polymer film to form a retardation film, and then the retardation film may be used as a transparent substrate. The method of imparting the retardation to the transparent substrate (polymer film) will be described later.

Among the polymer films, a film comprising a cellulose ester, a polycarbonate or a cyclic olefin resin (a cellulose ester film, a polycarbonate film, a cyclic olefin based resin film ) Is preferable. Hereinafter, these three types of polymer films will be described in detail.

In the cellulose ester constituting the cellulose ester film, at least a part of the hydroxyl groups contained in the cellulose is acetic esterified. A cellulose ester film comprising such a cellulose ester can be easily obtained on the market. Commercially available triacetylcellulose films include, for example, "Fuji Takku film" (Fuji Shashin Film Co., Ltd.); "KC8UX2M", "KC8UY", and "KC4UY" (Konica Minolta Opt Co., Ltd.). Such a commercially available triacetylcellulose film can be used as a transparent substrate after imparting a phase difference as is or when necessary. The surface of the prepared transparent substrate can be used as a transparent substrate after surface treatment such as antiglare treatment, hard coat treatment, antistatic treatment or antireflection treatment.

In order to impart the retardation to the polymer film, the polymer film is stretched or the like as described above. A plastic film, that is, a polymer film made of a thermoplastic resin can all be stretched, but a cycloolefin resin film is preferable in that it is easy to control the retardation. The cyclic olefin resin constituting the cyclic olefin based resin film is composed of a polymer or copolymer (cyclic olefin resin) of a cyclic olefin such as norbornene or a polycyclic norbornene monomer, and the cyclic olefin resin is partly , And an opening portion may be included. Further, a cyclic olefin resin containing a ring-opening may be hydrogenated. The cyclic olefin resin may be a copolymer of a cyclic olefin and a chain olefin or a vinyl aromatic compound (such as styrene) in view of not significantly impairing transparency, but not significantly increasing hygroscopicity. The cyclic olefin resin may have a polar group introduced into the molecule thereof.

When the cyclic olefin resin is a copolymer of a cyclic olefin and an aromatic compound having a chain olefin or vinyl group, examples of the chain olefin include ethylene and propylene, and examples of the vinylated aromatic compound include styrene, Styrene. In such copolymers, the content ratio of the structural units derived from the cyclic olefin is in the range of about 50 mol% or less, for example, about 15 mol% to 50 mol%, based on the total structural units of the cyclic olefin-based resin. When the cyclic olefin resin is a ternary copolymer obtained from a cyclic olefin, a chain olefin and a vinylated aromatic compound, for example, the content ratio of the structural unit derived from a chain olefin is preferably 5 mol% or more, To 80 mol%, and the content of the structural unit derived from the vinylated aromatic compound is about 5 mol% to 80 mol%. The cyclic olefin-based resin of such a ternary copolymer has an advantage that the amount of the expensive cycloolefin can be relatively small when the cyclic olefin-based resin is produced.

The cyclic olefin-based resin capable of producing the cyclic olefin based resin film is easily available on the market. Commercially available cyclic olefin resins include "Topas" (Ticona, Germany); "Atton" [JSR Corporation]; "ZEONOR" and "ZEONEX" [Nippon Zeon Co., Ltd.]; "Arpel" (manufactured by Mitsui Kagaku Co., Ltd.) and the like. Such a cycloolefin resin can be formed into a film (cyclic olefin resin film) by a known film-forming means such as a solvent casting method or a melt extrusion method. In addition, a cyclic olefin based resin film that has already been commercially available in the form of a film can also be used. Examples of commercially available cyclic olefin based resin films include "Essen" and "SCA40" (manufactured by Sekisui Chemical Co., Ltd.); "Zeonoah Film" [Optesis Corporation]; And "Aton film" [JSR Co., Ltd.].

Also, in the polycarbonate film, a film imparted with a phase difference can be easily obtained on the market. Examples of such a polycarbonate film include a uniaxially stretched film WRF-S (modified polycarbonate-based resin) manufactured by Dainippon Ink and Chemicals, Inc.).

Next, a method of imparting the phase difference to the polymer film will be briefly described. The polymer film can impart retardation by a known stretching method. For example, a roll (roll) in which a polymer film is wound on a roll is prepared, the film is continuously unwound from the roll, and the unwound film is returned to the heating furnace. The set temperature of the heating furnace is preferably in the range of from the vicinity of the glass transition temperature (占 폚) of the polymer film to the glass transition temperature +100 占 폚 (占 폚), preferably in the vicinity of the glass transition temperature (占 폚) (° C). In the heating furnace, when stretching in the film advancing direction or in the direction perpendicular to the advancing direction, uniaxial or biaxial thermal stretching treatment is performed by tilting at an arbitrary angle by adjusting the conveying direction and the tension. The magnification of the stretching is usually in the range of about 1.1 to 6 times, preferably in the range of about 1.1 to 3.5 times. The method of stretching in the oblique direction is not particularly limited as long as it can continuously tilt the orientation axis at a desired angle, and a known stretching method can be employed. Examples of such a stretching method include those described in JP-A-50-83482 and JP-A-2-113920.

In the use as a transparent substrate, the thickness of the polymer film is preferably as small as practically acceptable, and sufficient transparency can be ensured. However, when the polymer film is too thin, the strength is lowered, There is a tendency to fall behind. Therefore, suitable thicknesses of these films are, for example, about 5 to 300 占 퐉, and preferably 20 to 200 占 퐉. When the present polarizing film is used as a circularly polarizing plate to be described later, the thickness of the film is particularly preferably about 20 m to 100 m, since the display device using the circularly polarizing plate is assumed to be mobile. When retardation is imparted to the film by stretching, the thickness after stretching is determined by the thickness of the film before stretching and the stretch magnification.

<Orientation film>

It is preferable that an alignment film is formed on a substrate used for manufacturing the present polarizing film. In this case, the composition for forming a polarizing film is applied on the alignment film. For this reason, it is preferable that the alignment film has a solvent resistance to such an extent that it can not be dissolved by application of a composition for forming a polarizing film or the like. Further, it is preferable that it has a heat resistance in a heat treatment for removal of a solvent or orientation of a liquid crystal. As such an orientation film, an orientation polymer can be used.

Examples of the oriented polymer include polyamides and gelatins having amide bonds in the molecule, polyimides having imide bonds in the molecule, and hydrolyzates thereof, polyamic acids, polyvinyl alcohols, alkyl-modified polyvinyl alcohols, polyacrylamides, And polymers such as sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylic acid esters. Of these, polyvinyl alcohol is preferable. These orienting polymers for forming an alignment film may be used alone or in combination of two or more.

As the oriented polymer, an oriented polymer composition (a solution containing an oriented polymer) dissolved in a solvent may be coated on a substrate to form an oriented film on the substrate. The solvent used for the oriented polymer composition is not particularly limited, but specifically includes water; Alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, methyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate,? -Butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methyl amyl ketone and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorinated hydrocarbons such as chloroform and chlorobenzene, and the like. These organic solvents may be used alone or in combination of plural kinds.

As the oriented polymer composition for forming the alignment film, a commercially available alignment film material may be used as it is. Commercially available alignment film materials include SANEVA (registered trademark, manufactured by Nissan Chemical Industries, Ltd.) or Optomer (registered trademark, manufactured by JSR Corporation).

As a method for forming an alignment film on a substrate, for example, an alignment film can be formed on a substrate by applying an orienting polymer composition or a commercially available alignment film material on the substrate and then annealing. The thickness of the alignment film thus obtained is, for example, in the range of 10 nm to 10000 nm, preferably in the range of 10 nm to 1000 nm.

In order to impart the alignment regulating force to the alignment film, rubbing is preferably performed (rubbing method) if necessary. By giving the alignment regulating force, the polymerizable Smectic liquid crystal compound can be aligned in a desired one direction (orientation direction).

As a method of imparting the alignment restraining force by the rubbing method, for example, a rubbing roll wound around a rubbing cloth is prepared, a rotating rubbing roll is prepared, a laminate on which a coating film for forming an orientation film is formed is placed on a stage, Thereby bringing the coating film for forming an alignment film into contact with the rotating rubbing roll.

A so-called photo alignment film can also be used. The photo alignment layer may be formed by forming a photo-alignment organic layer and irradiating polarized light (preferably polarized UV) to give the alignment regulating force. In forming a photo-aligned organic layer, first, a composition containing a polymer or monomer having a photoreactive group and a solvent (hereinafter referred to as a &quot; composition for forming a photo alignment film &quot; The photoreactive group means a group which generates a liquid crystal aligning ability by irradiating light (light irradiation). Specifically, it generates a photoreaction, which is a source of liquid crystal aligning ability, such as orientation or isomerization of a molecule generated by irradiation of light, dimerization reaction, photo-crosslinking reaction, or photolysis reaction. Of the photoreactive groups, dimerization or photo-crosslinking reactions are preferred because they are excellent in orientation and maintain a smectic liquid crystal state at the time of polarizing film formation. As the photoreactive group capable of generating the above-described reaction, it is preferable to have an unsaturated bond, particularly a double bond, and a carbon-carbon double bond (C═C bond), a carbon-nitrogen double bond (C═N bond) A group having at least one member selected from the group consisting of a nitrogen-nitrogen double bond (N = N bond), and a carbon-oxygen double bond (C = O bond) is particularly preferable.

Examples of the photoreactive group having a C = C bond include a vinyl group, a polyene group, a stilbene group, a stilbazol group, a stilbazolol group, a chalcone group and a cinnamoyl group. Examples of the photoreactive group having a C = N bond include a group having a structure such as an aromatic sip base and an aromatic hydrazone. Examples of the photoreactive group having an N = N bond include those having an azobenzene group, an azonaphthalene group, an aromatic heterocyclic azo group, a bisazo group and a formamide group, and azoxybenzene as a basic structure. Examples of the photoreactive group having a C = O bond include a benzophenone group, a coumarin group, an anthraquinone group and a maleimide group. These groups may have substituents such as an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group and a halogenated alkyl group.

Among them, a photo-reactive group capable of generating a photo-dimerization reaction is preferred, and a photo-alignment layer having a relatively small amount of polarized light necessary for photo-alignment and excellent in thermal stability and stability over time is obtained It is preferable because it is easy. More specifically, as the polymer having a photoreactive group, it is particularly preferable that the polymer has a cinnamoyl group in which the terminal portion of the polymer side chain has a cinnamic acid structure.

The polymer or monomer having a photoreactive group is a composition for forming a photo alignment layer dissolved in a solvent and can be applied on a transparent substrate to form a photo-aligned organic layer on the transparent substrate. The solvent used in the composition is not particularly limited, and depending on the solubility of the polymer or monomer having a photoreactive group, a solvent as used in the above-mentioned oriented polymer composition can be applied.

The concentration of the polymer or monomer having a photoreactive group in the composition for forming a photo alignment layer can be appropriately adjusted depending on the kind of the polymer or monomer having the photoreactive group and the thickness of the photo alignment layer to be produced, Is preferably at least 0.2 mass%, particularly preferably from 0.3 mass% to 10 mass%. The composition for forming an alignment film may contain a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer within a range in which the properties of the photo alignment layer are not significantly impaired.

Examples of the method of applying the polymer or monomer having an orientation polymer or photoreactive group on a transparent substrate include a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method and an applicator method, A known method such as a printing method of printing is employed. When the present polarizing film production is carried out by a continuous production method of a roll to roll type to be described later, a printing method such as a gravure coating method, a die coating method or a flexo printing method is usually employed .

<Production Method of Polarizing Film>

On the alignment film formed on the substrate, a composition for forming a polarizing film is applied to obtain a coating film. As a method (application method) of applying the composition for forming a polarizing film on the alignment film, for example, the same method as that exemplified as a method of applying an orientation polymer or a polymer (monomer) having a photoreactive group on a transparent substrate can be mentioned.

Next, the solvent is dried and removed under the condition that the polymerizable smectic liquid crystal compound contained in the coating film does not polymerize, whereby a dry film is formed. Examples of the drying method include a natural drying method, a ventilation drying method, a heat drying method and a reduced pressure drying method. At this time, it is preferable that once the liquid crystalline state of the polymeric smectic liquid crystal compound contained in the dried film is changed to a nematic phase (nematic liquid crystal state), then the nematic phase is transferred to a smectic phase. In order to form the Smectic phase via the nematic phase as described above, for example, the polymerizable Smectic liquid crystal compound contained in the dried film is heated to a temperature above the phase transition to the nematic liquid crystal state, and then the polymerizable Smectic liquid crystal compound A method of cooling to a temperature showing the liquid crystal state of the mectic phase is adopted.

When the polymerizable Smectic liquid crystal compound in the dried film is changed to the Smectic liquid crystal state or the polymerizable Smectic liquid crystal compound is changed to the Smectic liquid crystal state via the nematic liquid crystal state, The conditions (heating conditions) for controlling the liquid crystal state can be easily obtained. The measurement conditions of this phase transition temperature measurement are described in the embodiments of the present application.

In order to favorably maintain the liquid crystal state of the smectic phase when polymerizing the polymerizable smectic liquid crystal compound, a composition for forming a polarizing film containing two or more polymerizable smectic liquid crystal compounds is used as the polymerizable smectic liquid crystal compound . It is possible to form a supercooled state temporarily after forming a smectic phase liquid crystal state via a nematic phase by using a composition for forming a polarizing film in which the content ratio of two or more polymerizable smectic liquid crystal compounds is adjusted, There is an advantage that it is easy to easily maintain the liquid crystal state of the higher order Smectic phase.

Next, the polymerization process of the polymerizable smectic liquid crystal compound will be described. Herein, the photopolymerization initiator is contained in the composition for forming a polarizing film, the liquid crystalline state of the polymerizable Smectic liquid crystal compound in the dried film is made Smectic, and the polymerizable Smectic liquid crystal compound Will be described in detail. The light to be irradiated on the dry film in the light polymerization is not particularly limited as long as the kind of the photopolymerization initiator contained in the dry film or the kind of the polymerizable smectic liquid crystal compound (in particular, the type of the light polymerizer of the polymerizable smectic liquid crystal compound) Can be appropriately performed by light or active electron rays selected from the group consisting of visible light, ultraviolet light and laser light. Of these, ultraviolet light is preferred because it is easy to control the progress of the polymerization reaction, and since it can be used as a device for photopolymerization widely used in the art. Therefore, it is preferable that the kind of the polymerizable smectic liquid crystal compound and the photopolymerization initiator contained in the composition for forming a polarizing film is selected so that light can be cured by the ultraviolet light. When the polymerization is carried out, the polymerization temperature may be controlled by cooling the dried coating with an appropriate cooling means together with ultraviolet light irradiation. By employing such cooling means, polymerization of the polymerizable smectic liquid crystal compound can be carried out at a lower temperature, and even if the above-mentioned transparent substrate has a relatively low heat resistance, the present polarizing film can be suitably formed .

By performing the above-mentioned photopolymerization, the polymerizable Smectic liquid crystal compound is polymerized while being maintained in a Smectic phase, preferably a higher order Smectic phase liquid crystal state as already exemplified, to form the present polarizing film. The main polarizing film obtained by polymerizing the polymerizable Smectic liquid crystal compound while maintaining the liquid crystal state of the Smectic phase depends on the action of the azo-based dye (1), and the conventional host guest type polarizing film, that is, There is an advantage that the polarizing film is much higher in polarizing performance than the polarizing film obtained by polymerizing the polymerizable liquid crystal compound or the like.

The thickness of the present polarizing film is preferably in the range of 0.5 占 퐉 to 10 占 퐉, more preferably 1 占 퐉 to 5 占 퐉. Therefore, the thickness of the coating film for forming the present polarizing film is determined in consideration of the thickness of the obtained polarizing film. The thickness of the present polarizing film is obtained by measurement of an interference film thickness meter, a laser microscope or a stylus film thickness meter.

The polarizing film thus formed is preferably a polarizing film of two or more dichroic dyes having different maximum absorption wavelengths, preferably two or more of the azo dyestuffs (1), particularly preferably two or more dyestuffs of the azo dyestuffs (1) (I) to (V) can be obtained by using the composition for forming a polarizing film, Particularly, when a composition containing a combination of the azo dye (1) shown in Table 1 is used as the composition for forming a polarizing film, it is possible to more easily obtain an image having an absorption spectrum satisfying the relations of the formulas (I) to (V) A polarizing film can be obtained.

It is particularly preferable that the polarizing film thus formed is one capable of obtaining a black peak in X-ray reflection measurement. As examples of the polarizing film in which such a black peak can be obtained, a polarizing film showing a diffraction peak derived from, for example, a hexate phase or a crystal phase can be mentioned.

Further, it is preferable that the polarizing film of the present invention is such that the visual sensitivity-corrected single-beam transmittance Ty is 43% or more and the visual sensitivity-corrected single-polarization degree Py is 90% or more. The visibility-corrected single unit transmittance Ty and the visibility-adjusted single unit polarization degree Py refer to the transmittance T ^{1 in the} transmission axis direction and the transmittance T in the absorption axis direction of the polarizing membrane in the wavelength range of 300 nm to 800 nm ² ) is measured, and then the unit transmittance and the degree of polarization are calculated using the following formulas (VI) and (VII), and the visibility is corrected by the second view field (C light source) of JIS Z8701.

Ty (%) = (T ¹ + T ² ) / 2 Equation (VI)

Py (%) = {(T ¹ -T ² ) / (T ¹ + T ² )} × 100 Formula (VII)

&Lt; Continuous Production Method of Polarizing Film (Original Circular Polarizer)

Although the outline of the manufacturing method of the present polarizing film has been described above, when the present polarizing film is commercially produced, a method capable of continuously producing the present polarizing film is required. Such a continuous production method is based on a roll-to-roll type, and is sometimes referred to as &quot; the present production method &quot;. Further, in the present manufacturing method, the case where a transparent substrate imparted with a phase difference is used as a substrate will be mainly described.

The present manufacturing method is, for example,

Preparing a first roll in which a transparent substrate is wound around a first winding core;

A step of continuously feeding the transparent substrate from the first roll,

A step of applying a composition containing a polymer having a photoreactive group and a solvent to continuously form a first coating film on a transparent substrate,

Drying the solvent from the first coated film to form a first dried film on the transparent substrate to continuously obtain the first laminated body,

A step of forming a photo alignment film by irradiating the first dry film with polarized UV to continuously obtain a second laminate,

A step of applying a composition containing a polymerizable smectic liquid crystal compound, a dichroic dye and a solvent on a photo alignment film to continuously form a second coating film on the photo alignment film,

Drying the second coating film under a condition that the polymerizable Smectic liquid crystal compound contained in the second coating film is not polymerized to thereby form a second dried film on the photo alignment film to continuously obtain the third laminate; ,

A step of continuously obtaining a polarizing film by polymerizing the polymerizable Smectic liquid crystal compound contained in the second dried film into a Smectic liquid crystal state and then polymerizing the polymerizable Smectic liquid crystal compound while maintaining the Smectic liquid crystal state; ,

And a step of winding the polarizing film continuously obtained on the second winding core to obtain a second roll. Here, with reference to Fig. 1, main parts of the present manufacturing method will be described.

The first roll 210, on which the transparent substrate is wound around the first winding core 210A, is easily available on the market, for example. Examples of the transparent substrate that can be obtained on the market in the form of rolls include a film made of cellulose ester, cyclic olefin resin, polyethylene terephthalate, polycarbonate or polymethacrylic acid ester among the transparent substrates already mentioned . It is also usable when the present polarizing film is obtained in the form of a circularly polarizing plate. The transparent substrate to which the retardation is imparted is also easily available on the market, and for example, a retardation film made of cellulose ester, polycarbonate or cycloolefin- And the like.

Subsequently, the transparent substrate is unwound from the first roll 210. The transparent substrate is unwound by rotating the first roll 210 with the rotating means provided on the winding core 210A of the first roll 210. [ A suitable auxiliary roll 300 may be provided in the direction of conveying the transparent substrate from the first roll 210 and the transparent substrate may be loosened by the rotating means of the auxiliary roll 300. In addition, both of the first winding core 210A and the auxiliary roll 300 may be provided with a rotating means so that the transparent substrate is loosened while a suitable tension is applied to the transparent substrate.

When the transparent substrate unwound from the first roll 210 passes through the coating device 211A, the composition for forming an alignment film is applied onto the surface of the transparent substrate by the coating device 211A. As described above, the coating device 211A is a printing method such as a gravure coating method, a die coating method, and a flexo printing method in order to continuously apply the composition for forming an alignment film.

The film passed through the coating device 211A corresponds to a laminate of a transparent substrate and a first coating film. The transparent substrate on which the first coated film is formed (laminated) in this manner is conveyed to the drying furnace 212A and heated by the drying furnace 212A to be transferred to the first laminated body composed of the transparent substrate and the first dried film Transformation). As the drying furnace 212A, for example, a hot air type drying furnace or the like is used. The set temperature of the drying furnace 212A is determined in accordance with the type of the solvent contained in the composition for forming an alignment film, which is applied by the application device 211A. The drying furnace 212A may be divided into a suitable zone and a set temperature may be different for each of a plurality of divided zones. A plurality of drying furnaces may be arranged in series, and each drying furnace may be operated at a different set temperature. It may be a form in which the film is sequentially transported to the drying furnace.

The first laminate continuously formed by passing through the heating furnace 212A is then continuously polarized by the polarizing UV irradiation device 213A on the surface of the laminate on the side of the first dried film or on the surface of the transparent substrate UV is irradiated, and the first dry film is called a photo-polarizing film. At this time, the angle formed by the transport direction D1 of the film and the alignment direction D2 of the photo alignment film to be formed is set to about 45 degrees. 2 is a diagram schematically showing the relationship between the alignment direction D2 of the photo alignment layer formed after the polarized UV irradiation and the transport direction D1 of the film. 1 shows the surface of the first laminate after passing through the polarizing UV irradiator 213A when viewed from the direction of transport D1 of the film and the alignment direction D2 of the photo alignment film, .

The first laminate thus formed continuously passes through the coating device 211B to apply the composition for forming a polarizing film on the photo alignment film of the first laminate and then passes through the drying furnace 212B The polymeric smectic liquid crystal compound contained in the second dried film of the second laminate or the second laminate becomes a laminate in which Smectic's liquid crystal state is formed. The drying furnace 212B has a function of drying and removing the solvent from the composition for forming a polarizing film applied on the photo alignment film and a thermal polymerization process in which the polymerizable smectic liquid crystal compound contained in the second dried film is thermally To the second dry film. In addition, as described above, in order to bring the polymerizable smectic liquid crystal compound into a liquid crystal state in a smectic phase, in order to make a once-polymerizable smectic liquid crystal compound into a liquid crystalline state in a nematic phase, , A multistage heat treatment must be performed on the first laminate. For this reason, as described in the drying furnace 212A, the drying furnace 212B is provided with a plurality of drying furnaces each having a set temperature different from each other but different from each other, and a plurality of drying furnaces are installed in series Is preferable.

In the film passed through the drying furnace 212B, the solvent contained in the composition for forming a polarizing film is sufficiently removed, and the polymerizable Smectic liquid crystal compound in the second dried film is irradiated with light And is conveyed to the apparatus 213B. By irradiation of light by the light irradiation device 213B, the polymerizable Smectic liquid crystal compound is photopolymerized while maintaining the liquid crystal state, and the present polarizing film is continuously formed on the alignment film.

The thus formed continuously polarized film is wound on the second winding core 220A in the form of a laminate including a transparent base material and an orientation film to obtain the shape of the second roll 220. [ When the formed polarizing film is wound to obtain the second roll, it may be wound together with a suitable spacer.

As described above, when the transparent substrate is used in the first roll / coating device 211A / drying furnace 212A / polarized UV irradiation device 213A / coating device 211B / drying furnace 212A / light irradiation device 213A , The present polarizing film is continuously produced on the photo alignment film on the transparent substrate.

1 shows a method for continuously producing the transparent film from the transparent substrate to the polarizing film. However, for example, when the transparent substrate is provided on the first roll / coating device 211A / drying furnace 212A / And a polarizing UV irradiator 213A in this order to wind the first laminate continuously formed on the winding core to form the first laminate in the form of a roll, to loosen the first laminate from the roll, The first laminated body may be passed through the application device 211B / the drying furnace 212A / the light irradiation device 213A in this order to manufacture the present polarizing film.

The structure and manufacturing method of the present polarizing film have been described above mainly in the case of a laminated body of a transparent substrate / photo alignment film / main polarizing film. However, as described above, May be peeled off, or a layer or film other than the transparent substrate / photo alignment film / main polarizing film may be laminated on the laminate. As described above, the polarizing film may further comprise a retardation film, and may further comprise an antireflection layer or a brightness enhancement film.

In addition, the transparent substrate itself may be a phase difference film to form a circularly polarizing plate or an elliptically polarizing plate in the form of a retardation film / photo alignment film / main polarizing film. For example, when a monoaxially stretched quarter-wave plate is used as the retardation film, it is preferable to manufacture the circularly polarizing plate by a roll-to-roll method by setting the irradiation direction of the polarized UV to be approximately 45 degrees with respect to the conveying direction of the transparent substrate It is possible. It is preferable that the 1/4 wavelength plate used when producing the circularly polarizing plate has such a characteristic that the in-plane retardation value for visible light becomes smaller as the wavelength becomes shorter.

A linearly polarizing plate roll in which the angle of the slow axis and the absorption axis of the polarizing film were shifted by using a 1/2 wavelength plate as the retardation film was prepared and a 1/4 wavelength plate was further provided on the opposite side of the plane on which the polarizing film was formed It is also possible to form a wide-band circularly polarizing plate.

In the present manufacturing method described above, the transparent substrate may be replaced with a substrate having no retardation. In this case, in order to manufacture the present circular polarizer, the present polarizer film is peeled from the laminate of the base material (having no retardation) / photo alignment film / main polarizer film obtained after the execution of the present manufacturing method, do. On the other hand, a winding body 230 on which the retardation film is wound is prepared. Then, the polarizing film viewed from the winding body 225, the retardation film from the winding body 230 are successively unwound, and these are adhered by an appropriate method, whereby the present circularly polarizing plate can be manufactured. The main part of this method is shown in Fig. In this case as well, it is sufficient to bond the retardation film and the main polarizing film so as to be approximately 45 占 with respect to the alignment direction. When bonding the present polarizing film and the retardation film, the present polarizing film and the retardation film may be bonded to each other through an adhesive layer formed from a pressure-sensitive adhesive by using a suitable pressure-sensitive adhesive.

In the case where the present polarizing film produced by the present production method has an absorption spectrum satisfying the relationship of the formulas (I) to (V), the present polarizing film is obtained as a monolayer by peeling off a transparent substance or the like The absorption spectrum of the main polarizing membrane of this monolayer can be measured by a method of measurement, but it is also possible to measure the absorption spectrum of a transparent substance or the like in advance and measure the absorption spectrum of the monolayer formed on the transparent substrate or the like A method of measuring an absorption spectrum of a main polarizing film of a base material or a method of measuring an absorption spectrum of a main polarizing film formed on a transparent base material or the like in advance by measuring the absorption spectrum of a transparent base material and the like, The difference between the absorption spectrum of the main polarizing film formed on the transparent substrate and the absorption spectrum of the transparent substrate or the like may be determined. By using means for measuring the absorption spectrum of these transparent substrates or the like in advance, the absorption spectrum of the present polarizing film can be easily obtained without peeling off the transparent substrate or the like.

&Lt; Uses of Polarizing Film &

This polarizing film makes it possible to manufacture a circularly polarizing plate which is very useful for organic EL (electroluminescence) display devices. The display device may be an inorganic electroluminescence (EL) display device.

Figs. 4 and 6 are schematic views schematically showing the cross-sectional structure of an EL display device (hereinafter, referred to as &quot; main organic EL display device &quot; in some cases) using the present polarizing film.

The present organic EL display device 30 using the present polarizing film will be described with reference to Fig. When the present polarizing film is used for the present organic EL display device, it is preferable to use the present polarizing film after converting it into a circularly polarizing plate (hereinafter referred to as &quot; original circularly polarizing plate &quot; The present circular polarizer plate has two embodiments. Therefore, before describing the configuration and the like of the organic EL display device 30, two embodiments of the present circular polarizer plate will be described with reference to Fig.

FIG. 5 (C1) is a cross-sectional view schematically showing the first embodiment of the present circular polarizer plate 110. FIG. The first embodiment is a circular polarizer 110 in which a retardation layer (retardation film) 4 is additionally provided on the polarizing film 3. FIG. 5C is a cross-sectional view schematically showing the second embodiment of the present circularly polarizing plate 110. FIG. The second embodiment is different from the first embodiment in that the transparent base material 1 itself is used as the retardation layer 4 by using a transparent base material (phase difference film) Function as a circular polarizer.

The organic EL display device 30 is obtained by laminating the organic functional layer 36 and the cathode electrode 37 on the substrate 33 on which the pixel electrode 35 is formed. The circularly polarizing plate 31 is disposed on the side opposite to the organic functional layer 36 with the substrate 33 interposed therebetween and the circularly polarizing plate 110 as the circularly polarizing plate 31 is used. A positive voltage is applied to the pixel electrode 35 and a negative voltage is applied to the cathode electrode 37 and a DC current is applied between the pixel electrode 35 and the cathode electrode 37 to cause the organic functional layer 36 to emit light . The organic functional layer 36 as a light emitting source includes an electron transporting layer, a light emitting layer, and a hole transporting layer. The light emitted from the organic functional layer 36 passes through the pixel electrode 35, the interlayer insulating film 34, the substrate 33, and the circularly polarizing plate 31 (circularly polarizing plate 110). Although the organic EL display device having the organic functional layer 36 is described, it may be applied to an inorganic EL display device having an inorganic functional layer.

In order to manufacture the organic EL display device 30, first, the thin film transistor 40 is formed on the substrate 33 in a desired shape. Then, an interlayer insulating film 34 is formed, and then a pixel electrode 35 is formed by a sputtering method and patterned. Thereafter, the organic functional layer 36 is laminated.

Then, a circularly polarizing plate 31 (original circularly polarizing plate 110) is provided on the surface of the substrate 33 opposite to the side where the thin film transistor 40 is provided.

When the present circular polarizer 110 is used as the circularly polarizing plate 31, the stacking order will be described with reference to an enlarged view of a portion C surrounded by a dotted line in Fig. When the circular polarizer 110 is used as the circular polarizer 31, the retarder layer 4 in the circular polarizer 110 is disposed on the substrate 33 side. 5C is an enlarged view of the circular polarizer plate 110 according to the first embodiment of the present invention as a circular polarizer plate 31. FIG. Is used as the circularly polarizing plate 31. Fig.

Next, members other than the main polarizing film 31 (circularly polarizing plate 110) of the organic EL display device 30 will be briefly described.

As the substrate 33, a sapphire glass substrate, a quartz glass substrate, a soda glass substrate and a ceramic substrate such as alumina; A metal substrate such as copper; A plastic substrate and the like. Although not shown, a thermally conductive film may be formed on the substrate 33. Examples of the thermally conductive film include a diamond thin film (DLC, etc.). When the pixel electrode 35 is of a reflective type, light is emitted in a direction opposite to the substrate 33. Therefore, not only a transparent material but also a non-transparent material such as stainless steel can be used. The substrate may be formed as a single substrate or may be formed as a laminated substrate by bonding a plurality of substrates with an adhesive. These substrates are not limited to plate-shaped substrates, but may be films.

As the thin film transistor 40, for example, a polycrystalline silicon transistor or the like may be used. The thin film transistor 40 is provided at the end of the pixel electrode 35 and has a size of about 10 nm to 30 m. The size of the pixel electrode 35 is about 20 탆 x 20 탆 to 300 탆 x 300 탆.

On the substrate 33, a wiring electrode of the thin film transistor 40 is provided. The wiring electrode has a low resistance and a function of electrically connecting to the pixel electrode 35 to suppress the resistance value. Generally, the wiring electrode is made of Al, Al, a transition metal (except for Ti), Ti And titanium nitride (TiN) may be used.

An interlayer insulating film 34 is provided between the thin film transistor 40 and the pixel electrode 35. The interlayer insulating film 34 is formed by depositing an inorganic material such as silicon oxide or silicon nitride such as SiO ₂ by sputtering or vacuum evaporation, a silicon oxide layer formed by SOG (spin on glass), a photoresist, a polyimide and an acrylic resin , And the like, may be used.

On the interlayer insulating film 34, the ribs 41 are formed. The ribs 41 are arranged in the peripheral portion (between adjacent pixels) of the pixel electrode 35. [ As the material of the ribs 41, an acrylic resin, a polyimide resin and the like can be given. The thickness of the ribs 41 is preferably 1.0 mu m or more and 3.5 mu m or less, more preferably 1.5 mu m or more and 2.5 mu m or less.

Next, an EL element including a pixel electrode 35 as a transparent electrode, an organic functional layer 36 as a light emitting source, and a cathode electrode 37 will be described. The organic functional layer 36 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 injecting layer sequentially.

As the pixel electrode 35, for example, ITO (indium tin oxide indium), IZO (zinc indium oxide indium), IGZO, ZnO, SnO ₂ and In ₂ O ₃ can be mentioned, and ITO and IZO are particularly preferable. The thickness of the pixel electrode 35 may be set to a thickness equal to or more than a certain level at which hole injection can be sufficiently performed, and is preferably set to about 10 nm to 500 nm.

The pixel electrode 35 can be formed by a vapor deposition method (preferably a sputtering method). The sputter gas is not particularly limited, and inert gases such as Ar, He, Ne, Kr, and Xe, or a mixed gas of these gases may be used.

Metal elements such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn and Zr may be used as the constituent material of the cathode electrode 37, In order to improve the operational stability, it is preferable to use an alloy system of two or three components selected from the exemplified metal elements. Examples of the alloy system include Ag · Mg (Ag: 1 at% to 20 at%), Al · Li (Li: 0.3 at% to 14 at%), In · Mg (Mg: 50 at% Al-Ca (Ca: 5 at% to 20 at%) and the like are preferable.

The cathode electrode 37 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, and more preferably 1 nm to 500 nm or more.

The hole injection layer has a function of facilitating the injection of holes from the pixel electrode 35. The hole transport layer has a function of transporting holes and a function of interrupting electrons and is also referred to as a charge injection layer or a charge transport layer .

The thickness of the light emitting layer, the total thickness of the hole injection layer and the hole transporting layer, and the thickness of the electron injection transporting layer are not particularly limited and are preferably 5 nm to 100 nm, although they vary depending on the forming method. Various organic compounds can be used for the hole injecting layer and the hole transporting layer. For the formation of the positive hole injection transport layer, the light emitting layer and the electron injection transport layer, a vacuum deposition method can be used in that a homogeneous thin film can be formed.

As the organic functional layer 36 serving as a light emitting source, it is possible to use light emission from a singlet exciton (fluorescence), use of light emitted from triplet excitons (phosphorescence), use of light emitted from singlet excitons (fluorescence) Including those using light emission (phosphorescence) from excitons, those formed with organic materials, those formed with organic materials and those formed with inorganic materials, polymer materials, low molecular materials, polymers and low molecular materials Can be used. However, the present invention is not limited to this, and the organic functional layer 36 using various known materials for the EL element can be used for the present organic EL display device 30.

A desiccant 38 is disposed in the space between the cathode electrode 37 and the sealing lid 39. This is because the organic functional layer 36 is weak in humidity. And the moisture is absorbed by the desiccant 38 to prevent deterioration of the organic functional layer 36.

6 is a schematic view showing a sectional configuration of another embodiment of the present organic EL display device 30. Fig. This organic EL display device 30 has a sealing structure using the thin film sealing film 41, and emitted light can also be obtained from the opposite side of the array substrate.

As the thin film sealing film 41, it is preferable to use a DLC film in which DLC (diamond-like carbon) is vapor-deposited on a film of an electrolytic capacitor. The DLC film has a characteristic that the water permeability is very poor, and the moisture-proof performance is high. Alternatively, a DLC film or the like may be formed directly on the surface of the cathode electrode 37 by vapor deposition. The thin film sealing film 41 may be formed by laminating a resin thin film and a metal thin film in multiple layers.

As described above, there is provided a novel organic EL display device comprising the novel polarizing film (original polarizing film) according to the present invention and the original polarizing plate including the present polarizing film.

The present organic EL display device is provided with the present circular polarizing plate including the present polarizing film. When the intensity of light of 450 nm wavelength is I450, the intensity of light of 550 nm wavelength is I550, and the intensity of light of 650 nm wavelength is I650 ,

1 < / = I450 / I550 &lt; 2 (X)

1 < / = I450 / I650 &lt; 2 (XI)

The light emission spectrum satisfying all of the relations expressed by the following expression In the present organic EL display device, since the polarizing film substantially does not absorb light from the organic EL light emitting element, particularly blue light having a short life span (light emitting element having a wavelength of 450 nm), the emission intensity of the organic EL light emitting element is increased Therefore, the number of organic EL image display devices can be increased. Therefore, the present polarizing film and the present circular polarizing plate are very valuable in industry.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples. In the examples, &quot;% &quot; and &quot; part &quot; are by mass% and part by mass unless otherwise specified.

In the present embodiment, the following polymerizable Smectic liquid crystal compound was used.

The compound (2-6) (the compound represented by the following formula (2-6)

Compound (2-6) can be synthesized by the method described in Lub et al. Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

[Measurement of Phase Transition Temperature]

The phase transition temperature of the compound (2-6) was confirmed by determining the phase transition temperature of the film composed of the compound (2-6). The operation is as follows.

A film made of the compound (2-6) was formed on a glass substrate having an orientation film formed thereon, and the phase transition temperature was confirmed by a texture observation with a polarization microscope (BX-51, manufactured by Olympus) while heating. The film made of the compound (2-6) underwent phase transitions in a nematic phase at 112 ° C and phase transitions in a Smectic A phase at 110 ° C and a phase transition at 94 ° C in a Smectic B phase, Respectively.

The compound (2-8) (the compound represented by the following formula (2-8)

Compound (2-8) was synthesized by reference to the synthesis of compound (2-6) described above.

[Measurement of Phase Transition Temperature]

The phase transition temperature of the compound (2-8) was confirmed in the same manner as the phase transition temperature measurement of the compound (2-6). Compound (2-8) underwent phase transition from nematic phase at 131 ° C to smectic A phase at 80 ° C and phase transition from Smectic B phase at 68 ° C Respectively.

Example 1

[Preparation of composition for forming polarizing film]

The ingredients shown in Table 3 were mixed and stirred at 80 占 폚 for 1 hour to obtain a composition for forming a polarizing film. The structure and composition of each component (the composition of the dichroic dye, see Table 3) are as follows.

Polymerizable smectic liquid crystal compounds; Compound (2-6) 90 parts

                           Compound (2-8) 10 parts

Dichroic dye;

Compound (1-5) 2.5 parts

Compound (1-8) 2.5 parts

Compound (1-21) 2.5 parts

A polymerization initiator;

6 parts of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (Irgacure 369; manufactured by Ciba Specialty Chemicals)

Leveling agents;

Polyacrylate compound (BYK-361N, manufactured by BYK-Chemie) 1.2 parts

solvent; Xylene 250 parts

[Measurement of Phase Transition Temperature]

(2-6) and a mixture (compound (2-8)) of the compound (2-6) and the compound (2-8) contained in the polarizing film forming composition prepared as described above in the same manner as in the case of the compound (2-6) 2-6) and the compound (2-8) was 90 parts: 10 parts). This polymerizable liquid crystal compound underwent phase transitions in a nematic phase at 116 ° C and a smectic A phase at 107 ° C at a temperature lowered to 140 ° C after the temperature was elevated to 140 ° C, .

[Production and Evaluation of Polarizing Film]

1. Formation of alignment film

A glass substrate was used as a transparent substrate.

A 2 mass% aqueous solution (oriented polymer composition) of polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type, manufactured by Wako Pure Chemical Industries, Ltd.) was applied on a glass substrate by a spin coat method, and after drying, Film. Subsequently, the surface of the obtained film was rubbed to form an alignment film. The rubbing treatment was carried out by means of a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Kako Co., Ltd.) using a semiautomatic rubbing apparatus (trade name: LQ-008 type, manufactured by Joyokogaku Co., Ltd.) 500 rpm, and 16.7 mm / s. By this rubbing treatment, a layered product 1 having an orientation film formed on a glass substrate was obtained.

2. Formation of polarizing film

A composition for forming a polarizing film was applied on the orientation film of the layered product 1 by a spin coat method and heated and dried on a hot plate at 120 DEG C for 1 minute and then cooled rapidly to room temperature to form a dried film on the orientation film Respectively. In this dry film, the liquid crystalline state of the polymerizable Smectic liquid crystal compound contained was a Smectic B phase. Subsequently, ultraviolet rays were irradiated onto the dried film at an exposure amount of 2000 mJ / cm 2 (based on 365 nm) using a UV irradiator (SPOT CURE SP-7, manufactured by Ushio DENKI KK) in a nitrogen atmosphere, Was polymerized while maintaining the liquid crystal state of the polymerizable liquid crystal compound to form a polarizing film from the dried film. The thickness of the polarizing film at this time was measured with a laser microscope (OLS 3000, manufactured by Olympus Corporation) to find that it was 1.8 탆.

4. Measurement of Absorbance and Transmittance

In order to confirm the usability of the polarizer, the absorbance was measured as follows. The absorbance (A ¹ ) in the direction of the transmission axis and the absorbance (A ² ) in the direction of the absorption axis were measured by a double beam method using a device with a polarizer attached to a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) 800 nm. &Lt; / RTI &gt; In the folder, the reference side was provided with a mesh that cuts the light amount by 50%. The values of absorbance A450, A550, A650, absorbance ratios A450 / A550 and A450 / A650 in the absorption axis directions at wavelengths of 450 nm, 550 nm and 650 nm were determined. In this spectrum measurement, the absorption spectrum of the layered product 1 for forming the present polarizing film was measured in advance, and the absorption spectrum was corrected by taking the absorption spectrum as a baseline.

Further, the visibility correction polarization degree Py and visibility sensitivity corrected transmittance Ty calculated from the dynamic spectrum results were obtained. The results of these measurements are shown in Table 2. The transmittance (T ¹ ) in the transmission axis direction and the transmittance (T ² ) in the absorption axis direction in the wavelength range of 300 nm to 800 nm are measured by the visibility correction polarization degree Py and visibility sensitivity corrected transmittance Ty, The values are obtained by calculating the unit transmittance and the degree of polarization using the following formulas (VI) and (VII), and correcting the visual sensitivity by the second view field (C light source) of JIS Z8701.

Ty (%) = (T ¹ + T ² ) / 2 Equation (VI)

Py (%) = {(T ¹ -T ² ) / (T ¹ + T ² )} × 100 Formula (VII)

Examples 2 to 8 also produced a polarizing film in the same manner as in Example 1 except that the kinds of the dichroic dye were changed. Table 1 shows the results of the addition amount of the dichroic dye and the film thickness of the prepared polarizing film. Also, the absorption spectrum was measured in the same manner. A550, A650, and absorbance ratios of A450 / A550 and A450 / A650 were measured at wavelengths of 450 nm, 550 nm and 650 nm in the absorption axis direction. Table 4 also shows the measurement results of the visibility-corrected polarization degree Py and visibility-corrected transmittance (Ty).

Reference Example 1

[Production of iodine PVA polarizer]

A polyvinyl alcohol film having an average degree of polymerization of about 2400 and a degree of saponification of 99.9 mol% or more and having a thickness of 75 mu m was uniaxially stretched by a dry method about 5.5 times and immersed in pure water at 60 DEG C for 60 seconds while maintaining the tension, And immersed in an aqueous solution of iodine / potassium iodide / water at a weight ratio of 0.05 / 5/100 at 28 ° C for 20 seconds. Then, it was immersed in an aqueous solution of 8.5 / 8.5 / 100 weight ratio of potassium iodide / boric acid / water at 72 ° C for 300 seconds. Subsequently, the film was washed with pure water at 26 DEG C for 20 seconds, and then dried at 65 DEG C to obtain a polarizing film in which iodine was adsorbed and oriented on the polyvinyl alcohol resin.

3 parts of a carboxyl group-modified polyvinyl alcohol (Kurarepo KL318 manufactured by Kuraray Co., Ltd.) and 3 parts of a water-soluble polyamide epoxy resin (Sumirez Resin 650 manufactured by Sumika Chemtex Co., Ltd. (aqueous solution with a solid concentration of 30% )], 1.5 parts of a polyvinyl alcohol-based adhesive, and a saponified triacetylcellulose film (KC8UX2MW manufactured by Konica Minolta Opt. Co., Ltd.) to protect both surfaces.

Reference Example 2

A polarizing film was produced in the same manner as in Comparative Example 1 except that the film was immersed in an aqueous solution of iodine / potassium iodide / water in an aqueous solution of 0.05 / 5/100 at 28 ° C for 35 seconds.

The thus prepared polarizing film was subjected to spectral measurement as in Example 1. The values of the absorbances A450, A550, A650, the absorbance ratios A450 / A550 and A450 / A650 in the absorption axis direction at wavelengths of 450 nm, 550 nm and 650 nm, the visibility correction polarization degree Py and the visibility corrected transmittance Ty The results are shown in Table 4.

[Table 3]

[Table 4]

Example 9

[Production of a photo alignment film on a retardation film]

(3) was prepared by using a retardation film (uniaxially stretched film WRF-S (modified polycarbonate resin), a retardation value of 137.5 nm and a thickness of 50 占 퐉, manufactured by Dainippon Ink & In 5% of xylene was applied by a bar coating method and dried at 120 캜 to obtain a dried coating film. On this dried film, polarized UV was irradiated in the direction of 45 DEG to the slow axis of the retardation film to obtain a photo alignment film. The polarizing UV treatment was performed under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ by using a UV irradiator (SPOT CURE SP-7; manufactured by Usuo Denki Co., Ltd.).

[Production of Circular Polarizer]

The composition for forming a polarizing film prepared in Example 1 was coated on the photo-alignment film by the bar coating method, heated and dried in a drying oven at 120 캜 for one minute, and then cooled to room temperature. In this dry film, the liquid crystal state of the polymerizable liquid crystal compound contained was Smectic B phase. Subsequently, an ultraviolet ray having an exposure dose of 2000 mJ / cm 2 (based on 365 nm) was irradiated to the layer formed from the composition for forming a polarizing film by using a UV irradiator (SPOT CURE SP-7, manufactured by Ushio DENKI KK) The polymerizable liquid crystal compound contained in the dried film was polymerized while maintaining the liquid crystal state of the polymerizable liquid crystal compound to form a polarizing film from the dried film.

The film thickness of the polarizing film at this time was measured by a laser microscope (OLS 3000, manufactured by Olympus Corporation) and found to be 1.8 탆.

Example 10

A circular polarizer was produced in the same manner as in Example 9, except that the polarizing film forming composition prepared in Example 2 was used in place of the polarizing film forming composition prepared in Example 1.

Example 11

A circular polarizer was produced in the same manner as in Example 9 except that the composition for forming a polarizing film in Example 8 was used in place of the composition for polarizing film prepared in Example 1.

Reference Example 3

The absorption axis of the polarizing film prepared in Referential Example 1 and the retardation axis of the retardation film (uniaxially stretched film WRF-S (modified polycarbonate resin), retardation value 137.5 nm, thickness 50 탆, manufactured by Dainippon Ink & Were bonded to each other through a pressure-sensitive adhesive so that the angle formed was 45 DEG, thereby producing a circularly polarizing plate.

Reference Example 4

A circular polarizer was produced in the same manner as in Reference Example 3 except that the polarizing film prepared in Reference Example 2 was used in place of the polarizing film prepared in Reference Example 1.

&Lt; Measurement of optical characteristics &

The retardation films of the circularly polarizing plates obtained in Examples 9 to 10 and Reference Examples 3 to 4 were joined to an aluminum metal plate through a pressure-sensitive adhesive, and the reflectance at 450 nm, 550 nm and 650 nm Were measured. Further, visual sensitivity correction was performed by a 2-degree field of view (C light source) of JIS Z8701 to calculate the visibility-corrected reflectance. The results are shown in Table 4.

It can be seen that the circularly polarizing plate produced from this polarizing film has a good antireflection property with respect to human visual sensitivity.

[Table 5]

This polarizing film is very useful in manufacturing a liquid crystal display, an (organic) EL display and a projection type liquid crystal display.

1: transparent substrate, 2: photo alignment layer. The present invention relates to a polarizing film and a method of manufacturing the polarizing film, and more particularly, to a polarizing film comprising a polarizer, a polarizer, a first laminate, a second laminate, a third laminate, a first laminate, And the polarizing film is wound around the winding core in a direction opposite to the direction in which the polarizing film is wound around the winding core. A thin film transistor having a thin film transistor and a method of manufacturing the thin film transistor according to the first aspect of the present invention includes the steps of: EL display device

Claims (9)

A polarizing film formed from a composition containing two or more kinds of dichroic dyes different in maximum absorption wavelength has an absorption spectrum satisfying all of the relations expressed by the following formulas (I) to (V) and having a one- Polarizing film having:
0.3? A450 / A550 <0.8 (I)
0.3? A450 / A650 < 1.0 (II)
0.5? A450? 2 (III)
1? A550? 3 (IV)
1? A? 650? 3 (V)
(Wherein,
A450 is the absorbance of the polarized light parallel to the alignment direction at a wavelength of 450 nm,
A550 is the absorbance of the polarized light parallel to the alignment direction at a wavelength of 550 nm,
And A650 represents the absorbance of the polarized light parallel to the alignment direction at a wavelength of 650 nm. The polarizing membrane according to claim 1, wherein the composition further comprises a polymerizable smectic liquid crystal compound. 3. The polarizing film according to claim 1 or 2, wherein the two or more dichroic dyes are all polyazo dye represented by the following formula (1).

[In the formula (1)
n is 1 or 2;
Ar ₁ and Ar ₃ each independently represent any one of the following groups.

Ar ₂ represents any one of the following groups.

A ₁ and A ₂ each independently represent any one of the following groups.

m is an integer of 0 to 10, and when two m are present in the same group, these two m are the same or different.] 4. The polarizing film according to any one of claims 1 to 3, wherein the visual sensitivity-corrected single unit transmittance (Ty) is 43% or more and the visual sensitivity-corrected individual polarization degree (Py) is 90% or more. A circularly polarizing plate having a polarizing film according to any one of claims 1 to 4 and a? / 4 layer and satisfying the following requirements (A1) and (A2):
(A1) an angle formed between the absorption axis of the polarizing film and the slow axis of the? / 4 layer is 45 °;
(A2) The value of the front retardation of the? / 4 layer measured with light having a wavelength of 550 nm is in the range of 100 nm to 150 nm. 6. The circular polarizer according to claim 5, wherein the front retardation value of the? / 4 layer with respect to visible light is reduced as the wavelength becomes shorter. A circularly polarizing plate having the polarizing film according to any one of claims 1 to 4, a? / 2 layer and a? / 4 layer in this order and satisfying the following requirements (B1) to (B4)
(B1) the angle formed by the absorption axis of the polarizing film and the slow axis of the? / 2 layer is 15 °;
(B2) an angle formed by the slow axis of the? / 2 layer and the slow axis of the? / 4 layer is 60 °;
(B3) the? / 2 layer has a value of the front retardation of the? / 4 layer measured with light having a wavelength of 550 nm in the range of 200 nm to 300 nm;
(B4) The λ / 4 layer has a front retardation value of 100 nm to 150 nm as measured by light having a wavelength of 550 nm. An organic EL display device comprising the circularly polarizing plate according to any one of claims 5 to 7 and an organic EL device. 9. The light emitting device according to claim 8, wherein, when light having a wavelength of 450 nm is I450, light having a wavelength of 550 nm is I550, and light having a wavelength of 650 nm is I650,
1 < / = I450 / I550 < 2 (X)
1 &lt; / = I450 / I650 &lt; 2 (XI)
And an emission spectrum that satisfies all of the relations expressed by the following expression: &quot; (1) &quot;

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