KR102073987B1 - Compound and dichroic dye, and polarizing film - Google Patents

Abstract

[식 (1)에서, Y는 식 (Y1) 또는 식 (Y2)로 표시되는 기이다.

R¹은 식 (R¹-1)∼식 (R¹-3) 중 어느 것으로 표시되는 기이다.

R²는 식 (R²-1)∼식 (R²-6) 중 어느 것으로 표시되는 기이다.

An object of this invention is to provide the novel compound which has the absorption maximum in wavelength 400-520 nm, and can form a polarizing film with a high dichroic ratio, the polarizing film containing this new compound, etc.
The compound represented by Formula (1), the composition containing this compound and a liquid crystalline compound, the polarizing film formed from this composition, etc. are provided.

[In Formula (1), Y is group represented by Formula (Y1) or Formula (Y2).

R ¹ is a group represented by any ^one of formulas (R ¹ -1) to (R ¹ -3).

R ² is a group represented by any one of formulas (R ² -1) to (R ² -6).

Description

Compound and dichroic dye, and polarizing film TECHNICAL FIELD

The present invention relates to novel compounds, dichroic dyes, and polarizing films using the dichroic dyes.

As a polarizer used for a liquid crystal display device, the film which consists of polyvinyl alcohol dyed with iodine is used normally. On the other hand, the liquid crystal display device of recent years is strongly demanded for thinning, and accordingly, a polarizer is also required to be thinner. It is known to contain a dichroic dye as a polarizing film which a thin polarizer has.

For example, Patent Document 1 describes a polarizing film formed by depositing a specific polyazo dye material, but since the formation of the polarizing film requires a special apparatus such as a vapor deposition apparatus, it cannot be said to be an industrially advantageous method. On the other hand, Patent Document 2 describes a polarizing film formed of a composition containing a polymerizable liquid crystal compound having a higher order smectic Sx phase and a dichroic dye, but a dichroic dye having an absorption maximum at a wavelength of 400 to 520 nm, and dichroism. Neither the composition containing a pigment | dye nor the polarizing film formed from this composition is described. As a yellow to orange dichroic dye having an absorption maximum at a wavelength of 400 to 520 nm, Patent Literature 3 describes a bis azo dye having a 1,4-naphthyl structure.

Patent Document 1: Japanese Patent No. 3687130 Patent Document 2: Japanese Patent No. 4719156 Patent Document 3: Japanese Patent No. 1454637

However, as a result of the inventor's examination, the dichroic dye (bisazo dye) described in Patent Document 3, when combined with a higher order smectic liquid crystal compound, is dispersed between dense molecular chains formed from the higher order smectic liquid crystal compound. It became clear that only a polarizing film with low dichroic ratio and inferior polarization performance was obtained. An object of the present invention comprises a compound having an absorption maximum at a wavelength of 400 to 520 nm and capable of forming a polarizing film having a high dichroic ratio, a dichroic dye containing the compound as an active ingredient, a dichroic dye and a polymerizable liquid crystal compound. It is providing the composition and the polarizing film formed from this composition.

The present invention includes the following inventions.

[1] A compound represented by the formula (1).

[In Formula (1), Y is group represented by Formula (Y1) or Formula (Y2).

(Wherein L is an oxygen atom or -NR- and R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

R ¹ is a group represented by formula (R ¹ -1), formula (R ¹ -2) or formula (R ¹ -3).

(In formula, ma is an integer of 0-10, and when there are two ma in the same group, these two ma are mutually same or different. * Represents a coupling | bonding number.)

R ² is a formula (R ² -1), formula (R ² -2), formula (R ² -3), formula (R ² -4), formula (R ² -5) or a group represented by the formula (R ² -6) Is represented by.

(Wherein mb is an integer of 0 to 10. * represents the number of bonds.)]

[2] A dichroic dye comprising the compound described in [1] as an active ingredient.

[3] A composition comprising the compound as described in [1] and a polymerizable liquid crystal compound.

[4] The composition according to [3], wherein the polymerizable liquid crystal compound is a compound exhibiting a smectic liquid crystal phase.

[5] The composition according to [3] or [4], further comprising a solvent.

[6] The composition according to any one of [3] to [5], further comprising a polymerization initiator.

[7] A polarizing film, which is formed from the composition according to any one of [3] to [6].

[8] The absorption maximum wavelength (λmax1) of the polarizing film is

The polarizing film as described in [7] characterized by shifting longer wavelength than the absorption maximum wavelength ((lambda) max2) of a dichroic dye.

[9] The polarizing film according to [7] or [8], wherein a difference between the absorption maximum wavelength (λmax1) of the polarizing film and the absorption maximum wavelength (λmax2) of the dichroic dye is 20 nm or more.

[10] The polarizing film according to any one of [7] to [9], wherein a Bragg peak is obtained in X-ray diffraction measurement.

[11] A polarizer comprising the polarizing film and the transparent substrate according to any one of [7] to [10].

[12] a step of preparing a laminate in which an alignment film is laminated on a transparent substrate;

Forming a coating film by applying the composition according to any one of [3] to [6] on the alignment film of the laminate;

It has a process of superposing | polymerizing the said polymeric liquid crystal compound contained in the said coating film, The manufacturing method of the polarizer characterized by the above-mentioned.

[13] forming a laminate by forming an optical alignment film on a transparent substrate;

Forming a coating film by applying the composition according to any one of [3] to [6] on the photoalignment film of the laminate;

It has a process of superposing | polymerizing the said polymeric liquid crystal compound contained in the said coating film, The manufacturing method of the polarizer characterized by the above-mentioned.

[14] A liquid crystal display device comprising the polarizing film as described in any one of [7] to [10].

[15] A circularly polarizing plate, comprising the polarizing film according to any one of [7] to [10] and a quarter wave plate, and satisfying the following requirements (A1) and (A2).

(A1) the angle between the absorption axis of the polarizing film and the slow axis of the quarter wave plate is approximately 45 °;

(A2) The value of the front retardation of the quarter wave plate measured in light of wavelength 550 nm is in the range of 100 to 150 nm.

[16] An organic EL display device comprising the circularly polarizing plate described in [15] and an organic EL element.

According to the present invention, a compound having an absorption maximum at a wavelength of 400 to 520 nm and capable of forming a polarizing film having a high dichroic ratio, a dichroic dye containing the compound as an active ingredient, and a dichroic dye and a polymerizable liquid crystal compound It is possible to provide a polarizing film formed of the composition and the composition.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the continuous manufacturing method of the polarizer (this polarizer) containing the polarizing film of this invention.
It is a schematic diagram which shows the relationship of the orientation direction D2 of a photo-alignment film, and the conveyance direction D1 of a film.
It is a schematic diagram which shows the cross-sectional structure of the liquid crystal display device using the polarizing film of this invention.
4 is a schematic diagram illustrating the layer order of the present polarizer used in the liquid crystal display of FIG. 3.
FIG. 5 is a schematic diagram illustrating the layer order of the present polarizer used in the liquid crystal display of FIG. 3. FIG.
6 is a schematic diagram showing a cross-sectional structure of an EL display device using the polarizing film of the present invention.
It is a schematic diagram which shows the cross-sectional structure of embodiment of this polarizer containing the polarizing film of this invention.
It is a schematic diagram which shows an example of the continuous manufacturing method of the circularly-polarizing plate (this circularly polarizing plate) containing the polarizing film of this invention.
9 is a schematic diagram showing the layer order of the circular polarizing plate used in the EL display device of FIG.
10 is a schematic diagram showing a cross-sectional structure of an EL display device using the polarizing film of the present invention.
Fig. 11 is a schematic diagram showing the configuration of a projection type liquid crystal display device using the polarizing film of the present invention.

The present invention is a compound represented by the formula (1) (hereinafter referred to as "compound (1)" in some cases), and a dichroic dye using compound (1) as an active ingredient (hereinafter referred to as "dichroic dye" (1) ", the composition containing this dichroic dye and a polymeric liquid crystal compound (henceforth" a composition for polarizing film formation "), and the polarizing film formed from the composition for polarizing film formation (henceforth And "called this polarizing film" in some cases. This polarizing film is not only suitably used for a liquid crystal display device, but also makes it possible to manufacture a circularly polarizing plate (hereinafter, referred to as "present circularly polarizing plate") suitable for an organic EL display device. First, compound (1) is demonstrated.

<Compound (1)>

Compound (1) is represented by said Formula (1).

Preferable embodiments of the compound (1) will be described taking the groups of the formula (1) and the like as an example.

The geometric isomer of the azobenzene moiety of the formula (1) is preferably trans.

Y in Formula (1) is group represented by said Formula (Y1) or Formula (Y2), Preferably it is group represented by Formula (Y1). In formulas (Y1) and (Y2), the straight lines at both ends represent a bond number, the bond number on the left is bonded to the phenylene group having an azo group, and the bond number on the right is bonded to the phenylene group having R ² . have. L is an oxygen atom or -NR-, and R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group etc. are mentioned as this alkyl group. Especially, if L is an oxygen atom or -NH-, it is preferable, and if it is an oxygen atom, it is more preferable.

R ¹ is a group represented by the above formula (R ¹ -1), formula (R ^1-2 ) or formula (R ^1-3 ), preferably formula (R ^1-2 ) and formula (R ^1- ) Is represented by 3). Two ma in the group represented by the formula (R ^1-2 ) may be the same or different, respectively, but are preferably the same. ma is more preferable if it is an integer of 0-5.

R ² is the above formula (R ² -1), formula (R ² -2), formula (R ² -3), formula (R ² -4), formula (R ² -5) or formula (R ^2- a group represented by 6), formula (R ² -2), formula (R ² -5), or (if the group represented by R ² -6), and more preferably, of the formula (R ² -6) It is more preferable if it is a group. If R ² is a group represented by formula (R ² -1), formula (R ² -2), formula (R ² -3), formula (R ² -5) or formula (R ² -6), Mb contained is preferable in it being an integer of 0-5, and more preferable in it being an integer of 0-3.

As a preferable compound (1), the compound etc. which are represented by following formula (1-1)-formula (1-8) are mentioned.

Especially, the compound represented by Formula (1-1), Formula (1-2), Formula (1-3), Formula (1-5), Formula (1-7), and Formula (1-8) is preferable, , The compounds represented by formulas (1-1), (1-2), (1-3) and (1-7) are particularly preferred.

Here, the manufacturing method of compound (1) is demonstrated. Compound (1) can be produced by, for example, a reaction represented by the following scheme from a compound [compound (1X)] represented by formula (1X) and a compound [compound (1Y)] represented by formula (1Y).

In the above scheme, R ¹ , R ^2, and Y have the same meanings as above, and Re ¹ and Re ² react with each other to be a group represented by Y. Examples of the combination of Re ¹ and Re ² include a combination of a carboxyl group and a hydroxyl group, a combination of a carboxyl group and an amino group (the amino group may be substituted by R), a combination of a carbonyl halide group and a hydroxyl group, a carbonyl halide group and an amino group (such an amino group And a combination of a carbonyloxyalkyl group and a hydroxyl group, and a combination of a carbonyloxyalkyl group and an amino group (the amino group may be substituted with R). In addition, although the compound (1X) which has R <^1> and the compound (1Y) which has R <^2> are demonstrated here, the compound which protected R <^1> with the suitable protecting group and the compound which protected R <^2> with the suitable protecting group react with each other, Then, compound (1) can also be manufactured by performing a suitable deprotection reaction.

Reaction conditions at the time of reacting compound (1X) and compound (1Y) can select an optimal well-known condition suitably according to the kind of compound (1X) and compound (1Y) to be used.

For example, a Re ¹ is carboxyl group, and Re ² is a hydroxyl group, Y is the number of the example, as the solvent -C (= O) -O- reaction conditions in the case of the conditions under which the condensation in the presence of an esterifying condensation agent. As a solvent, the solvent soluble in both compound (1X) and compound (1Y), such as chloroform, is mentioned. Diisopropyl carbodiimide (IPC) etc. are mentioned as esterification condensing agent. Here, it is preferable to use together bases, such as dimethylaminopyridine (DMAP) further. Although reaction temperature is selected according to the kind of compound (1X) and compound (1Y), For example, the range of -15-70 degreeC is mentioned, Preferably it is the range of 0-40 degreeC. The reaction time is, for example, in the range of 15 minutes to 48 hours.

The reaction time is appropriately sampled from the reaction mixture during the reaction, and the degree of loss of the compound (1X) and the compound (1Y) or the degree of formation of the compound (1) by known analytical means such as liquid chromatography or gas chromatography. You can also check and decide.

Compound (1) can be extracted from the reaction mixture after the reaction by a known method such as recrystallization, reprecipitation, extraction and various chromatography or by combining these operations.

Compound (1) is useful as a dichroic dye used for a polarizing film. Such a dichroic dye may contain compounds other than compound (1) as long as it does not significantly impair the one having an absorption maximum in the range of 400 to 520 nm, but is preferably a dichroic dye composed of only compound (1). The dichroic dye (1) is more preferable if its absorption maximum is 430-520 nm, and it is especially preferable if it is 440-510 nm. On the other hand, if the dichroic dye (1) shows an absorption maximum in the above range, the dichroic dye (1) may include a plurality of compounds (1).

<Composition for Polarizing Film Formation>

Next, the composition for polarizing film formation of this invention is demonstrated. The composition for polarizing film formation contains a polymeric liquid crystal compound.

The content of the dichroic dye (1) in the composition for forming a polarizing film is preferably 50 parts by mass or less with respect to 100 parts by mass of the polymerizable liquid crystal compound, more preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.1 The range of mass part or more and 5 mass parts or less is further more preferable. If it is in the said range, the solubility with respect to the solvent of the dichroic dye 1 is enough, and it is easy to obtain this polarizing film without the occurrence of a defect. Moreover, when content of the dichroic dye 1 is in the said range, in the formation of a polarizing film, the orientation of a polymeric liquid crystal compound is difficult to be disturbed, and it is preferable.

Structural components other than the dichroic dye (1) in the composition for polarizing film formation of this invention are demonstrated.

<Polymerizable Liquid Crystal Compound>

The composition for polarizing film formation containing a dichroic dye (1) and a polymeric liquid crystal compound turns into this polarizing film by superposing | polymerizing in the state which orientated the polymeric liquid crystal compound. A polymerizable liquid crystal compound is a liquid crystal compound which has a polymerizable group in a molecule | numerator, and this polymerizable group is especially preferable if it is a radically polymerizable group. A radically polymerizable group means the group which participates in a radical polymerization reaction.

The polymeric liquid crystal compound contained in the composition for polarizing film formation of this invention may show a nematic liquid crystal phase, may show a smectic liquid crystal phase, or may show both a nematic liquid crystal phase and a smectic liquid crystal phase. It is preferable if it is a polymeric smectic liquid crystal compound which shows at least a smectic liquid crystal phase. The composition for polarizing film formation containing a polymeric smectic liquid crystal compound is preferable at the point which can obtain the present polarizing film which was more excellent in polarization performance, and the dichroic dye (1) is also dense and formed from the polymeric smectic liquid crystal compound. Since the present polarizing film having a very high dichroic ratio can be obtained even in a state dispersed between molecular chains, the effect of the dichroic dye 1 can be further enjoyed.

As the smectic liquid crystal phase represented by the polymerizable smectic liquid crystal compound, a higher order smectic liquid crystal phase is preferable. The higher order smectic liquid crystal phase here is smectic b phase, smectic d phase, smectic e phase, smectic f phase, smectic g phase, smectic h phase, smectic i phase, smectic j phase, smect Mechtic K phase and Smectic L phase, Among them, Smectic B phase, Smectic F phase and Smectic I phase are more preferable. If the smectic liquid crystal phase represented by a polymerizable liquid crystal compound is these higher order smectic liquid crystal phases, this polarizing film with a higher degree of orientation order can be manufactured. Moreover, the Bragg peak derived from higher order structures, such as a hexatic phase and a crystal phase, is obtained in the X-ray diffraction measurement of this polarizing film produced by the high order smectic liquid crystal phase with high orientation order. The said Bragg peak is a peak derived from the surface periodic structure of molecular orientation, According to the composition for polarizing film formation of this invention, this polarizing film whose period interval is 3.0-5.0 microseconds can be obtained.

Whether the polymeric liquid crystal compound contained in the composition for polarizing film formation shows nematic liquid crystalline or smectic liquid crystalline can be confirmed as follows, for example. After preparing a suitable base material, apply | coating the composition for polarizing film formation to this base material, and forming a coating film, the solvent contained in a coating film is removed by heat-processing or pressure-reducing processing on conditions on which a polymeric liquid crystal compound does not superpose | polymerize. Next, the liquid crystal phase expressed by heating the coating film formed on the base material to isotropic temperature and gradually cooling is examined by texture observation by a polarizing microscope, X-ray diffraction measurement, or differential scanning calorimetry. In this test | inspection, the polymeric liquid crystal compound which shows a nematic liquid crystal phase by cooling, for example, and shows a smectic liquid crystal phase by further cooling is especially preferable. In the nematic liquid crystal phase and the smectic liquid crystal phase, the fact that the polymerizable liquid crystal compound and the dichroic dye (1) are not phase separated can be confirmed by, for example, surface observation with various microscopes and scattering measurement with haze meter.

Hereinafter, the specific example of a thing preferable as a polymeric liquid crystal compound used for the composition for polarizing film formation is given.

As a preferable polymeric liquid crystal composition, the compound (henceforth called a "compound (2)") is represented, for example by Formula (2).

U^One-V^One-W^One-X^One-Y^One-X²-Y²-X³-W²-V²-U² (2)

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

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

U ¹ represents a hydrogen atom or a polymerizable group.

U ² represents a polymerizable group.

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

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

In compound (2), it is preferable that at least 2 is a ¹ , 4- phenylene group which may have a substituent among X <^1> , X <^2> and X <^3> .

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

As a substituent which the 1, 4- phenylene group which may have a substituent, or the cyclohexane- 1, 4- diyl group which may have a substituent optionally has a C1-C4 alkyl group, such as a methyl group, an ethyl group, and a butyl group; Cyano group; Halogen atom etc. are mentioned.

Y ¹ of compound (2) is preferably -CH ₂ CH _2- , -COO- or a single bond, and Y ² is preferred if -CH ₂ CH ₂ -or -CH ₂ O-.

U ² is a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, and preferably a polymerizable group. If U ¹ and U ² is a polymerizable group together, and more preferably is a photopolymerization group together. Here, a photopolymerizable group means group which can participate in a polymerization reaction by active radical, acid, etc. which generate | occur | produced from the photoinitiator mentioned later. The polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can polymerize under lower temperature conditions.

In compound (2), although the polymerizable groups of U <^1> and U <^2> may mutually differ, it is preferable that they are the same kind of group. Examples of the polymerizable group include vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group and oxetanyl group. Especially, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group, and oxetanyl group are preferable, and acryloyloxy group is more preferable.

As a C1-C20 alkanediyl group in the C1-C20 alkanediyl group which may have a substituent represented by V <^1> and V <^{2>, it} is a methylene group, an ethylene group, a propane-1, 3- diyl group, butane-1 , 3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group , Decane-1,10-diyl group, tetradecane-1,14-diyl group and icosane-1,20-diyl group. V <^1> and V <^2> , Preferably they are a C2-C12 alkanediyl group, More preferably, they are a C6-C12 alkanediyl group.

As a substituent which the C1-C20 alkanediyl group which may have a substituent arbitrarily has a cyano group, a halogen atom, etc. are mentioned, The said alkanediyl group is preferable if it is unsubstituted and if it is unsubstituted and linear, it is more preferable.

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

As compound (2), the compound etc. which are represented by Formula (2-1)-formula (2-43) are mentioned. When the specific example of such compound (2) has a cyclohexane-1, 4-diyl group, it is preferable that such a cyclohexane-1, 4-diyl group is a trans body.

A polymerizable liquid crystal compound can be used individually or in mixture of 2 or more types for the composition for polarizing film formation. Moreover, when mixing 2 or more types, it is preferable that at least 1 type is compound (2). The mixing ratio in the case of mixing two types of polymerizable liquid crystal compounds is 1: 99-50: 50 normally, Preferably it is 5: 95-50: 50, More preferably, it is 10: 90-50: 50.

Among the exemplified compounds (2), formula (2-5), formula (2-6), formula (2-7), formula (2-8), formula (2-9), formula (2-10), formula (2-11), formula (2-12), formula (2-13), formula (2-14), formula (2-15), formula (2-22), formula (2-24), formula ( The compounds represented by 2-25), formula (2-26), formula (2-27), formula (2-28) and formula (2-29) are preferable. By interacting with other polymerizable liquid crystal compounds, these compounds can be polymerized under temperature conditions easily below the crystal phase transition temperature, that is, while sufficiently maintaining a high-order smectic liquid crystal state. Specifically, these compounds can be polymerized under a temperature condition of 70 ° C. or lower, preferably 60 ° C. or lower, while sufficiently maintaining a high degree of smectic liquid crystal state.

50-99.9 mass% is preferable with respect to solid content of the composition for polarizing film formation, and, as for the content rate of the polymeric liquid crystal compound in the composition for polarizing film formation, 80-99.9 mass% is more preferable. When the content ratio of the polymerizable liquid crystal compound is in the above range, the orientation of the polymerizable liquid crystal compound tends to be high, and thus is preferable. Here, solid content means the total amount of the component except volatile components, such as a solvent, in the composition for polarizing film formation.

Polymerizable liquid crystal compounds are described, for example, in Lub et al. Recl. Trav. Chim. It is produced by the known method described in Pays-Bas, 115, 321-328 (1996) or Japanese Patent No. 4,719,156.

<Solvent>

It is preferable that the composition for polarizing film formation in this invention contains a solvent. As a solvent, the solvent which can melt | dissolve a polymeric liquid crystal compound and a dichroic dye (1) completely is preferable. Moreover, it is preferable that it is a solvent inert to the polymerization reaction of the polymeric liquid crystal compound contained in the composition for polarizing film formation.

As a solvent, 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, γ-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 hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-containing solvents, such as chloroform and chlorobenzene, etc. are mentioned. These solvents may be used alone or in combination of a plurality thereof.

As for the content rate of a solvent, 50-98 mass% is preferable with respect to the total amount of the composition for polarizing film formation. In other words, 2-50 mass% of solid content in the composition for polarizing film formation is preferable. If solid content is 2 mass% or more, it exists in the tendency which is easy to obtain a thin this polarizing film, and is preferable. Moreover, since the viscosity of the composition for polarizing film formation becomes it low that the said solid content is 50 mass% or less, since the thickness of this polarizing film becomes substantially uniform, there exists a tendency which becomes difficult to produce a stain in this polarizing film, and is preferable. In addition, such solid content can be determined in consideration of the thickness of a polarizing film.

<Polymerization reaction preparation>

It is preferable that the composition for polarizing film formation in this invention contains a polymerization initiator. A polymerization initiator is a compound which can start the polymerization reaction of a polymeric liquid crystal compound. As a polymerization initiator, a photoinitiator is preferable at the point which can start the polymerization reaction under low temperature conditions. Specifically, a compound which generates an active radical or an acid by the action of light is used as the photopolymerization initiator. It is more preferable to generate active radicals by the action of light among photopolymerization initiators.

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

As a benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycar Carbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morph Polynophenyl) butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethan-1-one, 2-hydride Hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2-methyl-1- [4- And oligomers of (1-methylvinyl) phenyl] propan-1-one.

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

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4 -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) Tenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like Can be mentioned.

Commercially available polymerization initiators may be used. Commercially available polymerization initiators include "Irgacure 907", "Irgacure 184", "Irgacure 651", "Irgacure 819", "Irgacure 250", "Irgacure 369" ( Chiba Japan Co., Ltd .; "Seiquiol BZ", "Seiquiol Z", "Seiquiol BEE" (Seiko Chemical Co., Ltd.); "Kayacure BP100" (Nippon Kayaku Co., Ltd.); "Kayakure UVI-6992" (manufactured by Dausa); "ADEKA OPTOMA SP-152", "ADEKA OPTOMA SP-170" (ADEKA Co., Ltd.); "TAZ-A", "TAZ-PP" (Nihon Siberhegsa); And "TAZ-104" (Sanwa Chemical Co., Ltd.).

When the composition for polarizing film formation contains a polymerization initiator, the content can be suitably adjusted according to the kind and quantity of the polymeric liquid crystal compound contained in the composition for polarizing film formation, Usually content of 100 masses of a polymeric liquid crystal compound Content of the polymerization initiator with respect to a part is 0.1-30 mass parts, Preferably it is 0.5-10 mass parts, More preferably, it is 0.5-8 mass parts. If content of a polymerization initiator exists in the said range, since it can superpose | polymerize without disturbing the orientation of a polymeric liquid crystal compound, it is preferable.

When the composition for polarizing film formation contains a photoinitiator, the composition for polarizing film formation may contain a photosensitizer. As a photosensitizer, For example, xanthone compounds, such as xanthone and thioxanthone (for example, 2, 4- diethyl thioxanthone, 2-isopropyl thioxanthone, etc.); Anthracene compounds such as anthracene and an alkoxy group-containing anthracene (eg, dibutoxyanthracene); Phenothiazine, rubrene, and the like.

When the composition for polarizing film formation contains a photoinitiator and a photosensitizer, the polymerization reaction of the polymeric liquid crystal compound contained in the composition for polarizing film formation is accelerated | stimulated more.

Although content of such a photosensitizer can be suitably adjusted according to the kind and quantity of the photoinitiator and polymeric liquid crystal compound used together, it is 0.1-30 mass parts normally with respect to 100 mass parts of content of a polymeric liquid crystal compound, Preferably Is 0.5-10 mass parts, More preferably, it is 0.5-8 mass parts.

The composition for forming a polarizing film may contain a polymerization inhibitor in order to stably advance the polymerization reaction of the polymerizable liquid crystal compound. The degree of progress of the polymerization reaction of the polymerizable liquid crystal compound can be controlled by the polymerization inhibitor.

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

When the composition for polarizing film formation contains a polymerization inhibitor, the content is suitably adjusted according to the kind and quantity of the polymeric liquid crystal compound to be used, content of a photosensitizer, etc., but content of 100 mass parts of a polymeric liquid crystal compound is normally It is 0.1-30 mass parts with respect to, Preferably it is 0.5-10 mass parts, More preferably, it is 0.5-8 mass parts. If content of a polymerization inhibitor is in the said range, since it can superpose | polymerize without disturbing the orientation of the polymeric liquid crystal compound contained in the composition for polarizing film formation, it is preferable.

<Leveling agent>

It is preferable that the composition for polarizing film formation contains a leveling agent. A leveling agent has a function which adjusts the fluidity | liquidity of the composition for polarizing film formation, and makes the coating film obtained by apply | coating the composition for polarizing film formation more flat, surfactant, etc. are mentioned. As a preferable leveling agent, the leveling agent which has a polyacrylate compound as a main component, the leveling agent which has a fluorine atom containing compound as a main component, etc. are mentioned.

As a leveling agent mainly containing a polyacrylate compound, "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK-355", "BYK-358N", "BYK- 361N "," BYK-380 "," BYK-381 ", and" BYK-392 "[BYK Chemie Corporation].

Leveling agents mainly composed of fluorine atom-containing compounds include "mega park R-08", copper "R-30", copper "R-90", copper "F-410", copper "F-411", copper "F -443 ", East" F-445 ", East" F-470 ", East" F-471 ", East" F-477 ", East" F-479 ", East" F-482 "and East" F- 483 "[DIC Corporation]; "Suplon S-381", "S-382", "S-383", "S-393", "SC-101", "SC-105", "KH-40" and " SA-100 "[AGC Chemicals Co., Ltd.]; "E1830", "E5844" [Daikin Fine Chemical Genkyu Sho]; "E-top EF301", the "EF303", the "EF351", and the "EF352" [Misubishimaterialden Shigasei Co., Ltd.] etc. are mentioned.

When the composition for polarizing film formation contains a leveling agent, the content is 0.3 mass part or more and 5 mass parts or less with respect to 100 mass parts of content of a polymeric liquid crystal compound normally, Preferably they are 0.5 mass part or more and 3 mass parts or less. . When content of a leveling agent is in the said range, since it is easy to horizontally align a polymeric liquid crystal compound and the polarizing film obtained tends to become smoother, it is preferable. When content of the leveling agent with respect to a polymeric liquid crystal compound exceeds the said range, there exists a tendency for a stain to be easy to arise in the present polarizing film obtained. In addition, the said composition for polarizing film formation may contain two or more types of leveling agents.

<Formation method of this polarizing film>

Next, the method of forming this polarizing film with the composition for polarizing film formation is demonstrated. In this method, this polarizing film is formed by apply | coating the composition for polarizing film formation to a base material, Preferably it is a transparent base material. Hereinafter, a transparent base material is demonstrated.

<Transparent substrate>

A transparent base material is a base material which has transparency enough to permeate | transmit light, especially visible light. The said transparency means the characteristic that the transmittance | permeability with respect to the light ray over wavelength 380-780 nm becomes 80% or more. Specifically, a glass substrate, a plastic substrate, etc. are mentioned as a transparent base material. As a plastic which comprises a plastic base material, For example, Polyolefin, such as polyethylene, a polypropylene, norbornene-type polymer; Cyclic olefin resins; Polyvinyl alcohol; Polyethylene terephthalate; Polymethacrylic acid ester; Polyacrylic acid ester; Cellulose esters such as triacetyl cellulose, diacetyl cellulose and cellulose acetate propionate; Polyethylene naphthalate; Polycarbonate; Polysulfones; Polyether sulfone; Polyether ketones; Plastics, such as a polyphenylene sulfide and a polyphenylene oxide, are mentioned. Among them, particularly preferred are cellulose esters, cyclic olefin resins, polyethylene terephthalates or polymethacrylic acid esters from the viewpoint of being easily available on the market or excellent in transparency. In manufacturing the present polarizing film using such a transparent substrate, when supporting or storing the transparent substrate, it can be easily handled without causing breakage such as tearing. You may put it. In addition, although mentioned later, when manufacturing a circular polarizing plate with this polarizing film, retardation may be provided to a plastic base material. In this case, what is necessary is just to provide phase difference to a plastic base material by extending | stretching process, etc.

When providing retardation property to a plastic base material, since it is easy to control the retardation value, the plastic base material which consists of cellulose ester or cyclic olefin resin is preferable.

In the cellulose ester, at least a part of the hydroxyl groups contained in the cellulose is esterified with acetate. The cellulose ester film which consists of such cellulose esters can be obtained easily in a market. As a commercial triacetyl cellulose film, it is "Fuji tag film" (Fuji Shashin Film Co., Ltd.), for example; "KC8UX2M", "KC8UY" and "KC4UY" (Konica Minolta Opt Co., Ltd.), etc. are mentioned. Such a commercially available triacetyl cellulose film can be used as a transparent base material after providing retardation as it is or as needed. Moreover, it can use as a transparent base material, after surface-treating, such as an anti-glare process, a hard-coat process, an antistatic process, or an antireflective process, on the surface of the prepared transparent base material.

In order to provide retardation to a plastic base material, it extends by the method of extending | stretching a plastic base material as mentioned above. Although all the plastic base materials which consist of thermoplastic resins can be extended | stretched, the plastic base material which consists of cyclic olefin resin is more preferable at the point that it is easy to control retardation. A cyclic olefin resin is comprised from the polymer or copolymer of cyclic olefins, such as a norbornene and a polycyclic norbornene-type monomer, for example, and this cyclic olefin resin may contain a ring-opening part partially. Moreover, you may hydrogenate cyclic olefin resin containing a ring-opening part. The cyclic olefin resin may be a copolymer of, for example, a cyclic olefin, a chain olefin, a vinylated aromatic compound (styrene, etc.), etc., in that it does not significantly impair transparency or does not significantly increase hygroscopicity. In addition, the cyclic olefin resin may have a polar group introduced into the molecule.

When the cyclic olefin resin is a copolymer of a cyclic olefin and an aromatic compound having a chain olefin or a vinyl group, the chain olefins are ethylene, propylene and the like, and the vinylated aromatic compounds are styrene, α-methyl styrene, alkyl substituted styrene, and the like. . In such a copolymer, the content rate of the structural unit derived from cyclic olefin is 50 mol% or less, for example, about 15-50 mol% with respect to the total structural units of cyclic olefin resin. When the cyclic olefin resin is a ternary copolymer obtained from a cyclic olefin, a chain olefin, and a vinylated aromatic compound, the content ratio of the structural unit derived from the chain olefin is, for example, about 5 to 80 mol% with respect to the entire structural units of the cyclic olefin resin. The content rate of the structural unit derived from a vinylated aromatic compound is about 5-80 mol%. The cyclic olefin resin of such a terpolymer has the advantage that the usage-amount of expensive cyclic olefin can be comparatively small when manufacturing the said cyclic olefin resin.

Cyclic olefin resin is easily available on the market. Commercially available cyclic olefin resins include "Topas" [Ticona (Germany)]; "Aton" [JSR Corporation]; "ZEONOR" and "ZEONEX" (Nippon Xeon Co., Ltd.); "Apel" (made by Mitsui Chemicals, Inc.), etc. are mentioned. Such cyclic olefin resin can be formed into a film (cyclic olefin resin film) by well-known film forming means, such as a solvent casting method and a melt-extrusion method, for example. Moreover, the cyclic olefin resin film already marketed in the form of a film can also be used. As such a commercially available cyclic olefin resin film, it is "Esshina" and "SCA40" [Sekisuga Chemical Co., Ltd.]; "Zeonor Film" [Optes Co., Ltd.]; "Aton Film" [JSR Co., Ltd.], etc. are mentioned.

Next, the method of providing retardation property to a plastic base material is demonstrated. The plastic substrate can impart retardation by a known stretching method. For example, the roll (winding body) in which the plastic base material is wound up by the roll is prepared, the plastic base material is continuously unwound from such a winding body, and the unpacked plastic base material is conveyed to a heating furnace. The set temperature of the furnace is in the range of near the glass transition temperature (° C.) to [glass transition temperature +100] (° C.) of the plastic substrate, preferably near the glass transition temperature (° C.) to [glass transition temperature +50] (° C.). We assume range of). In this heating furnace, when extending | stretching to the advancing direction of a plastic base material or a direction orthogonal to a advancing direction, the conveyance direction and tension are adjusted, and it inclines at arbitrary angles, and carries out the uniaxial or biaxial thermal stretching process. A draw ratio is a range of about 1.1 to 6 times normally, Preferably it is a range of about 1.1 to 3.5 times. Moreover, as a method of extending | stretching in an oblique direction, if the orientation axis | shaft can be continuously inclined at a desired angle, it will not specifically limit, A well-known extending | stretching method can be employ | adopted. Examples of such stretching methods include methods described in JP-A-50-83482 and JP-A 2-113920.

Although the thickness of a transparent base material is the weight of the grade which can be practically handled, and the point which can ensure sufficient transparency, a thinner one is preferable, but when it is too thin, there exists a tendency for intensity | strength to fall and inferior to workability. The suitable thickness of a glass base material is about 100-3000 micrometers, for example, Preferably it is about 100-1000 micrometers. The suitable thickness of a plastic base material is about 5-300 micrometers, for example, Preferably it is about 20-200 micrometers. When using this polarizing film as a circularly-polarizing plate mentioned later, about 20-100 micrometers is preferable for the thickness of the transparent base material especially when using as a circularly-polarizing plate for mobile device uses. On the other hand, when providing retardation to a film by extending | stretching, the thickness after extending | stretching is determined by the thickness before extending | stretching, and a draw ratio.

<Alignment Film>

It is preferable that the orientation film is formed in the base material used for manufacture of this polarizing film. In that case, the composition for polarizing film formation is apply | coated on an oriented film. For this reason, it is preferable that the said orientation film has solvent tolerance of the grade which does not melt | dissolve by application | coating of the composition for polarizing film formation, etc. Moreover, it is preferable to have heat resistance in heat processing for removal of a solvent and the orientation of a liquid crystal. An orientation polymer can be used for formation of such an orientation film.

Examples of the oriented polymer include polyamides and gelatin having amide bonds in the molecule, polyimides having imide bonds in the molecule, and polyamic acid, polyvinyl alcohol, alkyl modified polyvinyl alcohol, polyacrylamide and polyoxa which are hydrolyzates thereof. And polymers such as sol, polyethyleneimine, polystyrene, polyvinylpyrrolidone, polyacrylic acid or polyacrylic acid esters. Among these, polyvinyl alcohol is preferable. These alignment polymers which form the alignment film may be used alone or in combination of two or more thereof.

The orientation polymer can be formed on the substrate by applying the orientation polymer on the substrate as an orientation polymer composition (a solution containing the orientation polymer) dissolved in a solvent. As said solvent, 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, γ-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; Nitrile solvents such as aromatic hydrocarbon solvents such as toluene and xylene, acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; And chlorine-substituted hydrocarbon solvents such as chloroform and chlorobenzene. These organic solvents may be used alone or in combination of two or more thereof.

Moreover, you may use a commercially available alignment film material as an orientation polymer composition for forming an alignment film. Examples of commercially available alignment film materials include San Eva (registered trademark, manufactured by Nissan Chemical Industries, Ltd.), Optoma (registered trademark, manufactured by JSR Corporation), and the like.

As a method of forming an oriented film in the said base material, the method of apply | coating and annealing the said oriented polymer composition or a commercially available oriented film material to a base material, etc. are mentioned, for example. The thickness of the alignment film thus obtained is usually in the range of 10 to 10000 nm, preferably in the range of 10 to 1000 nm.

It is preferable to perform rubbing as needed (rubbing method) in order to provide orientation control force with respect to the said oriented film. By providing an orientation regulation force, a polymeric liquid crystal compound can be oriented in a desired direction.

As a method of imparting the orientation regulating force by the rubbing method, for example, a rubbing cloth is rolled up, a rotating rubbing roll is prepared, a laminate formed with a coating film for forming an alignment film on a substrate is placed on a stage, and toward the rotating rubbing roll. By conveying, the method of making the said coating film for oriented film formation and the rotating rubbing roll contact is mentioned.

In addition, a so-called photoalignment film can also be used. A photo-alignment film is a composition (hereinafter referred to as "composition for forming a photo-alignment layer") containing a polymer or a monomer having a photoreactive group and a solvent applied to a substrate to irradiate polarized light (preferably polarized UV). By this, the alignment film which provided the orientation regulation force is said. A photoreactive group means group which generate | occur | produces a liquid-crystal orientation ability by irradiating light (light irradiation). Specifically, a photoreaction which causes the origin of the liquid crystal alignment ability, such as the orientation organic or isomerization reaction, dimerization reaction, photocrosslinking reaction or photolysis reaction of molecules produced by irradiation with light, is caused. Among these photoreactive groups, generating a dimerization reaction or a photocrosslinking reaction is preferable in terms of excellent orientation and maintaining a smectic liquid crystal state during polarizing film formation. As a photoreactive group which can cause the above reaction, it is preferable if it is an unsaturated bond, especially a double bond, A carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), nitrogen-nitrogen Particularly preferred are groups having at least one selected from the group consisting of double bonds (N = N bonds) and carbon-oxygen double bonds (C = O bonds).

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

Among them, a photoreactive group capable of causing a photodimerization reaction is preferable, and since a cinnamoyl group and a chalcone group have a relatively small amount of polarization irradiation required for optical alignment, it is easy to obtain an optical alignment film having excellent thermal stability and stability over time. desirable. In other words, as the polymer having a photoreactive group, one having a cinnamoyl group in which the terminal portion of the polymer side chain has a cinnamic acid structure is particularly preferable.

It is preferable to melt | dissolve the polymer and monomer which have a photoreactive group as a solvent of the composition for photo-alignment layer formation, The solvent used for the orientation polymer composition mentioned above as this solvent is mentioned, for example.

The concentration of the polymer or monomer having a photoreactive group with respect to the composition for forming the photoalignment layer may be appropriately adjusted according to the type of the polymer or monomer having the photoreactive group or the thickness of the photoalignment layer to be prepared. It is preferable to set it as 0.2 mass%, and the range of 0.3-10 mass% is especially preferable. In addition, the composition for forming the alignment layer may contain a polymer material such as polyvinyl alcohol or polyimide or a photosensitizer so long as the properties of the photo-alignment film are not significantly impaired.

As a method for applying the alignment polymer composition or the composition for forming an optical alignment layer to a substrate, coating methods such as spin coating method, extrusion method, gravure coating method, die coating method, bar coating method and applicator method, flexographic method and the like Known methods such as the printing method are employed. On the other hand, when performing this polarizing film manufacture by the RolltoRoll type continuous manufacturing method mentioned later, the coating method is the printing method, such as the gravure coating method, the die coating method, or the flexographic method, normally.

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

<The manufacturing method of this polarizing film>

The coating film is obtained by apply | coating the composition for polarizing film formation on the said base material or the orientation film formed in the base material. As a method of apply | coating, the method similar to what was illustrated as a method of apply | coating an orientation polymer composition or the composition for photo-alignment layer formation to a base material is mentioned, for example.

Next, a dry film is formed by drying and removing a solvent on the conditions which the polymerizable liquid crystal compound contained in the said coating film does not superpose | polymerize. As a drying method, a natural drying method, a ventilation drying method, heat drying, a vacuum drying method, etc. are mentioned, for example.

Next, as a preferable aspect, once the liquid crystal state of the polymeric liquid crystal composition contained in the said dry film is made into a nematic liquid crystal phase, the nematic liquid crystal phase is transferred to a smectic liquid crystal phase.

Thus, in order to form a smectic liquid crystal phase via a nematic liquid crystal phase, the polymeric liquid crystal compound contained in a dry film, for example is heated above the temperature which shows a nematic liquid crystal phase, and then the said polymeric liquid crystal compound is a smectic liquid crystal The method of cooling to the temperature which shows a phase is employ | adopted.

By measuring the phase transition temperature of the polymerizable liquid crystal compound to be used when the polymerizable liquid crystal compound in the dry film is a smectic liquid crystal phase or the polymerizable liquid crystal compound is a smectic liquid crystal phase via a nematic liquid crystal phase, The conditions (heating conditions) for controlling the liquid crystal state can be obtained. Measurement conditions of this phase transition temperature are described in the Examples herein.

Next, the superposition | polymerization process of a polymeric liquid crystal compound is demonstrated. Here, after containing a photoinitiator in the composition for polarizing film formation and making the liquid crystal state of the polymeric liquid crystal compound in a dry film into a smectic liquid crystal phase, the said polymeric liquid crystal compound is maintained, maintaining the liquid crystal state of this smectic liquid crystal phase. The method of photopolymerizing is explained in full detail. In photopolymerization, as light irradiated to a dry film, it is suitable according to the kind of photoinitiator contained in the dry film, the kind of polymeric liquid crystal compound (especially the kind of polymeric group which the said polymeric liquid crystal compound has), and its quantity. It can be performed by the light selected from the group consisting of visible light, ultraviolet light and laser light or an active electron beam. Among these, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction and that a device widely used in the art can be used as an apparatus for photopolymerization. Therefore, it is preferable to select the kind of the polymeric liquid crystal compound and the photoinitiator contained in the composition for polarizing film formation so that photopolymerization may be carried out by ultraviolet light. In addition, when superposing | polymerizing, superposition | polymerization temperature can also be controlled by cooling a dry film with suitable cooling means with ultraviolet light irradiation. By employ | adopting such a cooling means, if superposition | polymerization of a polymeric liquid crystal compound can be performed at a low temperature, even if the thing with comparatively low heat resistance is used for the base material mentioned above, there exists also an advantage that this polarizing film can be formed suitably. On the other hand, at the time of photopolymerization, this polarizing film patterned by masking, image development, etc. can also be obtained.

By performing photopolymerization as described above, the polymerizable liquid crystal compound is polymerized while maintaining a nematic liquid crystal phase and a smectic liquid crystal phase, preferably a higher order smectic liquid crystal phase as already exemplified, thereby forming the present polarizing film. This polarizing film obtained by superposing | polymerizing with a polymeric liquid crystal compound holding the liquid crystal state of a smectic liquid crystal phase maintains the conventional host guest type polarizing film, ie, the nematic liquid crystal state according to the action of the dichroic dye (1). It has the advantage that a polarization performance is high compared with the polarizing film obtained by superposing | polymerizing a polymeric liquid crystal compound etc. with it. Further, there is an advantage that the strength is excellent as compared with the application of only the lyotropic dichroic dye.

The range of 0.5 micrometer or more and 10 micrometers or less is preferable, and, as for the thickness of this polarizing film formed in this way, 1 micrometer or more and 5 micrometers or less are more preferable. Therefore, the thickness of the coating film for this polarizing film formation is determined in consideration of the thickness of the present polarizing film obtained. In addition, the thickness of this polarizing film is calculated | required by the measurement of an interference film thickness meter, a laser microscope, or a stylus film thickness meter.

Moreover, this polarizing film formed in this way is especially preferable if Bragg peak is obtained in X-ray diffraction measurement as mentioned above. As this polarizing film from which such a Bragg peak is obtained, this polarizing film which shows the diffraction peak derived from a hexatic phase or a crystal phase is mentioned, for example.

This polarizing film exists in the absorption maximum wavelength ((lambda) max1) 400-520 nm. This absorption maximum wavelength (lambda max1) is preferable to exist in the range of 430-520 nm, and it is more preferable to exist in the range of 440-510 nm. Moreover, it is preferable if the absorption maximum wavelength ((lambda) max1) of this polarizing film is shifted longer than the absorption maximum wavelength ((lambda) max2) of the dichroic dye used for manufacture of this polarizing film. This absorption maximum wavelength ((lambda) max2) prepares the solution which melt | dissolved the dichroic dye in the suitable solvent, and measures it in this solution state. The solvent which melt | dissolves a dichroic dye can fully melt | dissolve the said dichroic dye, and the thing which does not have absorption in wavelength light of 350-550 nm is selected. Expression of such a long wavelength shift is that when the dichroic dye 1 is dispersed between molecular chains formed of the polymerizable liquid crystal compound in the present polarizing film, the dichroic dye 1 strongly interacts with the molecular chain. It is present. On the other hand, the long wavelength shift means that the difference (λmax1-λmax2) of the absorption maximum wavelength becomes a positive value. The difference is preferably 20 nm or more, more preferably 30 nm or more.

In addition, this polarizing film has a high dichroic ratio and is excellent in polarization performance. Specifically, dichroic ratio is 15 or more normally, Preferably it is 25 or more.

<Continuous manufacturing method of this polarizing film>

As mentioned above, although the outline | summary of the manufacturing method of this polarizing film was demonstrated, when manufacturing this polarizing film commercially, the method which can manufacture this polarizing film continuously is calculated | required. This continuous manufacturing method is based on the RolltoRoll type, and is called "this manufacturing method" in some cases. In addition, in this manufacturing method, it demonstrates centering around a case where a base material is a transparent base material. When a base material is a transparent base material, what is finally obtained becomes a polarizer (henceforth "this polarizer" in some cases) which has a transparent base material and this polarizing film.

The present production method is, for example,

The process of preparing the 1st roll by which a transparent base material is wound by the 1st core,

Continuously sending the transparent substrate from the first roll;

Continuously forming an alignment film on the transparent substrate,

Continuously applying the composition for forming a polarizing film on the alignment film;

Drying the coated composition for forming a polarizing film under conditions such that the polymerizable liquid crystal compound is not polymerized, thereby continuously forming a dry film on the alignment film;

After making the polymeric liquid crystal compound contained in the said dry film into a nematic liquid crystal phase, preferably a smectic liquid crystal phase, the said polymerizable liquid crystal compound is superposed | polymerized, maintaining this smectic liquid crystal phase, and a polarizing film is continuously The step of obtaining a polarizer,

It has a process of winding this polarizer obtained continuously in a 2nd core and obtaining a 2nd roll. Here, with reference to FIG. 1, especially this manufacturing method is demonstrated about the case where a photo-alignment film is used as an orientation film.

The 1st roll 210 by which the transparent base material is wound by 210 A of 1st windings can be obtained easily in the market, for example. As a transparent base material available on the market in the form of such a roll, the film etc. which consist of a cellulose ester, cyclic olefin resin, polyethylene terephthalate, a polycarbonate, or polymethacrylic acid ester among the transparent base materials already illustrated are mentioned. In addition, in using this polarizing film as a circularly polarizing plate, the transparent base material to which retardation was previously given can also be obtained easily in a market, For example, the retardation film which consists of cellulose ester or cyclic olefin resin, etc. are mentioned.

Subsequently, the transparent substrate is released from the first roll 210. The method of releasing a transparent base material is performed by providing a suitable rotating means in the core 210A of the said 1st roll 210, and rotating the 1st roll 210 by this rotating means. In addition, the auxiliary roll 300 suitable for the direction which conveys a transparent base material from the 1st roll 210 may be provided, and the form which removes a transparent base material by the rotation means of this auxiliary roll 300 may be sufficient. In addition, both the 1st winding core 210A and the auxiliary roll 300 may be a form which unwinds a transparent base material, providing a suitable tension to a transparent base material by providing a rotation means.

When the transparent base material unwound from the said 1st roll 210 passes through the coating device 211A, the composition for photo-alignment layer formation is apply | coated by the said coating device 211A on the surface. Thus, in order to apply | coat a composition for photo-alignment layer formation continuously, printing methods, such as the gravure coating method, the die-coating method, the flexographic method, are performed by the said coating apparatus 211A as mentioned above.

The transparent base material which passed through the coating device 211A is conveyed to the drying furnace 212A, it is heated by this drying furnace 212A, and forms a 1st dry film continuously on a transparent base material. As the drying furnace 212A, for example, a hot air drying furnace is used. The setting temperature of the drying furnace 212A is determined according to the kind of solvent contained in the said composition for optical orientation layer formation apply | coated by the coating device 211A, etc. The drying furnace 212A may be divided into a plurality of zones, and may be a type having a different set temperature for each of the divided zones, or a plurality of drying furnaces may be arranged in series and may be a drying furnace having a different set temperature for each drying furnace.

The first dry film continuously formed by passing through the heating furnace 212A is then irradiated with polarized UV on the surface of the first dry film side or the surface of the transparent substrate side by the polarized UV irradiation device 213A, and the first dry film is dried. The film forms a (photo) alignment film. In that case, you may make it the angle which the conveyance direction D1 of a transparent base material and the orientation direction D2 of the photo-alignment film formed form to cross | intersect. It is a schematic diagram which shows the relationship of the orientation direction D2 of the photo-alignment film formed after polarizing UV irradiation, and the conveyance direction D1 of a transparent base material. That is, FIG. 2 shows that when the surface of the 1st laminated body after passing through the polarization UV irradiation apparatus 213A is seen by the conveyance direction D1 of the transparent base material, and the orientation direction D2 of the optical alignment film, the angle which they make shows approximately 45 degrees. have.

In this way, the transparent base material (1st laminated body) in which the photo-alignment film was continuously formed is then passed through the coating apparatus 211B, and the composition for polarizing film formation is apply | coated on the photo-alignment film, and then passes through the drying furnace 212B. By passing through the drying furnace 212B, the polymeric liquid crystal compound contained in the composition for polarizing film formation forms a nematic liquid crystal phase, Preferably a smectic liquid crystal phase, and a 2nd dry film is formed.

As for the transparent base material which passed through the said drying furnace 212B, the solvent contained in the composition for polarizing film formation was fully removed, and the polymeric liquid crystal compound in a 2nd dry film is a nematic liquid crystal phase, Preferably the smectic liquid crystal state It is conveyed to the light irradiation apparatus 213B, maintaining. By the light irradiation by the light irradiation apparatus 213B, the said polymeric liquid crystal compound photopolymerizes, maintaining the said liquid crystal state, this polarizing film is formed continuously on an alignment film, and this polarizer is obtained.

In this way, this polarizer formed continuously is a form of the laminated body containing a transparent base material and an orientation film, it is wound up by 220 A of 2nd cores, and the form of the 2nd roll 220 is obtained. When winding up this formed polarizing film and obtaining a 2nd roll, you may perform the air winding using a suitable spacer.

Thus, the transparent base material is in order of 1st roll / coating apparatus 211A / drying furnace 212A / polarization UV irradiation apparatus 213A / coating apparatus 211B / drying furnace 212B / light irradiation apparatus 213B. By passing through, the present polarizing film is continuously formed on the photo-alignment film on the transparent substrate to produce the present polarizer.

In addition, although the manufacturing method shown to FIG. 1 showed the method of manufacturing continuously from a transparent base material to this polarizing film, the transparent base material was made into the 1st roll / coating apparatus 211A / drying furnace 212A / polarization, for example. The first laminated body formed continuously by winding in order of UV irradiation apparatus 213A is wound up to the core, the 1st laminated body is manufactured in the form of a roll, and the 1st laminated body is unwound from this roll, The present polarizer may be manufactured by passing the first laminate in the order of the coating device 211B / drying furnace 212B / light irradiation apparatus 213B.

The present polarizer obtained by the present production method is a film or elongate shape. When this polarizer is used for a liquid crystal display device or the like described later, the polarizer is cut and used so as to have a desired dimension in accordance with the scale of the liquid crystal display device.

As mentioned above, although the structure and manufacturing method of this polarizer were demonstrated centering on the case of the laminated body of a transparent base material / an optical orientation film / this polarizing film, this polarizing film was peeled off by peeling an optical orientation film and a transparent base material from this polarizer as mentioned above. It can also be obtained in a single layer. Moreover, you may make it the form which laminated | stacked layers or films other than a transparent base material / optical orientation film / this polarizing film on this polarizer. As these layers and films, as mentioned above, the form which further provided the retardation film may be sufficient, and the form which further provided the antireflection layer or the brightness improving film may be sufficient.

Moreover, it can also be set as the circularly-polarizing plate or elliptical polarizing plate of the form of retardation film / optical orientation film / this polarizing film by making transparent base material itself into retardation film. For example, when the uniaxially stretched quarter wave plate is used as the retardation film, it is possible to produce a circularly polarizing plate by RolltoRoll by setting the irradiation direction of polarized UV so that it may be set to approximately 45 degrees with respect to the conveyance direction of a transparent base material. Thus, it is preferable that the quarter wave plate used when manufacturing a circularly polarizing plate has the characteristic that an in-plane phase difference value with respect to visible light becomes small as a wavelength becomes short.

Moreover, using a 1/2 wavelength plate as a retardation film, the linear polarizing plate roll set by shifting the angle of the slow axis and the absorption axis of a polarizing film was produced, and the 1/4 wavelength plate was prepared on the opposite side to the surface which formed this polarizing film. By further forming, it is also possible to make a broadband circular polarizing plate.

<Use of this polarizing film>

This polarizing film can be used for various display devices. The display device is a device having a display element, and includes a light emitting element or a light emitting device as a light emitting source. As the display device, for example, a liquid crystal display device, an organic electroluminescence (EL) display device, an inorganic electroluminescence (EL) display device, an electron emission display device (for example, an electric field emission display device (FED), a surface field emission display device ( SED), electronic paper (display device using electronic ink or electrophoretic element, plasma display device, projection display device (e.g., display device having a grating light valve (GLV) display device, digital micromirror device (DMD)), and piezoelectric And a ceramic display, etc. The liquid crystal display device includes any of a transmissive liquid crystal display device, a transflective liquid crystal display device, a reflective liquid crystal display device, a direct view liquid crystal display device, a projection liquid crystal display device, and the like. The display apparatus which displays a two-dimensional image may be sufficient, and the stereoscopic display apparatus which displays a three-dimensional image may be sufficient.

Especially this polarizing film can be used effectively for the display apparatus of an organic electroluminescent (EL) display apparatus or an inorganic electroluminescent (EL) display apparatus.

FIG. 3: is a schematic diagram which shows the cross-sectional structure of the liquid crystal display device (henceforth "this liquid crystal display device") 10 using this polarizing film. The liquid crystal layer 17 is sandwiched by two substrates 14a and 14b.

6 and 10 are schematic diagrams showing a cross-sectional structure of an EL display device (hereinafter, referred to as a "main EL display device") using the present polarizing film.

It is a schematic diagram which shows the structure of the projection type liquid crystal display device using this polarizing film.

First, the present liquid crystal display device 10 shown in FIG. 3 will be described.

The color filter 15 is arranged on the liquid crystal layer 17 side of the substrate 14a. The color filter 15 is disposed at a position facing the pixel electrode 22 with the liquid crystal layer 17 therebetween, and the black matrix 20 is disposed at a position facing the boundary between the pixel electrodes. The transparent electrode 16 is disposed on the liquid crystal layer 17 side so as to cover the color filter 15 and the black matrix 20. On the other hand, an overcoat layer (not shown) may be provided between the color filter 15 and the transparent electrode 16.

The thin film transistor 21 and the pixel electrode 22 are regularly arranged on the liquid crystal layer 17 side of the substrate 14b. The pixel electrode 22 is disposed at a position opposite to the color filter 15 with the liquid crystal layer 17 therebetween. An interlayer insulating film 18 having a connection hole (not shown) is disposed between the thin film transistor 21 and the pixel electrode 22.

As the board | substrate 14a and the board | substrate 14b, a glass substrate and a plastic substrate are used. Such a glass substrate and a plastic substrate can employ | adopt the thing of the same material as what was illustrated as the transparent base material used for this polarizing film manufacture. In addition, the transparent substrate 1 of this polarizing film may serve as the board | substrate 14a and the board | substrate 14b. When manufacturing the color filter 15 formed on the board | substrate and the thin film transistor 21, when the process of heating at high temperature is required, a glass substrate or a quartz substrate is preferable.

As the thin film transistor, an optimal one can be adopted depending on the material of the substrate 14b. Examples of the thin film transistor 21 include a high temperature polysilicon transistor formed on a quartz substrate, a low temperature polysilicon transistor formed on a glass substrate, and an amorphous silicon transistor formed on a glass substrate or a plastic substrate. In order to further reduce the size of the liquid crystal display device, a driver IC may be formed on the substrate 14b.

The liquid crystal layer 17 is disposed between the transparent electrode 16 and the pixel electrode 22. In the liquid crystal layer 17, spacers 23 are disposed in order to keep the distance between the substrate 14a and the substrate 14b constant. In addition, although shown as a columnar spacer in FIG. 3, this spacer is not limited to a columnar shape, The shape is arbitrary as long as the distance between the board | substrate 14a and the board | substrate 14b can be kept constant.

Each member includes a substrate 14a, a color filter 15 and a black matrix 20, a transparent electrode 16, a liquid crystal layer 17, a pixel electrode 22, an interlayer insulating film 18 and a thin film transistor 21, And the substrate 14b in this order.

Of the board | substrate 14a and 14b which sandwich this liquid crystal layer 17, the polarizer 12a and 12b is provided in the outer side of the board | substrate 14b, and the polarizer which this saw is used for at least one of them. .

Moreover, it is preferable that retardation layers (for example, 1/4 wavelength plate and optical compensation film) 13a and 13b are laminated | stacked. By arranging this polarizer in the polarizer 12b among the polarizers 12a and 12b, the function of converting incident light into linearly polarized light can be imparted to the present liquid crystal display device 10. On the other hand, the retardation films 13a and 13b may not be disposed depending on the structure of the liquid crystal display device and the kind of the liquid crystal compound included in the liquid crystal layer 17, and the transparent substrate is a retardation film, and the original containing the polarizing film When the polarizing plate is used, since the retardation film can be used as a retardation layer, the retardation layer 13a and / or 13b of FIG. 3 can also be abbreviate | omitted. You may provide a polarizing film further on the light output side (outer side) of the polarizer containing this polarizing film.

Moreover, the anti-reflective film which prevents reflection of external light may be arrange | positioned outside the polarizer containing this polarizing film (outside when the polarizing film is further provided in this polarizing film).

As described above, the present polarizer can be used for the polarizer 12a or 12b of the present liquid crystal display device 10 of FIG. 3. By using this polarizer for the polarizers 12a and / or 12b, there is an effect that the thinning of the liquid crystal display device 10 can be achieved.

When using this polarizer for the polarizer 12a or 12b, the lamination order is not specifically limited. This will be described with reference to enlarged views of portions A and B surrounded by the dotted lines in FIG. 3.

4 is an enlarged schematic cross-sectional view of a portion A of FIG. 3. In FIG. 4A, when the present polarizer 100 is used as the polarizer 12a, the polarizing film 3, the optical alignment film 2, and the transparent substrate 1 viewed from the phase difference layer 13a side are in this order. It is installed so that it is arrange | positioned. 4 (A2) shows that the transparent base material 1, the optical alignment film 2, and the present polarizing film 3 are arranged in this order from the phase difference layer 13a side.

5 is an enlarged schematic view of a portion B of FIG. 3. In FIG. 5B, when the present polarizer 100 is used as the polarizer 12b, the transparent substrate 1, the optical alignment film 2, and the present polarizing film 3 are in this order from the retardation film 13b side. Installed to be deployed. In FIG. 5B, when the polarizer 100 is used as the polarizer 12b, the polarizing film 3, the optical alignment film 2, and the transparent substrate 1 viewed from the retardation film 13b side are in this order. Installed to be deployed.

The backlight unit 19 which is a light emitting source is arrange | positioned outside the polarizer 12b. The backlight unit 19 includes a light source, a light guide, a reflector, a diffusion sheet, and a viewing angle adjustment sheet. As a light source, an electroluminescent, a cold cathode tube, a hot cathode tube, a light emitting diode (LED), a laser light source, a mercury lamp, etc. are mentioned. Moreover, the kind of polarizing film seen according to the characteristic of such a light source can be selected.

In the case where the liquid crystal display device 10 is a transmissive liquid crystal display device, white light generated from the light source in the backlight unit 19 enters the light guide, and the path is changed by the reflecting plate and diffused in the diffusion sheet. The diffused light is incident on the polarizer 12b from the backlight unit 19 after being adjusted to have the desired directivity by the viewing angle adjusting sheet.

Of the non-polarized incident light, only one linearly polarized light passes through the polarizer 12b of the liquid crystal panel. The linearly polarized light is converted into circularly or elliptically polarized light by the phase difference layer 13b, and sequentially passes through the substrate 14b, the pixel electrode 22, and the like to reach the liquid crystal layer 17. FIG.

Here, by the presence or absence of a potential difference between the pixel electrode 22 and the opposing transparent electrode 16, the alignment state of the liquid crystal molecules included in the liquid crystal layer 17 is changed, and the light emitted from the liquid crystal display device 10 is present. The luminance of is controlled. When the liquid crystal layer 17 is in an alignment state in which the polarized light is converted and transmitted, the polarized light passes through the liquid crystal layer 17 and the transparent electrode 16, and light of a specific wavelength range passes through the color filter 15. The polarizer 12a is reached, and the liquid crystal display displays the color determined by the color filter brightest.

On the contrary, when the liquid crystal layer 17 is in an alignment state that transmits polarized light as it is, light transmitted through the liquid crystal layer 17, the transparent electrode 16, and the color filter 15 is absorbed by the polarizer 12a. As a result, this pixel displays black. In the intermediate alignment state between these two states, since the luminance of light emitted from the liquid crystal display device 10 also becomes the middle of the above, the pixel displays the intermediate color.

When this liquid crystal display device 10 is a semi-transmissive liquid crystal display device, it is preferable to use what laminated | stacked the 1/4 wavelength plate further on this polarizing film side (circular polarizing plate) of this polarizer. At this time, the pixel electrode 22 has a transmissive portion formed of a transparent material and a reflecting portion formed of a material that reflects light, and the transmissive portion displays an image in the same manner as the above-described transmissive liquid crystal display device. On the other hand, in the reflecting portion, external light enters the liquid crystal display device, circularly polarized light transmitted through the polarizing film by the action of the quarter wave plate further provided in the polarizing film passes through the liquid crystal layer 17, and the pixel electrode ( Is reflected by 22) and used for display.

Next, the present EL display device 30 using the present polarizing film will be described with reference to FIG. 6. When using this polarizing film for this EL display device, it is preferable to use it after making this polarizing film into a circularly polarizing plate (henceforth "this circularly polarizing plate"). This circular polarizing plate has two embodiments. Therefore, two embodiments of the circular polarizing plate will be described with reference to FIG. 7 before explaining the configuration and the like of the EL display device 30.

FIG. 7A is a cross-sectional view schematically showing the first embodiment of the circular polarizing plate 110. This 1st Embodiment is this circular polarizing plate 110 which further provided the retardation layer (phase difference film) 4 on this polarizing film 3 in this polarizer 100. FIG. 7B is a schematic diagram illustrating a second embodiment of the circular polarizing plate 110. In this second embodiment, the phase difference of the transparent base material 1 itself is obtained by using the transparent base material 1 (phase difference film 4) to which the phase difference property is imparted beforehand to the transparent base material 1 used when manufacturing this polarizer. This circular polarizing plate 110 has a function as the layer 4.

As the present circular polarizing plate including the present polarizing film, since the configuration is simple, the second embodiment of the present circular polarizing plate described above is preferable, and in this case, it is preferable to use a quarter wave plate as the transparent substrate, and furthermore, a transparent substrate. It is preferable to use a quarter wave plate as the following and satisfy the following requirements (A1) and (A2).

(A1) the angle between the absorption axis of the polarizing film and the slow axis of the quarter wave plate is approximately 45 °;

(A2) The value of the front retardation of the quarter wave plate measured in light of wavelength 550 nm is in the range of 100 to 150 nm.

Here, the manufacturing method of this circular polarizing plate 110 is demonstrated. As described above, the second embodiment of the circular polarizing plate 110 is, in the present manufacturing method for manufacturing the present polarizer 100, the transparent base material 1, that is, the phase difference film, to which the phase difference is imparted in advance as the transparent base material 1. It can manufacture by using. In the first embodiment of the circular polarizing plate 110, the phase difference layer 4 may be formed by bonding a phase difference film on the present polarizing film 3 produced by the present production method B. FIG. On the other hand, when this polarizing film 100 was manufactured in the form of the 2nd roll 220 by this manufacturing method B, the polarizing film 100 seen from the said 2nd roll 220 was unwound, and predetermined dimension Although the shape which bonds retardation film to the cut this polarizing film 100 after cutting with may be sufficient, this circular polarizing plate whose shape is a film-shaped and elongate shape is prepared by preparing the 3rd roll by which the retardation film is wound by the core ( 110 may also be produced continuously.

A method of continuously manufacturing the first embodiment of the circular polarizing plate 110 will be described with reference to FIG. 8. This manufacturing method,

Unwinding the polarizing film 100 seen continuously from the second roll 220 and simultaneously unwinding the retardation film from the third roll 230 on which the retardation film is wound;

Forming a circularly polarizing plate 110 by continuously bonding the polarizing film formed on the present polarizing film 100 released from the second roll 220 and the retardation film released from the third roll;

The formed circular polarizing plate 110 is wound on the fourth winding core 240A, thereby obtaining a fourth roll 240.

As mentioned above, although the manufacturing method of 1st Embodiment of this circular polarizing plate 110 was demonstrated, when bonding this polarizing film 3 and retardation film in the polarizer 100, the adhesive formed by this adhesive using an appropriate adhesive The polarizing film 3 and the retardation film which were seen through the layer may be bonded.

Next, the EL display device provided with the circular polarizing plate 110 will be described with reference to FIG. 6 again.

In the EL display device 30, an organic functional layer 36 and a cathode electrode 37 serving as light emitting sources are stacked on a substrate 33 on which a 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 therebetween, and the circularly polarizing plate 110 is used as the circularly polarizing plate 31. The organic functional layer 36 emits light by applying a positive voltage to the pixel electrode 35 and a negative voltage to the cathode electrode 37, and applying a direct current between the pixel electrode 35 and the cathode electrode 37. The organic functional layer 36 as a light emitting source is composed of an electron transporting layer, a light emitting layer, a hole transporting layer, and the like. Light emitted from the organic functional layer 36 passes through the pixel electrode 35, the interlayer insulating film 34, the substrate 33, and the circular polarizing plate 31 (this circular polarizing plate 110). Although the organic electroluminescence display which has the organic functional layer 36 is demonstrated, you may apply also to the inorganic electroluminescence display which has an inorganic functional layer.

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

Subsequently, the circularly polarizing plate 31 (this circularly polarizing plate 110) is provided on the surface opposite to the surface on which the thin film transistor 40 of the substrate 33 is provided.

When the circular polarizing plate 110 is used as the circular polarizing plate 31, the stacking order thereof will be described with reference to an enlarged view of the portion C surrounded by the dotted lines in FIG. When the circular polarizing plate 110 is used as the circular polarizing plate 31, the phase difference layer 4 in the circular polarizing plate 110 is disposed on the substrate 33 side. FIG. 9C is an enlarged view using the first embodiment of the circular polarizing plate 110 as the circular polarizing plate 31, and FIG. 9 (C2) is the second embodiment of the circular polarizing plate 110. It is an enlarged view used as the polarizing plate 31.

Next, members other than the present polarizing film 31 (circular polarizing plate 110) of the present EL display device 30 will be described.

As the board | substrate 33, Ceramic substrates, such as a sapphire glass substrate, a quartz glass substrate, a soda glass substrate, and an alumina; Metal substrates such as copper; Plastic substrates; Although not shown, a thermally conductive film may be formed on the substrate 33. As a thermally conductive film, a diamond thin film (DLC etc.) etc. are mentioned. When the pixel electrode 35 is a reflective type, light is emitted in a direction opposite to the substrate 33. Therefore, not only a transparent material but also a non-transmissive material, such as stainless steel, can be used. The substrate may be formed singly or may be formed as a laminated substrate by joining a plurality of substrates with an adhesive. In addition, these board | substrates are not limited to being plate-shaped, A film may be sufficient.

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 its size is about 10 to 30 μm. On the other hand, the size of the pixel electrode 35 is about 20 µm × 20 µm to 300 µm × 300 µm.

Wiring electrodes of the thin film transistor 40 are provided on the substrate 33. The wiring electrode has a low resistance and has a function of electrically connecting with the pixel electrode 35 to suppress the resistance value. Generally, the wiring electrode has Al, Al, and transition metal (except Ti), Ti, or nitride. Any one or two or more kinds of titanium (TiN) are used.

An interlayer insulating layer 34 is formed between the thin film transistor 40 and the pixel electrode 35. The interlayer insulating film 34 is formed by sputtering or vacuum evaporating inorganic materials such as silicon oxide and silicon nitride such as SiO ₂ , silicon oxide layer formed of SOG (spin on glass), photoresist, polyimide, acrylic resin, and the like. Any may be used as long as it has insulation such as a coating film of a resin-based material.

The ribs 41 are formed on the interlayer insulating film 34. The rib 41 is disposed at the periphery (between adjacent pixels) of the pixel electrode 35. Examples of the material of the ribs 41 include acrylic resins and polyimide resins. The thickness of the ribs 41 is preferably 1.0 µm or more and 3.5 µm or less, and more preferably 1.5 µm or more and 2.5 µm or less.

Next, an EL element including the pixel electrode 35 serving as a transparent electrode, the organic functional layer 36 serving as a light emitting source, and the cathode electrode 37 will be described. The organic functional layer 36 has at least one hole transport layer and a light emitting layer, respectively, and has, for example, an electron injection transport layer, a light emitting layer, a hole transport layer, and a hole injection layer in sequence.

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

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

As the constituent material of the cathode electrode 37, metal elements such as K, Li, Na, Mg, La, Ce, Ca, Sr, Ba, Al, Ag, In, Sn, Zn and Zr may be used. In order to improve the operational stability, it is preferable to use an alloy system of two or three components selected from the illustrated metal elements. Examples of the alloy system include Ag.Mg (Ag: 1 to 20 at%), Al.Li (Li: 0.3 to 14 at%), In.Mg (Mg: 50 to 80 at%), and Al.Ca (Ca: 5 -20 at%), etc. are preferable.

The cathode electrode 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, preferably 1 to 500 nm.

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 called a charge injection layer or a charge transport layer.

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

The organic functional layer 36 as a light emitting source uses light emission from the singlet excitons (fluorescence), light emission from the triplet excitons (phosphorescence), light emission from the singlet excitons (fluorescence) and triplet excitons. Comprising using luminescence (phosphorescence) from, including those formed by organics, those formed by organics and those formed by inorganics, including polymer materials, low molecular materials, high molecular materials and low molecular materials Etc. 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 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. Moisture is absorbed by the desiccant 38 to prevent deterioration of the organic functional layer 36.

10 is a schematic view showing a cross-sectional structure of another embodiment of the EL display device 30. This EL display device 30 has a sealing structure using the thin film sealing film 42, and can emit light from the opposite side of the array substrate.

As the thin film sealing film 42, it is preferable to use a DLC film in which DLC (diamond-like carbon) is deposited on a film of an electrolytic capacitor. The DLC film has a property of having very poor moisture permeability and has high moisture resistance. The DLC film or the like may be formed by directly depositing the surface of the cathode electrode 37. The thin film sealing film 42 may be formed by laminating a resin thin film and a metal thin film in multiple layers.

As mentioned above, the novel display apparatus (this liquid crystal display device and this EL display device) provided with this polarizing film, this polarizer, this circularly polarizing plate, and this polarizing film is provided.

Finally, a projection type liquid crystal display device using this polarizing film will be described.

Fig. 11 is a schematic diagram showing a projection type liquid crystal display device using the present polarizing film.

This polarizing film is used as the polarizer 142 and / or the polarizer 143 of this projection type liquid crystal display device.

The bundle of rays emitted from the light source (for example, the high-pressure mercury lamp) 111 that is the light emitting source is first used for the first lens array 112, the second lens array 113, the polarization converting element 114, and the overlapping lens 115. By passing through, uniformity and polarization of the luminance in the cross section of the anti-ray bundle is achieved.

Specifically, the light bundle emitted from the light source 111 is divided into a plurality of minute light bundles by the first lens array 112 in which the minute lenses 112a are formed in a matrix. The second lens array 113 and the overlapping lens 115 are provided so that each of the divided bundles of rays irradiates all three liquid crystal panels 140R, 140G, and 140B to be illuminated, so that each liquid crystal panel incident side surface Is almost uniform in total.

The polarization converting element 114 is constituted by a polarization beam splitter array, and is disposed between the second lens array 113 and the overlapping lens 115. As a result, the random polarized light from the light source is converted into polarized light having a specific polarization direction in advance, thereby reducing the amount of light loss at the incident side polarizer to be described later, thereby improving the brightness of the screen.

As described above, the luminance uniformized and polarized light are sequentially red, green, and blue channels by dichroic mirrors 121, 123, and 132 for separating the three primary colors of RGB via the reflection mirror 122. And incident on the liquid crystal panels 140R, 140G, and 140B, respectively.

Polarizers 142 are disposed on the incident side of the liquid crystal panels 140R, 140G, 140B, and polarizers 143 are disposed on the exit side, respectively. The polarizer film can be used for the polarizer 142 and the polarizer 143.

The polarizer 142 and the polarizer 143 arrange | positioned at each optical path of RGB are arrange | positioned so that each absorption axis may orthogonally cross. Each liquid crystal panel 140R, 140G, 140B disposed in each optical path has a function of converting the polarization state controlled for each pixel by the image signal to the amount of light.

The polarizing film 100 is useful as a polarizing film having excellent durability even in optical paths such as a blue channel, a green channel, and a red channel by selecting a kind of dichroic dye suitable for the corresponding channel.

Optical images created by transmitting incident light at different transmittances for each pixel according to the image data of the liquid crystal panels 140R, 140G, 140B are synthesized by the cross dichroic prism 150, and the screen 180 is projected by the projection lens 170. Is projected enlarged.

Examples of electronic paper include those represented by molecules such as optical anisotropy and dye molecular orientation, those represented by particles such as electrophoresis, particle movement, particle rotation, phase change, those represented by the movement of one end of the film, What is indicated by the color development / phase change, what is represented by the light absorption of a molecule | numerator, what is displayed by self-luminescence by combining an electron and a hole, etc. are mentioned. More specifically, microcapsule type electrophoresis, horizontal moving type electrophoresis, vertical moving type electrophoresis, spherical twist ball, magnetic twist ball, circumferential twist ball method, charging toner, electromagnetic fluid, magnetophoretic type, magnetic thermal type, electrophoresis Wetting, light scattering (transparency / cloudy change), cholesteric liquid crystal / photoconductive layer, cholesteric liquid crystal, bistable nematic liquid crystal, ferroelectric liquid crystal, dichroic dye-liquid crystal dispersion type, movable film, color development by leuco dye, Photochromic, electrochromic, electrodeposition, flexible organic EL, etc. are mentioned. The electronic paper may be used not only for personal use of texts or images but also for advertisement signage. According to this polarizing film, the thickness of an electronic paper can be made thin.

As a stereoscopic display device, for example, a method of arranging different phase difference films alternately, such as a micropole method, has been proposed (Japanese Patent Laid-Open No. 2002-185983). Since it is easy, the manufacturing process of a display apparatus can be shortened and a retardation film becomes unnecessary.

Example

Hereinafter, the present invention will be described in more detail with reference to examples. "%" And "part" in an example are the mass% and a mass part, unless there is particular notice.

Example 1 Preparation of Compound (1A) (Compound Represented by (1A)).

Compound (1A) was synthesized by the following scheme.

5.00 g of the compound [Compound (1B)] represented by the formula (1B), 4.63 g of 4-hydroxyethyl benzoate, 0.23 g of dimethylaminopyridine (DMAP), and 25 g of chloroform were mixed to each other at 5 ° C under a light-shielding / nitrogen atmosphere. It stirred for 10 minutes. 2.58 g of diisopropyl carbodiimide (IPC) was dripped at the obtained liquid mixture over 5 minutes, and also it stirred for 4 hours. 75 g of methanol was added to the obtained reaction solution, crystallized, and the crystals were collected by filtration. The crystals were further washed with the same amount of methanol and then vacuum dried to yield 6.78 g of Compound (1A). The yield was 87% based on compound (1B).

¹ H-NMR (CDCl ₃ ) of Compound (1A): δ (ppm) 1.41 (t, 3H), 3.12 (s, 6H), 4.40 (m, 2H), 6.76 (m, 2H), 7.33 (m, 2H), 7.93 (dd, 4H), 8.15 (m, 2H), 8.30 (m, 2H).

Example 2 [Compound (1D) (Compound represented by the following (1D))]

Compound (1D) was synthesized by the following scheme.

5.00 g of compound (1B), 4.63 g of 4-butyloxyphenol, 0.23 g of DMAP, and 25 g of chloroform were mixed and stirred for 10 minutes at 5 ° C under a light-shielding / nitrogen atmosphere. IPC 2.58g was dripped at the obtained liquid mixture over 5 minutes, and also it stirred for 4 hours. 75 g of methanol was added to the obtained reaction solution, crystallized, and the crystals were collected by filtration. The crystals were dissolved in 50 g of dimethylacetamide, and the insolubles were filtered through Celite. The filtrate was recovered and crystallized with water. The obtained crystal was further dissolved in 50 g of tetrahydrofuran to remove the insolubles by filtration, and then heptane was added, crystallized, and vacuum dried to obtain 4.66 g of compound (1D). The yield was 60% based on compound (1B).

¹ H-NMR (CDCl ₃ ) of Compound (1D): δ (ppm) 0.99 (t, 3H), 1.45 (m, 2H), 1.78 (m, 2H), 3.12 (s, 6H), 3.98 (t, 2H), 6.77 (m, 2H), 6.93 (m, 2H), 7.15 (m, 2H), 7.92 (dd, 4H), 8.29 (dd, 2H).

Example (production of this polarizing film etc.) and reference example

[Polymerizable Liquid Crystal Compound]

As a polymerizable liquid crystal compound contained in the composition for polarizing film formation, The compound represented by following formula (2-6) [Compound (2-6)], The compound represented by following formula (2-8) [Compound (2- 8)], a compound [compound (2-22)] represented by the following formula (2-22) and a compound [compound (2-25)] represented by the following formula (2-25) were used.

On the other hand, compound (2-6) is Lub et al. Recl. Trav. Chim. It synthesize | combined by the method described by Pays-Bas, 115, 321-328 (1996). Moreover, compound (2-8) was manufactured based on this method.

Compound (2-22) and compound (2-25) were produced in accordance with the method described in Japanese Patent No. 4719156.

Compound (2-6):

[Measurement of Phase Transition Temperature]

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

The phase transition temperature was confirmed by the observation of the texture by a polarizing microscope (BX-51, Olympus company), forming and heating the film | membrane which consists of a compound (2-6) on the glass substrate in which the oriented film was formed. When the film made of Compound (2-6) is heated to 120 ° C and then the temperature is lowered, the film is phase-shifted at 112 ° C to the nematic phase, at 110 ° C to the Smectic A phase, and at 94 ° C. Phase transition to B phase.

Compound (2-8):

[Measurement of Phase Transition Temperature]

The phase transition temperature of the compound (2-8) was confirmed by the same method as the phase transition temperature measurement of the compound (2-6). Compound (2-8) raises the temperature to 140 ° C, and when lowering the temperature, phase transitions to nematic phase at 131 ° C, phase transition to Smectic A phase at 80 ° C, and Smectic B phase at 68 ° C. It was confirmed that the phase transition to.

Compound (2-22):

[Measurement of Phase Transition Temperature]

The phase transition temperature of the compound (2-22) was confirmed by the same method as the phase transition temperature measurement of the compound (2-6). Compound (2-22) raises the temperature to 140 ° C and then, when lowering the temperature, phase transitions to a nematic phase at 106 ° C, phase transition to Smectic A phase at 103 ° C, and smectic B phase at 86 ° C. Phase transition.

Compound (2-25):

[Measurement of Phase Transition Temperature]

The phase transition temperature of the compound (2-25) was confirmed by the same method as the phase transition temperature measurement of the compound (2-6). Compound (2-25) raises the temperature to 140 ° C and then, when lowering the temperature, phase-transfers to nematic phase at 119 ° C, phase-transfers to Smectic A phase at 100 ° C, and smectic B phase at 77 ° C. Phase transition.

Example 3

[Preparation of Composition for Polarizing Film Formation]

The following component was mixed and stirred for 1 hour at 80 degreeC, and the composition (G) for polarizing film formation was obtained.

Polymerizable liquid crystal compounds; 75 parts of compounds (2-6)

25 parts of compounds (2-8)

Dichroic dyes; 2.5 parts of compounds (1A)

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

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

solvent; Toluene 250 parts

[Measurement of Phase Transition Temperature]

In the same manner as in the case of the compound (2-6) and the compound (2-8), the phase transition temperature of the polymerizable liquid crystal composition contained in the composition for polarizing film formation (G) was determined. After raising temperature to 140 degreeC, this polymeric liquid crystal composition phase-transforms into a nematic phase at 115 degreeC, phase-transforms into a smectic A phase at 105 degreeC, and smectic B phase at 75 degreeC. Phase transition.

[Production and Evaluation of This Polarizing Film]

1. Formation of alignment film

A glass substrate was used as a transparent base material.

On the glass substrate, a 2 mass% aqueous solution (orientation polymer composition) of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was applied by spin coating, dried, and then, thickness was 100. nm film was formed. Next, the alignment film was formed by performing a rubbing process on the surface of the obtained film. The rubbing treatment was carried out with a cloth (brand name: YA-20-RW, manufactured by Yoshikawa Kako Co., Ltd.) using a semi-automatic rubbing device (brand name: LQ-008 type, manufactured by Joyo Kogaku Co., Ltd.), 0.15 mm. And the rotation speed was 500 rpm and the conditions of 16.7 mm / s. By this rubbing process, the laminated body 1 in which the alignment film was formed on the glass substrate was obtained.

2. Formation of Polarizing Film

The composition (G) for polarizing film formation was apply | coated by the spin-coat method on the orientation film of the laminated body 1, and it heat-dried for 1 minute on a 120 degreeC hotplate, and then cooled to room temperature quickly, and a dry film is formed on the said orientation film. Formed. Subsequently, using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.), ultraviolet rays are irradiated to the dry film at an exposure dose of 2000 mJ / cm 2 (365 nm standard), thereby polymerizing the polymer contained in the dry film. The liquid crystal compound was polymerized while maintaining the liquid crystal state of the said polymeric liquid crystal composition, the polarizing film was formed with the dry film, and the laminated body 2 was obtained.

It was 1.7 micrometers when the thickness of the polarizing film at this time was measured by the laser microscope (OLS3000 by Olympus Co., Ltd.).

3. X-ray diffraction measurement

About the present polarizing film of the obtained laminated body 2, X-ray diffraction measurement was performed using the X-ray-diffraction apparatus X'Pert PRO MPD (made by SPECTLESS Corporation). Using Cu as a target, X-rays generated under conditions of X-ray tube current of 40 mA and X-ray tube voltage of 45 kV were obtained by rubbing direction (preliminarily, the rubbing direction of the alignment film under the polarizing film) through the fixed divergence slit 1/2 °. ), And measured by scanning in 2θ = 0.01671 ° steps in the range of 2θ = 4.0 to 40.0 °, and a sharp diffraction peak (Bragg) of peak half width (FWHM) = 0.31 ° around 2θ = 20.1 ° Peaks) were obtained. Moreover, the equivalent result was obtained also in incidence from the rubbing vertical direction. The order period (d) determined from the peak position was about 4.4 Hz, indicating that a structure reflecting the higher order smectic phase was formed.

4. Measurement of dichroic ratio

In order to confirm the utility of this polarizer, the dichroic ratio was measured as follows.

The absorbance of the transmission axis direction of the absorption maximum wavelength (A ¹⁾ and the absorbance (A ²⁾ of the spectrophotometer of the absorption axis direction (manufactured by Shimadzu Seisakusho Co., Ltd. Preparation UV-3150), the apparatus sets a folder having a polarizer on It was measured by the double beam method using. In the folder, the reference side installed a mesh that cuts the amount of light by 50%. The ratio (A ² / A ¹ ) was calculated from the values of the measured absorbance (A ¹ ) in the transmission axis direction and the absorbance (A ² ) in the absorption axis direction to be a dichroic ratio. Absorption maximum wavelength ((lambda) max1) was 506 nm, and the dichroic ratio in this wavelength was 30 high. It can be said that the higher the dichroic ratio is, the more useful as the polarizing film. Moreover, it turned out that the absorption maximum wavelength ((lambda) max2) measured with the dichroic dye used for this composition for polarizing film formation as a solution is 450 nm and has long wavelength shift. The result of this long wavelength shift is that when compound (1A) is dispersed among the dense molecular chains in which the polymerizable liquid crystal compound is polymerized in the polarizing film, the compound (1A) interacts strongly with the molecular chain. It is present.

Example 4

This polarizing film was produced like Example 3 except having used compound (1B) instead of compound (1A). Similarly, when the absorption maximum wavelength and dichroic ratio were measured, the absorption maximum wavelength (λmax1) was 494 nm and the dichroic ratio was 30, which was high. The absorption maximum wavelength ((lambda) max2) which measured the dichroic dye solution was 446 nm, and it turned out that it shifts long wavelength. This result indicates that the compound (1A) strongly interacts with the molecular chain when the compound (1A) is dispersed between the dense molecular chains formed by polymerization of the polymerizable liquid crystal compound in the present polarizing film. will be.

Example 5

A polarizing film was produced in the same manner as in Example 3 except that compound (2-22) was used instead of compound (2-6) and compound (2-25) was used instead of compound (2-8), respectively. Similarly, when the absorption maximum wavelength and dichroic ratio were measured, the absorption maximum wavelength (λmax1) was 500 nm and the dichroic ratio was 27, which was high. The absorption maximum wavelength ((lambda) max2) which measured the dichroic dye solution was 450 nm, and turned out to be a long wavelength shift.

Example 6

A polarizing film was produced in the same manner as in Example 4 except that Compound (2-22) was used instead of Compound (2-6) and Compound (2-25) was used instead of Compound (2-8), respectively. Similarly, when the absorption maximum wavelength and dichroic ratio were measured, the absorption maximum wavelength (λmax1) was 492 nm and the dichroic ratio was 28, which was high. The absorption maximum wavelength ((lambda) max2) which measured the dichroic dye solution was 446 nm, and it turned out that it shifts long wavelength.

Example 7

A polarizing film was produced in the same manner as in Example 3 except that 100 parts of the polymerizable nematic liquid crystal compound (trade name LC242 manufactured by BASF Corporation) was used instead of the compound (2-6) and the compound (2-8). Similarly, when the absorption maximum wavelength and dichroic ratio were measured, the absorption maximum wavelength ((lambda) max1) was 464 nm and dichroic ratio was 10. The absorption maximum wavelength ((lambda) max2) which measured the dichroic dye solution was 450 nm.

Example 8

A polarizing film was produced in the same manner as in Example 4 except that 100 parts of the polymerizable nematic liquid crystal (trade name LC242 manufactured by BASF Corporation) was used instead of the compound (2-6) and the compound (2-8). Similarly, when the absorption maximum wavelength and dichroic ratio were measured, the absorption maximum wavelength was 462 nm and dichroic ratio was 10. The absorption maximum wavelength ((lambda) max2) which measured the dichroic dye solution was 446 nm.

Comparative Example 1

A polarizing film was produced in the same manner as in Example 3 except that the compound of "pigment number 5" described in Japanese Patent 1454637 was used instead of compound (1A). Similarly, when the absorption maximum wavelength and dichroic ratio were measured, the absorption maximum wavelength ((lambda) max1) was 398 nm and dichroic ratio was 20. The absorption maximum wavelength ((lambda) max2) which measured the dichroic dye solution was 386 nm. The absorption maximum wavelength of this dichroic dye was 400 nm or less, and the long wavelength shift amount was small.

Compound of "pigment number 5"

Comparative Example 2

A polarizing film was produced in the same manner as in Example 3, except that the compound of "pigment number 1" described in Japanese Patent 1454637 was used instead of compound (1A). Similarly, when the absorption maximum wavelength and dichroic ratio were measured, the absorption maximum wavelength was 446 nm and dichroic ratio was 4. The absorption maximum wavelength ((lambda) max2) which measured the dichroic dye solution was 436 nm. The dichroic ratio was low and the long wavelength shift amount was small.

Compound of "pigment number 1"

The novel compounds of the present invention are very useful as dichroic dyes for polarizing film production, and have high industrial value.

1: transparent base material 2: photo-alignment film
3: pattern polarizer 100: pattern polarizer
210: first roll 210A: core
220: second roll 220A: core
230: third roll 230A: core
240: fourth roll 240A: core
211A, 211B: Coating apparatus 212A, 212B: Drying furnace
213A: polarized UV irradiation device 213B: light irradiation device
300: auxiliary roll 10: liquid crystal display
12a, 12b: polarizer 13a, 13b: retardation layer
14a, 14b: substrate 15: color filter
16: transparent electrode 17: liquid crystal layer
18: interlayer insulating film 19: backlight unit
20: black matrix 21: thin film transistor
22: pixel electrode 23: spacer
30: EL display device 31: circularly polarizing plate
32: retardation film 33: substrate
34: interlayer insulating film 35: pixel electrode
36: organic functional layer 37: cathode electrode
38: desiccant 39: sealing lid
40: thin film transistor 41: rib
42: thin film sealing film 44: EL display device
111: light source 112: first lens array
112a: lens 113: second lens array
114: polarization conversion element 115: superposition lens
121, 123, 132: dichroic mirror 122: reflective mirror
140R, 140G, 140B: Liquid Crystal Panels 142, 143: Polarizer
150: cross dichroic prism 170: projection lens
180: screen

Claims (16)

delete delete delete A composition comprising a compound represented by formula (1) and a smectic liquid crystal phase, and containing a polymerizable liquid crystal compound represented by formula (2):

[In Formula (1), Y is group represented by Formula (Y1) or Formula (Y2).

(Wherein L is an oxygen atom or -NR- and R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
R ¹ is a group represented by formula (R ¹ -1), formula (R ¹ -2) or formula (R ¹ -3).

(In formula, ma is an integer of 0-10, and when there are two ma in the same group, these two ma are mutually same or different. * Represents a coupling | bonding number.)
R ² is a formula (R ² -1), formula (R ² -2), formula (R ² -3), formula (R ² -4), formula (R ² -5) or a group represented by the formula (R ² -6) Is represented by.

(Wherein mb is an integer of 0 to 10. * represents the number of bonds.)]
U ¹ -V ¹ -W ¹ -X ¹ -Y ¹ -X ² -Y ² -X ³ -W ² -V ² -U ² (2)
[In formula (2), X <^1> , X <^2> and X <^3> represent the cyclohexane- 1, 4- diyl group which may have a ¹ , 4- phenylene group which may have a substituent independently of each other, or a substituent. Provided that at least one of X ¹ , X ² and X ³ is a 1,4-phenylene group which may have a substituent. -CH ₂ -constituting a cyclohexane-1,4-diyl group which may have a substituent may be substituted with -O-, -S- or -NR-. R is a C1-C6 alkyl group or a phenyl group.
Y ¹ and Y ² independently of one another are -CH ₂ CH _2- , -CH ₂ O-, -COO-, -OCOO-, single bond, -N = N-, -CR ^a = CR ^b- , -C≡ C- or -CR ^a = N-.
R ^a and R ^b independently of one another represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
U ¹ represents a hydrogen atom or a polymerizable group.
U ² represents a polymerizable group.
W ¹ and W ² independently represent a single bond, -O-, -S-, -COO- or -OCOO-.
V ¹ and V ² independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ -constituting the alkanediyl group is substituted with -O-, -S- or -NH-. May be done] The composition according to claim 4, further comprising a solvent. The composition according to claim 4 or 5, further comprising a polymerization initiator. It is formed from the composition of Claim 4 or 5, The polarizing film characterized by the above-mentioned. The absorption maximum wavelength (λmax1) of the polarizing film,
A wavelength shifted longer than the absorption maximum wavelength (λmax2) of the dichroic dye. 8. The polarizing film according to claim 7, wherein the difference between the absorption maximum wavelength [lambda] max1 of the polarizing film and the absorption maximum wavelength [lambda] max2 of the dichroic dye is 20 nm or more. 8. The polarizing film according to claim 7, wherein a Bragg peak is obtained in X-ray diffraction measurement. It has a polarizing film of Claim 7, and a transparent base material, The polarizer characterized by the above-mentioned. Preparing a laminate in which an alignment film is laminated on a transparent substrate,
Process of apply | coating the composition of Claim 4 or 5 on the said oriented film of the said laminated body, and forming a coating film,
Process of polymerizing the said polymerizable liquid crystal compound contained in the said coating film
It has a manufacturing method of light polarizer characterized by the above-mentioned. Forming a laminate by forming an optical alignment film on the transparent substrate,
Process of apply | coating the composition of Claim 4 or 5 on the said photo-alignment film of the said laminated body, and forming a coating film,
Process of polymerizing the said polymerizable liquid crystal compound contained in the said coating film
It has a manufacturing method of light polarizer characterized by the above-mentioned. The polarizing film of Claim 7 is provided, The liquid crystal display device characterized by the above-mentioned. The circularly polarizing plate which has the polarizing film of Claim 7 and a quarter wave plate, and satisfy | fills the requirements of the following (A1) and (A2):
(A1) the angle between the absorption axis of the polarizing film and the slow axis of the quarter wave plate is 45 °;
(A2) The value of the front retardation of the said quarter wave plate measured with the light of wavelength 550 nm shall be 100-150 nm. The organic electroluminescence display provided with the circularly-polarizing plate of Claim 15, and organic electroluminescent element.

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