KR20130098914A - Polarizing film, circular polarizing plate and method of producing the same - Google Patents

Abstract

PURPOSE: A polarizing film, a circular polarizing plate, and a manufacturing method thereof are provided to effectively execute a thin film process and to offer an excellent neutral color property. CONSTITUTION: A polarizing film comprises a polymer, one-kind dichroic dye, and two-kind dichroic dye. The polymer is comprised of a polymeric liquid-crystalline compound. The one-kind dichroic dye forms the absorption range of 380-550nm when the optical absorption is measured by dispersing the one-kind dichroic dye among the polymers. The two-kind dichroic dye forms the absorption range of 550-700nm. The two-kind dichroic dye includes a dichroic dye which forms the absorption range of 600-700nm.

Description

Polarizing film, circular polarizing plate and manufacturing method thereof {POLARIZING FILM, CIRCULAR POLARIZING PLATE AND METHOD OF PRODUCING THE SAME}

The present invention relates to a polarizing film, a circular polarizing plate, a production method thereof, and the like.

Since the polarizer used in the liquid crystal display device has high transmittance and polarization degree, a film (polarizing film) made of polyvinyl alcohol (iodine dye PVA), which has been dyed with a dichroic dye such as iodine and stretched, is generally used. have. For example, Patent Document 1 describes a polarizing film made of iodine dye PVA.

Patent Document 1: Japanese Patent Application Laid-Open No. 7-142170

However, a polarizing film made of iodine-dyed PVA tends to have a yellow color, and has a problem that the so-called neutral color is inferior. In addition, since a polarizing film made of iodine-dyed PVA is difficult to thin, there has been a limitation in applying it to a recent display device that requires a thinner thickness. Then, the objective of this invention is providing the polarizing film which is easy to thin-film and excellent in neutral color property, the polarizer containing the said polarizing film, its manufacturing method, etc.

The present invention includes the following inventions.

[1] a polymer formed of a polymerizable liquid crystal compound and at least one dichroic dye (1) having an absorption maximum in a range of 380 to 550 nm in the case where light absorption is measured by dispersing in the polymer; The polarizing film containing at least 2 types of dichroic dyes (2) which have absorption maximum in the range of wavelength 550-700 nm.

[2] The polarization according to [1], in which the dichroic dye (1) is dispersed in a polymer formed of a polymerizable liquid crystal compound and the light absorption is measured, having an absorption maximum in a wavelength of 400 to 550 nm. membrane.

[3] In the case where the light absorption is measured by dispersing in the polymer, at least two dichroic dyes (2) having an absorption maximum in the wavelength range of 550 to 700 nm,

In the case where the light absorption is measured by dispersing in the polymer,

Dichroic dye (2-1) which has an absorption maximum in the range of 550-600 nm of wavelengths,

The polarizing film as described in [1] or [2] containing the dichroic dye (2-2) which has an absorption maximum in the range of 600-700 nm of wavelengths.

[4] The polarizing film according to any one of [1] to [3], wherein the polymerizable liquid crystal compound is a compound showing a smectic liquid crystal phase.

[5] The polarizing film according to any one of [1] to [4], in which a Bragg peak is obtained in X-ray diffraction measurement.

[6] The color coordinates a * and b * values in the L * a * b * colorimetric system described in any of [1] to [5], in which the relationship between the following formulas (1F) and (2F) is satisfied: One polarizing film.

-3≤ chromaticity a * ≤3 (1F)

-3≤ chroma b * ≤3 (2F)

[7] The polarizing film according to any one of [1] to [6], wherein the dichroic dye (1) and the dichroic dye (2) are azo compounds.

[8] The polarizing film according to any one of [1] to [7], wherein the dichroic dye (2) is made of a compound represented by formula (2).

[In formula (2), n is 1 or 2.

Ar ¹ and Ar ³ are each independently a group represented by any one of formulas (AR-1) to (AR-4).

Ar ² is a group represented by formula (AR2-1), formula (AR2-2) or formula (AR2-3).

A ₁ and A ₂ are each independently a group represented by any one of formulas (A-1) to (A-9), and * represents a bonding number.

(mc is an integer of 0-10, and when two mcs are in the same group, these two mcs are the same or different.)

[9] The polarizing film according to any one of [1] to [8], wherein the dichroic dye (1) is made of a compound represented by 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 any ^one of formulas (R ¹ -1) to (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 the same or different from each other. * Represents a bond number.)

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

(Wherein mb is an integer of 0 to 10).]

[10] A polarizer formed by forming a polarizing film as described in any one of [1] to [9] on a transparent substrate.

[11] The method for producing a polarizer according to [10],

Preparing a laminate having an alignment film on a transparent substrate;

Dichroic dye which has absorption maximum in the range of wavelength 380-550 nm when disperse | distributing in a polymerizable liquid crystal compound and the polymer formed from the said polymeric liquid crystal compound on the said oriented film of the said laminated body, and measuring light absorption. (1) 1 type, the process of apply | coating the composition containing 2 types of dichroic dyes (2) which have absorption maximum in the range of 550-700 nm, and a solvent,

The manufacturing method which has a process of superposing | polymerizing the said polymeric liquid crystal compound contained in the said composition.

[12] The production method according to [11], wherein the transparent substrate is a plastic substrate and the alignment film is a photoalignment film.

[13] A liquid crystal display device comprising the polarizing film as described in any one of [1] to [9].

[14] A circular polarizing plate having the polarizing film as described in any one of [1] to [9] and a λ / 4 layer, which satisfies the following requirements (A1) and (A2).

(A1) the angle between the absorption axis of the polarizing film and the slow axis of the λ / 4 layer is approximately 45 °;

(A2) The value of the front retardation of the [lambda] / 4 layer measured in light having a wavelength of 550 nm is in the range of 100 to 150 nm.

[15] An organic EL display device comprising the circular polarizing plate described in [14] and an organic EL element.

According to the present invention, it is possible to provide a polarizing film which is easy to thin and excellent in neutral color and a polarizer including the polarizing film.

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.
FIG. 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 which shows the layer order of this polarizer used for the liquid crystal display of 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.
FIG. 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.
11 is a schematic view showing the configuration of a projection type liquid crystal display device using the polarizing film of the present invention.

The polarizing film (henceforth called "this polarizing film" of this invention) of this invention is characterized by including the polymer formed from a polymeric liquid crystal compound, and specific 3 or more types of dichroic dyes. It is preferable that this polarizing film is formed from the composition (The "polarizing film formation composition" is what follows) containing a polymeric liquid crystal compound and the said 3 or more types of dichroic dye. First, the composition for polarizing film formation is demonstrated.

1. Composition for Polarizing Film Formation

It is preferable that the composition for polarizing film formation of this invention contains a polymeric liquid crystal compound and specific 3 or more types of dichroic dyes as mentioned above, and also contains a solvent further. The present polarizing film formed from the composition for forming a polarizing film is easily thinned. First, each of the structural components contained in the composition for polarizing film formation is demonstrated.

1-1. Dichroic pigment

When the dichroic dye contained in the composition for polarizing film formation is disperse | distributed to the polymer formed from the polymeric liquid crystal compound, and light absorption is measured, at least 1 type of dichroic dye which has absorption maximum in the range of wavelength 380-550 nm. In the same measurement as (1), at least 2 dichroic dyes (2) which have an absorption maximum in the range of wavelength 550-700 nm are included.

1-1-1. Dichroic Dye (1)

The dichroic dye (1) has an absorption maximum in the range of 380 to 550 nm when the light absorption is measured by dispersing it in a polymer formed of a polymerizable liquid crystal compound. On the other hand, this measurement prepares the composition for maximum absorption measurement which replaced the dichroic dye of the composition for polarizing film formation in this invention with the dichroic dye which wants to measure an absorption maximum, and uses for polarizing film formation mentioned later What is necessary is just to form the absorption maximum measurement film | membrane by the method similar to the method of forming this polarizing film with a composition, and to measure the light absorption of this absorption maximum measurement film | membrane. The specific method of the said absorption maximum measurement is the same as the method described in the Example of this application.

As a dichroic dye (1), an azo compound is mentioned, for example. Preferably, the compound (henceforth called "compound (1)") represented by said formula (1) is mentioned.

The geometric isomer of the azobenzene moiety of the compound (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. As said alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, etc. are mentioned. 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 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) a group represented by the formula (R ² -2), formula (R ² -5) or a group represented by the formula is a group represented by (R ² -6), and more preferably, is a group represented by the formula (R ² -6) More preferred. When 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 0-10, and more preferable in it being an integer of 0-5.

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 preferable.

The dichroic dye (1) has an absorption maximum in the range of wavelength 380 to 550 nm when light absorption is obtained by the above measurement, and preferably has an absorption maximum in the range of wavelength 400 to 550 nm, and preferably has a wavelength of 400 to 520. It is more preferable to have an absorption maximum in the range of nm, it is more preferable to have an absorption maximum in the range of wavelength 430-520 nm, and it is especially preferable to have an absorption maximum in the range of wavelength 440-510 nm. As long as it has absorption maximum in the said range, multiple types of compound (1) can also be used as a dichroic dye (1).

Here, the manufacturing method of compound (1) is demonstrated. Compound (1) can be produced, for example, by a reaction represented by the following scheme with 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 with 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, a combination of a carbonyloxyalkyl group and an amino group (the amino group may be substituted with R), and the like. In addition, although the compound (1X) which has R <^1> and the compound (1Y) which have 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 appropriate 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 the reaction mixture during the reaction, and the degree of disappearance 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.

1-1-2. Dichroic dye (2)

The dichroic dye 2 has an absorption maximum in the range of 550-700 nm in wavelength when the said measurement is performed. The measuring method of absorption maximum is the same as that of the dichroic dye (1).

The dichroic dye (2) includes two or more kinds in the composition for forming a polarizing film, and among them, the dichroic dye (2-1) having an absorption maximum in the range of 550 to 600 nm, and a wavelength of 600 to 700 nm. It is more preferable to include the dichroic dye (2-2) which has an absorption maximum in the range of. Here, the dichroic dye (2-1) is more preferable if it has an absorption maximum in the range of 570-600 nm, and dichroic dye (2-2) is more preferable if it has an absorption maximum in the range of 600-680 nm. Do.

Examples of the dichroic dyes (2) include azo compounds. It is preferable that the dichroic dye (2) is a compound represented by the formula (2) (hereinafter referred to as "compound (2)" in some cases).

The geometric isomer of the azobenzene moiety of the compound (2) is preferably trans.

In the combination of each group of the compound (2), the dichroic dye (2- by combining Ar ¹ , Ar ² and Ar ^{3 such} that the compound (2) has an absorption maximum in the range of 550 to 600 nm in the measurement. The compound (2) which can be used as 1) is determined. As a specific dichroic dye (2-1), the compound (2) shown by the combination of each group in Table 1 is mentioned. The compound (2-1) which shows the combination of each group in Table 1 shows the case where n in Formula (2) is 1. In Table 1, for example, groups represented by the formula (AR-1) and the like are represented by "(AR-1)" or the like.

Subsequently, in the combination of each group of the compound (2), the dichroic dye (2) by combining Ar ¹ , Ar ² and Ar ^{3 such} that the compound (2) has absorption in the range of 600 to 700 nm in the measurement. Compound (2) which can be used as -2) is determined. As a specific dichroic dye (2-2), the compound (2) shown by the combination of each group in Table 2 is mentioned. The compound (2-2) which shows the combination of each group in Table 2 shows the case where n in Formula (2) is 1. In addition, notation of group in Table 2 is the same as that of Table 1.

Here, when compound (2) is shown concretely, the compound etc. which are respectively represented by Formula (2-11)-Formula (2-39) are mentioned.

In the specific example of the compound (2) mentioned here, as a dichroic dye (2-1), it is Formula (2-12), Formula (2-13), Formula (2-18), Formula (2-20), Expression (2-21), Expression (2-22), Expression (2-23), Expression (2-24), Expression (2-26), Expression (2-27), Expression (2-28), Expression What is represented by (2-29) and Formula (2-30), respectively, corresponds to a dichroic dye (2-2), Formula (2-31), Formula (2-32), Formula (2-33), The thing represented by Formula (2-34), Formula (2-35), and Formula (2-36) respectively corresponds. In addition, what is respectively represented by Formula (2-11), Formula (2-15), and Formula (2-16) is not a pigment | dye which shows absorption in wavelength 550-700 nm, but complementarily uses it together with the pigment | dye of Formula (1). can do.

Among the specific examples of the compound (2), examples of the dichroic dye (2) included in the composition for forming a polarizing film include Formula (2-15), Formula (2-16), Formula (2-18), and Formula (2-20). ), Formula (2-21), formula (2-22), formula (2-23), formula (2-27), formula (2-29), formula (2-31), formula (2-32) More preferably, it is represented by Formula (2-33), Formula (2-34), and Formula (2-35), respectively. Among these, when dichroic dye (2) is represented by 2 or more types of combinations chosen from the specific example of a compound (2), although it changes with a mixing ratio, it is as showing in Table 3, for example. In this Table 3, the compound (2) represented, for example by Formula (2-11) shall be represented by "(2-11)".

Content of the dichroic dye (1) in the composition for polarizing film formation is represented by content with respect to 100 mass parts of polymerizable liquid crystal compounds mentioned later, 50 mass parts or less are preferable, and 0.1 mass part or more and 10 mass parts or less are more preferable. Preferably, 0.1 mass part or more and 5 mass parts or less are more preferable.

Content of the dichroic dye (2) in the composition for polarizing film formation is represented by content with respect to 100 mass parts of polymerizable liquid crystal compounds mentioned later, 10 mass parts or less are preferable, and 0.1 mass part or more and 5 mass parts or less are more. Preferably, 0.1 mass part or more and 3 mass parts or less are more preferable.

Moreover, the total content of the dichroic dye (1) and the dichroic dye (2) in the composition for polarizing film formation is represented by content with respect to 100 mass parts of polymeric liquid crystal compounds mentioned later, 30 mass parts or less are preferable, 0.1 mass part or more and 20 mass parts or less are more preferable, and 1 mass part or more and 15 mass parts or less are further more preferable.

When content of each dichroic dye exists in the said range, since the dichroic dye in the composition for polarizing film formation shows sufficient solubility with respect to a solvent, when this polarizing film was manufactured using the said composition for polarizing film formation, it is a defect. The present polarizing film without generation of can be obtained. On the other hand, as mentioned above, although the composition for polarizing film formation should contain 1 or more types of dichroic dyes (1) and 2 or more types of dichroic dyes (2), the said composition for polarizing film formation is a dichroic dye (1). (2) Even if it contains 2 or more types, you may contain 3 or more types of dichroic dyes (2). When it contains 2 or more types of dichroic dyes (1), content of the dichroic dye (1) is made into the total amount of 2 or more types of dichroic dyes (1), and contains 3 or more types of dichroic dyes (2). , Content of dichroic dye (2) is taken as the total amount of 3 or more types of dichroic dyes (2).

The dichroic dye (2) is produced by the known method described in, for example, Japanese Patent Application Laid-Open No. 58-38756, Japanese Patent Application Laid-Open No. 63-301850, Japanese Patent Application Laid-Open No. 58-104984, and the like.

Next, structural components other than the dichroic dye in the composition for polarizing film formation are demonstrated.

1-2. Polymerizable Liquid Crystal Compound

A polymeric liquid crystal compound is a liquid crystal compound which can superpose | polymerize with orientation, and has a polymeric group in a molecule | numerator. The composition for polarizing film formation containing a polymeric liquid crystal compound forms this polarizing film by superposing | polymerizing in the state which orientated the polymeric liquid crystal compound. It is especially preferable if it is a radically polymerizable group. A radically polymerizable group means group which participates in a radical polymerization reaction.

Although the polymeric liquid crystal compound contained in the composition for polarizing film formation of this invention shows a nematic liquid crystal phase (henceforth a "nematic liquid crystal phase"), a smectic liquid crystal phase (henceforth, Although it may show the "smectic liquid crystal phase" in some cases, and 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 forming a polarizing film containing a polymerizable smectic liquid crystal compound is a polarizing film having a very good neutral colorability due to the interaction between the dichroic dye (1) and the dichroic dye (2) and having excellent polarization performance. You can get it.

As the smectic liquid crystal phase represented by the polymerizable smectic liquid crystal compound, a higher order smectic liquid crystal phase is more 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. In addition, this polarizing film produced by the high order smectic liquid crystal phase with a high degree of orientation order obtains Bragg peak derived from higher order structures, such as a hexatic phase and a crystal phase, in X-ray diffraction measurement. 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 a nematic liquid crystal phase or a smectic liquid crystal phase can be confirmed as follows, for example. After preparing a suitable base material, apply | coating the composition for polarizing film formation to the said base material, and forming a coating film, the solvent contained in a coating film is removed by heat-processing or depressurizing on condition that 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 are not phase separated can be confirmed by, for example, surface observation by various microscopes and scattering measurement by 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 "compound (4)") is represented, for example by Formula (4).

U^One-V^One-W^One-X^One-Y^One-X²-Y²-X³-W²-V²-U² (4)

[In formula (4), 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-. It may be done.]

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

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

Y ¹ of compound (4) is preferably -CH ₂ CH _2- , -COO- or a single bond, and Y ² is preferably -CH ₂ CH ₂ -or -CH ₂ O-.

U ² is a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, preferably a polymerizable group. If U ¹ and U ² is a polymerizable group together is preferred, and more preferred is a photopolymerization group together. A photopolymerizable group means the 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 (4), 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 are preferably alkanediyl groups having ² to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.

Examples of the substituent optionally having an optionally substituted alkanediyl group having 1 to 20 carbon atoms include a cyano group and a halogen atom. The alkanediyl group is preferably unsubstituted and unsubstituted or linear alkanediyl group. It is more preferable.

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

As compound (4), the compound etc. which are represented by Formula (4-1)-formula (4-43) are mentioned. When the specific example of such compound (4) has cyclohexane-1, 4-diyl group, it is preferable that such 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 (4). 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 (4), formula (4-5), formula (4-6), formula (4-7), formula (4-8), formula (4-9), formula (4-10), formula (4-11), formula (4-12), formula (4-13), formula (4-14), formula (4-15), formula (4-22), formula (4-24), formula ( The compounds represented by 4-25), formula (4-26), formula (4-27), formula (4-28) and formula (4-29) are preferable. These compounds can be polymerized under the temperature conditions below the crystal phase transition temperature easily by interaction with other polymerizable liquid crystal compounds, i.e., 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 increased, which is preferable. Here, solid content means the total amount of components 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 manufactured by the well-known method described in Pays-Bas, 115, 321-328 (1996) or Japanese Patent No. 4719156 etc.

1-3. solvent

It is preferable that the composition for polarizing film formation contains a solvent. As a solvent, the solvent which can melt | dissolve a polymeric liquid crystal compound and a dichroic dye completely is preferable. Moreover, it is preferable that it is a solvent inactive for 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 content of a solvent, 50-98 mass% is preferable with respect to the total amount of the said 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 to obtain the thin this polarizing film which is one of the objectives of this invention, and it 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 a polarizing film becomes substantially uniform, it exists in the tendency for a stain to hardly arise in the said polarizing film, and it is preferable. In addition, such solid content can be determined in consideration of the thickness of a polarizing film.

1-4. Other additives

The composition for polarizing film formation in this invention arbitrarily contains additives other than a dichroic dye, a polymeric liquid crystal compound, and a solvent.

1-4-1. Polymerization reaction aid

It is preferable that the composition for polarizing film formation contains a polymerization initiator. The polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound. As a polymerization initiator, a photoinitiator is preferable at the point which can start a 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 the 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-trimethyl benzophenone, etc. are mentioned.

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.

A polymerization initiator can also use a commercially available thing. 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, 100 mass of the total 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.

1-4-2. Photosensitizer

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, etc.); 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.

1-4-3. Polymerization inhibitor

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 polymerization inhibitor is included in the composition for forming a polarizing film, the content thereof is appropriately adjusted depending on the type and amount of the polymerizable liquid crystal compound to be used, the content of the photosensitizer, and the like. It 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 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.

1-4-4. 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.

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

Leveling agents mainly composed of fluorine atom-containing compounds include "mega park R-08", copper "R-30", copper "R-90", copper "F-410", 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 Gensho Co., Ltd.]; "E-top EF301", the "EF303", the "EF351", and the "EF352" [Misubishimaterialden Shigasei Co., Ltd.] etc. are mentioned.

When a leveling agent is contained in the composition for polarizing film formation, 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, 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.

2. Formation method of this polarizing film

Next, the method of forming this polarizing film with the composition for polarizing film formation is demonstrated. In such a 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.

2-1. Transparent substrate

A transparent base material is a base material which is transparent 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, as a transparent base material, a glass base material, a plastic base material, etc. are mentioned, Preferably it is a plastic 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, a supporting substrate or the like can be adhered to the transparent substrate in that the transparent substrate can be easily handled without causing damage such as tearing when carrying or storing the transparent substrate. You may put it. In addition, although mentioned later, when manufacturing a circularly-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", "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 substrates which consist of thermoplastic resins can be extended | stretched, the plastic substrate 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 monomer, for example, The said 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 linear olefin, a vinylated aromatic compound (styrene or the like), 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.

In the case where the cyclic olefin resin is a copolymer of a cyclic olefin with 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 total 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, "Esshina" and "SCA40" [Sekisuga Chemical Co., Ltd.]; "Zeonor Film" [Optes Corporation]; "Aton Film" [JSR Corporation] 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 unwrapped plastic base material is returned to a heating furnace. The setting temperature of a heating furnace is the range of the glass transition temperature vicinity (degreeC)-[glass transition temperature +100] (degreeC) of a plastic base material, Preferably it is near glass transition temperature (degreeC)-[glass transition temperature +50] (degreeC). We assume range of). In the said heating furnace, when extending | stretching to the advancing direction of a plastic base material or a direction orthogonal to a advancing direction, a conveyance direction and a tension are adjusted, and it inclines at arbitrary angles, and carries out the uniaxial or biaxial thermal stretching process. The draw ratio is usually in the range of about 1.1 to 6 times, and preferably in the range of about 1.1 to 3.5 times. Moreover, as a method of extending | stretching in an oblique direction, if it can continuously incline an orientation axis | shaft to 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 Japanese Patent Laid-Open No. 50-83482 and Japanese Patent Laid-Open No. 2-113920.

Although the thickness of a transparent base material is the weight of the grade which can be handled practically, and the point which can ensure sufficient transparency, a thinner one is preferable, but when it is too thin, there exists a tendency for the 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. In addition, 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.

2-2. 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 the heat processing for removal of a solvent and orientation of a liquid crystal. Such an alignment film can be formed by an oriented polymer.

Examples of the oriented polymer include polyamides and gelatin having amide bonds in the molecule, polyimides having imide bonds in the molecule, and polyamic acid, polyvinyl alcohol, alkyl modified polyvinyl alcohol, polyacrylamide, 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, and acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-substituted hydrocarbon solvents, such as chloroform and chlorobenzene, etc. are mentioned. 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 a base material, the method of apply | coating and annealing the said oriented polymer composition or a commercially available oriented film material on a base material, etc. are mentioned, for example. The thickness of the alignment film thus obtained is usually in the range of 10 nm to 10000 nm, preferably in the range of 10 nm 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 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 liquid crystal aligning ability by irradiating light (light irradiation). Specifically, a photoreaction that causes the origin of the liquid crystal alignment ability, such as the alignment organic or isomerization reaction, dimerization reaction, photocrosslinking reaction or photolysis reaction of molecules generated by irradiation with light, is caused. It is preferable at the point which raises a dimerization reaction or a photocrosslinking reaction among the said photoreactive group, is excellent in orientation, and maintains the smectic liquid crystal state at the time of polarizing film formation. As a photoreactive group which can cause the above reaction, it is preferable to have an unsaturated bond, especially a double bond, and a carbon-carbon double bond (C = C bond), a carbon-nitrogen double bond (C = N bond), nitrogen Particular preference is given to groups having at least one selected from the group consisting of -nitrogen 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, stilazole group, stilbazolium group, chalcone group and cinnamoyl group. Examples of the photoreactive group having a C═N bond include groups having structures such as aromatic sieve bases and aromatic hydrazones. As a photoreactive group which has N = N bond, 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 a cinnamoyl group and a chalcone group are preferable because they have a relatively small amount of polarization irradiation required for optical alignment, and are easy to obtain an optical alignment film having excellent thermal stability and stability over time. Do. 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 above-mentioned orientation polymer composition is mentioned as said solvent, 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 film 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 and a photosensitizer in a range in which the properties of the photo-alignment film are not significantly impaired.

As a method of apply | coating an orientation polymer composition or the composition for photo-alignment layer formation on a base material, coating methods, such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, and an applicator method, a flexographic method, etc. 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 several area | region (pattern) from which an orientation direction differs.

2-3. 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 composition for polarizing film formation, the method similar to what was illustrated as a method of apply | coating an orientation polymer or a composition for photoreaction 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, natural drying method, ventilation drying method, heat drying, reduced pressure 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 smectic The method of cooling to the temperature which shows a liquid crystal 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 made into a smectic liquid crystal phase or the polymerizable liquid crystal compound is made into 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 such phase transition temperatures 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 the said 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, or 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 preferred in that 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 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 employing such cooling means, if the polymerizable liquid crystal compound can be polymerized at a lower temperature, there is an advantage that the present polarizing film can be appropriately formed even if a relatively low heat resistance is used for the substrate described above. On the other hand, the present polarizing film patterned by masking, image development, etc. at the time of photopolymerization can also be obtained.

By performing photopolymerization as described above, the polymerizable liquid crystal compound is polymerized while maintaining a nematic liquid crystal phase, a smectic liquid crystal phase, preferably a higher order smectic liquid crystal phase as already exemplified, thereby forming the polarizing film. The polarizing film obtained by superposing | polymerizing with a polymeric liquid crystal compound holding a smectic liquid crystal phase is a conventional host guest polarizing film, ie, the polarizing film obtained by superposing | polymerizing a polymeric liquid crystal compound etc., maintaining the liquid crystal state of a nematic liquid crystal phase. Compared with that, there is an advantage that the polarization performance is high. 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 this 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 Bragg peak is obtained, the present polarizing film which shows the diffraction peak derived from a hexatic phase or a crystal phase is mentioned, for example.

In addition, this polarizing film manufactured in this way is excellent in neutral color property. Here, the polarizing film which is excellent in neutral color property means that the color coordinate a * value and b * value in a L * a * b * (Lab) colorimetric system satisfy | fill the relationship of following formula (1F) and formula (2F). It is. In addition, these color coordinate a * value and b * value are calculated | required by the measuring method demonstrated in the Example of this application, for example.

-3≤ chromaticity a * ≤3 (1F)

-3≤ chroma b * ≤3 (2F)

Each of the color coordinate a * value and b * value here is also called "chromaticity a *" and "chromaticity b *". It is determined that a * and b * are polarizing films exhibiting a neutral color as they are closer to 0 (zero) together. In the display device provided with such a polarizing film, good white display without coloration can be obtained.

In addition, in the color of a polarizing film, when two polarizing films are overlapped so that an absorption axis may mutually orthogonally cross, the color at that time is calculated | required in the same way as mentioned above, and when "orthogonal a *" and "orthogonal b *" are calculated, such orthogonality is obtained. It is more preferable that each of a * and orthogonal b * satisfies the relationship of the following formula (1F ') and formula (2F'). These orthogonal a * and orthogonal b * are indicators which show whether the color of a black display is neutral in a display apparatus provided with a polarizing film. As the orthogonal a * and the orthogonal b * are closer together to 0 (zero), the better black display without coloration can be obtained.

-3≤orthogonal a * ≤3 (1F ')

-3≤orthogonal b * ≤3 (2F ')

3. 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 layer;

The process of continuously forming a dry film on the said oriented film by drying the apply | coated polarizing film formation composition on condition that a polymeric liquid crystal compound does not superpose | polymerize,

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, a polarizing film is continuously made by superposing | polymerizing the said polymeric liquid crystal compound, maintaining the said smectic liquid crystal phase. The step of obtaining a polarizer,

It has the process of winding up the polarizer continuously obtained by the 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 up by 210 A of 1st cores 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 are mentioned among the transparent base materials already illustrated above. Moreover, in using this polarizing film as a circularly polarizing plate, the transparent base material to which retardation was previously provided 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 the said 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 the said auxiliary roll 300 may be sufficient. In addition, both the 1st winding core 210A and the auxiliary roll 300 provide a rotation means, and the form which unwinds a transparent base material, giving a suitable tension to a transparent base material may be sufficient.

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. As described above, in order to continuously apply the composition for forming the photo-alignment layer, a printing method such as a gravure coating method, a die coating method, a flexographic method, etc. is performed by the coating device 211A.

The transparent base material which passed through the coating device 211A is conveyed to the drying furnace 212A, it is heated by the said 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 polarizing UV irradiation device 213A, and the first drying is performed. 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 (first 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.

In 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 with 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 polarizing film continuously formed is wound up by 220 A of 2nd cores in the form of the laminated body containing a transparent base material and an orientation film, 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 optical alignment film on the transparent base material, and the present polarizer is produced.

In addition, although the manufacturing method shown to FIG. 1 showed the method of manufacturing continuously from the 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, the 1st laminated body is unwound from the said 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 in shape. When this polarizing film is used for the liquid crystal display device mentioned later, it is cut and used so that it may become a desired dimension according to the scale etc. of the liquid crystal display device.

As mentioned above, although the structure and manufacturing method of this polarizer have been demonstrated centering on the case of the laminated body of a transparent base material / an optical orientation film / this polarizing film, this polarizing film can also be obtained in a single layer by peeling an optical alignment film or a transparent base material from this polarizer. have. 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 described above, the present polarizing film may further include a retardation film, or may further include an antireflection layer or a brightness enhancing film.

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 which shifted and set the angle of the slow axis and the absorption axis of a polarizing film was produced, and produced a 1/4 wavelength plate on the opposite side to the surface in which the said polarizing film was formed. By further forming, it is also possible to make a broadband circular polarizing plate.

4. 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. In addition, you may have the overcoat layer (not shown) between the color filter 15 and the transparent electrode 16. FIG.

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 and thin film transistor 21 formed on a board | substrate, when the process of heating at high temperature is necessary, 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, the said 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, quarter wave plate and optical compensation film) 13a and 13b are laminated | stacked. By arranging this polarizing film 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 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 or 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 this polarizer.

Moreover, the antireflection film for preventing reflection of external light may be arrange | positioned outside the present polarizer (outside when a 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 providing the present polarizer in 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 retardation 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 so as to be arranged in the above order from the retardation layer 13a side.

5 is an enlarged schematic view of a portion B of FIG. 3. When (B1) of FIG. 5 uses this polarizer 100 as a polarizer 12b, the transparent base material 1, the photo-alignment film 2, and this polarizing film 3 are in this order from the retardation film 13b side. Installed to be deployed. In FIG. 5B, when the present 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 electroluminescence, 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 present liquid crystal display device 10 is changed. 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. Thus, the 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, this 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 (circular polarizing plate) on this polarizing film side 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 schematic diagram showing the first embodiment of the circular polarizing plate 110. The said 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. This 2nd Embodiment uses the transparent base material 1 (retardation film 4) in which phase difference property was previously provided to the transparent base material 1 used when manufacturing this polarizer, and the transparent base material 1 itself is This circular polarizing plate 110 has a function as the phase difference layer 4.

As this circular polarizing plate containing this polarizing film, since the structure is simple if it is 2nd Embodiment of this circular polarizing plate mentioned above, it is preferable, In this case, it is preferable to use a 1/4 wavelength plate as a transparent base material, Furthermore, a transparent base material 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, according to the second embodiment of the circular polarizing plate 110, in the present manufacturing method of manufacturing the present polarizing film 100, the transparent base material 1, that is, the phase difference, which is previously given a phase difference as the transparent base material 1, is used. It can manufacture by using a film. 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 manufactured by the present production method B. FIG. On the other hand, when the present polarizing film 100 is manufactured in the form of the second roll 220 by the present production method B, the polarizing film 100 viewed from the second roll 220 is released, and a predetermined dimension is obtained. 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. In this manufacturing method,

Unwinding the polarizer 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 successively bonding a polarizing film formed on the present polarizer 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 a fourth core 240A to obtain 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, it forms with the said adhesive using a suitable adhesive. The polarizing film 3 and the retardation film may be bonded through the pressure-sensitive adhesive layer.

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 arranged 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, the thin film transistor 40 is first 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 procedure will be described with reference to an enlarged view of the portion C surrounded by the dotted line in FIG. When the circular polarizing plate 110 is used as the circular polarizing plate 31, the retardation 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 alumina; Metal substrates such as copper; Plastic substrates; Although not shown, a thermally conductive film may be formed on the substrate 33. A diamond thin film (DLC etc.) etc. are mentioned as a thermally conductive film. 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 a plate-shaped thing, 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 metals (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 vapor deposition of 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, and In ₂ O ₃ , but 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 mixed gas thereof 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 a two- or three-component alloy system selected from the illustrated metal elements. Examples of the alloy system include Ag.Mg (Ag: 1 to 20 at%), Al.Li (Li: 0.3 to 14 at%), In.Mg (Mg: 50 to 80 at%), and Al.Ca (Ca: 5 -20 at%), etc. are preferable.

The cathode electrode 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. Various organic compounds can be used for the hole injection layer and the hole transport layer. The vacuum evaporation method can be used in that a homogeneous thin film can be formed for formation of a hole injection transport layer, a light emitting layer, and an electron injection transport layer.

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 diagram 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 the film of the electrolytic capacitor. DLC membrane has the characteristic that the water permeability is very bad, and high moisture-proof performance. A DLC film or the like may also 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 polarizing film (this polarizing film) which concerns on this invention, and the novel display apparatus (this liquid crystal display device and this EL display device) provided with this polarizing film are provided.

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

11 is a schematic view 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 liquid crystal display device.

The bundle of rays emitted from a light source (eg, a high-pressure mercury lamp) 111 that is a light emitting source first includes 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 light beam bundles irradiates all three liquid crystal panels 140R, 140G, and 140B to be illuminated, and for this reason, each liquid crystal panel incident side The surface is roughly uniform throughout.

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 polarization from the light source is converted into polarization 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. Are separated, and are 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 into 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 a 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 molecule orientation, those represented by particles such as electrophoresis, particle movement, particle rotation, and phase change, those represented by movement of one end of the film, molecular What is indicated by color development / phase change, what is represented by light absorption of a molecule, 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). With this polarizing film, patterning is performed by printing, inkjet, photolithography, or the like. 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. In the examples, &quot;% &quot; and &quot; part &quot; are parts by mass and parts by mass unless otherwise specified.

In the present Example, the following dichroic dye (1) was used.

Preparation of compound (1-1) (compound represented by the following (1-1))

Compound (1-1) 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 (1-1). The yield was 87% based on compound (1B).

¹ H-NMR (CDCl ₃ ) of Compound (1-1): 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).

Preparation of compound (1-7) (compound represented by the following (1-7))

Compound (1-7) 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 it stirred further 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, followed by crystallization by adding heptane, followed by vacuum drying to obtain 4.66 g of compound (1-7). The yield was 60% based on compound (1B).

¹ H-NMR (CDCl ₃ ) of Compound (1-7): 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).

In the present Example, the following polymeric liquid crystal compound was used.

Compound (4-6) (compound represented by the following formula (4-6))

Compound (4-6) is described by Lub et al. Recl. Trav. Chim. It synthesize | combined by the method described by Pays-Bas, 115, 321-328 (1996).

[Measurement of Phase Transition Temperature]

The phase transition temperature of compound (4-6) was confirmed by calculating | requiring the phase transition temperature of the film | membrane which consists of compound (4-6). The operation is as follows.

The film | membrane which consists of a compound (4-6) was formed on the glass substrate in which the oriented film was formed, and the phase transition temperature was confirmed by the texture observation by a polarizing microscope (BX-51, Olympus company), heating. When the film made of compound (4-6) 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 (4-8) (compound represented by the following formula (4-8))

Compound (4-8) was synthesized with reference to the synthesis method of compound (4-6) described above.

[Measurement of Phase Transition Temperature]

The phase transition temperature of the compound (4-8) was confirmed by the same method as the phase transition temperature measurement of the compound (4-6). Compound (4-8), after raising the temperature to 140 ° C, when the temperature is lowered, phase transition to the nematic phase at 131 ° C, phase transition to the Smectic A phase at 80 ° C, to Smectic B phase at 68 ° C Phase transition.

Compound (4-22) (compound represented by the following formula (4-22))

Compound (4-22) was synthesized with reference to the synthesis method described in Japanese Patent No. 4719156.

[Measurement of Phase Transition Temperature]

The phase transition temperature of the compound (4-22) was confirmed by the same method as the phase transition temperature measurement of the compound (4-6). Compound (4-22) raises the temperature to 140 ° C., and then, when the temperature is lowered, phase transitions to a nematic phase at 106 ° C., phase transition to Smectic A phase at 103 ° C., and to Smectic B phase at 86 ° C. Phase transition.

Compound (4-25) (compound represented by the following formula (4-25))

Compound (4-25) was synthesized with reference to the synthesis method described in Japanese Patent No. 4719156.

[Measurement of Phase Transition Temperature]

The phase transition temperature of the compound (4-25) was confirmed by the same method as the phase transition temperature measurement of the compound (4-6). When compound (4-25) raises the temperature to 140 degreeC, and at the time of lowering temperature, it phase-transfers into a nematic phase at 119 degreeC, phase-transforms into a Smectic A phase at 100 degreeC, and a Smectic B phase at 77 degreeC. Phase transition.

Example 1 [Preparation of Composition (A) for Polarizing Film Formation]

The following components were mixed and stirred at 80 degreeC for 1 hour, and the composition (A) for polarizing film formation was obtained. In addition, the "compound (1-7)" of the dichroic dye used here means the compound represented by said Formula (1-7), and the compound used as another dichroic dye also conforms to the formula number. The same applies to the following.

Polymerizable liquid crystal compounds; 75 parts of compounds (4-6)

25 parts of compound (4-8)

Dichroic dyes; 3.0 parts of compound (1-7)

2.5 parts of compounds (2-17)

1.5 parts of compounds (2-29)

2.0 parts of compounds (2-32)

Polymerization initiator; 6 parts of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (irgacure 369; Chiba Specialty Chemicals Co., Ltd.)

Leveling agents; 1.2 parts of polyacrylate compounds (BYK-361N; manufactured by BYK-Chemie)

solvent; Toluene 250 parts

1. X-ray diffraction measurement

A 2 mass% aqueous solution (composition for forming an alignment layer) of polyvinyl alcohol (polyvinyl alcohol 1000 fully saponified, manufactured by Wako Pure Chemical Industries, Ltd.) was coated on a glass substrate by spin coating, dried, and then A 100 nm film was formed. Next, the alignment layer was formed by performing a rubbing treatment on the surface of the obtained film. The rubbing treatment is carried out with a cloth (trade name: YA-20-RW, manufactured by Yoshikawa Kako Co., Ltd.) using a semi-automatic rubbing device (trade 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. The polarizing film-forming composition (A) was applied onto the alignment film thus prepared by spin coating, heated and dried for 1 minute on a 120 ° C hotplate, and then rapidly cooled to room temperature and dried on the alignment layer. A film was formed. Subsequently, the ultraviolet-ray is irradiated to a dry film by exposure amount 2000mJ / cm <2> (365 nm standard) using a UV irradiation apparatus (SPOT CURE SP-7; the product made by Ushio Denki Co., Ltd.), and the polymeric property contained in the dry film is carried out. The liquid crystal compound was polymerized while maintaining the liquid crystal state of the polymerizable liquid crystal composition, and a polarizing film was formed from the dry film. It was 1.7 micrometers when the thickness of the polarizing film at this time was measured by the laser microscope (OLS3000 by Olympus Corporation). X-ray diffraction measurement was similarly performed on the polarizing film using an X-ray diffractometer X'Pert PRO MPD (manufactured by SPECTRESS Co., Ltd.). As a result, peak half width (FWHM) = approximately 0.17 ° around 2θ = 20.2 °. A sharp diffraction peak (Bragg peak) of was 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, and it was confirmed that a structure reflecting the higher order smectic phase was formed.

2. Preparation of Photoalignment Film on Transparent Film

Using a triacetyl cellulose film (KC8UX2M, manufactured by Konica Minolta Co., Ltd.) as a transparent substrate, a liquid obtained by dissolving a photo-alignment polymer represented by the following formula (3) in toluene by 5% was applied by a bar coat method, and 120 It dried at ° C and obtained a dry film. Polarized UV was irradiated on this dry film, and the photo-alignment film was obtained. The polarization UV treatment was performed under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.).

3. Fabrication of Polarizing Film

On the film with the photo-alignment film obtained as mentioned above, the composition (A) for polarizing film formation was apply | coated by the bar coat method (# 5 17 mm / s), and it heat-dried for 1 minute in 120 degreeC drying oven, and It cooled to room temperature. Subsequently, using a UV irradiation apparatus (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.), ultraviolet rays having an exposure dose of 2000 mJ / cm 2 (365 nm standard) were irradiated to the layer formed of the composition for forming a polarizing film, thereby drying the same. The polymerizable liquid crystal compound contained in the film was polymerized while maintaining the liquid crystal state of the polymerizable liquid crystal composition, and a polarizing film was formed from the dry film. It was 1.6 micrometers when the film thickness of the polarizing film at this time was measured with the laser microscope (OLS3000 by Olympus Corporation). What was obtained in this way is a polarizer containing a polarizing film and a transparent base material.

4. Measurement of polarization degree, transmittance and color

In order to confirm the usefulness of a polarizer, the visibility correction polarization degree, the visibility correction transmittance | permeability, chromaticity a * value, chromaticity b * value, orthogonal a *, and orthogonal b * were measured as follows.

In the wavelength range of 380 nm to 780 nm, a folder having a polarizer was set in the spectrophotometer (UV-3150 manufactured by Shimadzu Seisakusho Co., Ltd.) for transmission (T ¹ ) in the transmission axis direction and transmission (T ² ) in the absorption axis direction. It measured by the double beam method using one apparatus. In the folder, the reference side installed the mesh which cuts the amount of light by 50%. Using the following formulas (Formula 1) and (Formula 2), monolithic transmittance and polarization degree at each wavelength were calculated, and the visibility correction was performed by the 2-degree field of view (C light source) of JIS Z 8701, and the visibility correction monolith was obtained. The transmittance Ty and the visibility correction polarization degree Py were calculated. In addition, the chromaticity a * and b * in the L * a * b * (CIE) colorimeter were computed from the monochromatic transmittance measured by the same formula using the orange color function of the C light source. In addition, orthogonal a * and orthogonal b * in the L * a * b * (CIE) colorimeter were calculated from the orthogonal transmittance measured similarly using the C-light source function. Chromaticity a *, chromaticity b *, orthogonal a *, and orthogonal b * may be determined to be neutral colors as the value approaches 0. These results are shown in Table 4.

Monolithic transmittance (%) = (T1 + T2) / 2 (Equation 1)

Polarization degree (%) = (T1-T2) / (T1 + T2) × 100 (Equation 2)

Example 2

1. Fabrication of Polarizing Film

A polarizing film was produced in the same manner as in Example 1 except for changing the wire width and the coating speed of the bar coater bar (# 7 15 mm / s). It was 1.8 micrometers when the film thickness of the polarizing film at this time was measured by the laser microscope (OLS3000 by Olympus Corporation).

2. Measurement of polarization degree, transmittance and color

The measurement results of visibility correction monolithic transmittance (Ty) and visibility correction polarization (Py) and chromaticity a *, chromaticity b *, orthogonal a *, and orthogonal b * of the prepared polarizing film were measured in the same manner as in Example 1. Indicates.

Example 3 [Preparation of Composition (B) for Polarizing Film Formation]

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

Polymerizable liquid crystal compounds; 75 parts of compounds (4-22)

25 parts of compound (4-25)

Dichroic dyes; Compound (1-1) 3.0 parts

2.5 parts of compounds (2-15)

1.2 parts of compounds (2-20)

2.5 parts of compounds (2-33)

Polymerization initiator; 6 parts of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (irgacure 369; Chiba Specialty Chemicals Co., Ltd.)

Leveling agents; 1.2 parts of polyacrylate compounds (BYK-361N; manufactured by BYK-Chemie)

solvent; Toluene 250 parts

1. Fabrication of Polarizing Film

The polarizing film-forming composition (A) was changed to the polarizing film-forming composition (B), and the same as in Example 1 except for changing the wire width and coating speed of the bar coater bar (# 5 25 mm / s). To produce a polarizing film. It was 1.7 micrometers when the film thickness of the polarizing film at this time was measured with the laser microscope (OLS3000 by Olympus Corporation).

2. Measurement of polarization degree, transmittance and color

The measurement results of visibility correction monolithic transmittance (Ty) and visibility correction polarization (Py) and chromaticity a *, chromaticity b *, orthogonal a *, and orthogonal b * of the prepared polarizing film were measured in the same manner as in Example 1. Indicates.

Example 4

1. Fabrication of Polarizing Film

A polarizing film was produced in the same manner as in Example 3 except that the wire width and the coating speed of the bar coater's bar were changed (# 7 20 mm / s). It was 2.0 micrometers when the film thickness of the polarizing film at this time was measured with the laser microscope (OLS3000 by Olympus Corporation).

2. Measurement of polarization degree, transmittance and color

The measurement results of visibility correction monolithic transmittance (Ty) and visibility correction polarization (Py) and chromaticity a *, chromaticity b *, orthogonal a *, and orthogonal b * of the prepared polarizing film were measured in the same manner as in Example 1. Indicates.

Example 5

1. Fabrication of Black Polarizing Film

A polarizing film was produced in the same manner as in Example 3 except that the wire width and the coating speed of the bar coater's bar were changed (# 5 50 mm / s). It was 2.2 micrometers when the film thickness of the polarizing film at this time was measured with the laser microscope (OLS3000 by Olympus Corporation).

2. Measurement of polarization degree, transmittance and color

The measurement results of visibility correction monolithic transmittance (Ty) and visibility correction polarization (Py) and chromaticity a *, chromaticity b *, orthogonal a *, and orthogonal b * of the prepared polarizing film were measured in the same manner as in Example 1. Indicates.

Example 6 [Preparation of Composition (C) for Polarizing Film Formation]

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

Polymerizable liquid crystal compounds; 75 parts of compounds (4-6)

25 parts of compound (4-8)

Dichroic dyes; 3.6 parts of compounds (1-1)

3.0 parts of compounds (2-15)

1.5 parts of compounds (2-18)

2.0 parts of a compound (2-27)

1.5 parts of compounds (2-32)

Polymerization initiator; 6 parts of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butan-1-one (irgacure 369; Chiba Specialty Chemicals Co., Ltd.)

Leveling agents; 1.2 parts of polyacrylate compounds (BYK-361N; manufactured by BYK-Chemie)

solvent; Toluene 250 parts

1. Fabrication of Polarizing Film

The polarizing film-forming composition (A) was changed to the polarizing film-forming composition (C), and the same as in Example 1 except for changing the wire width and coating speed of the bar coater bar (# 7 20 mm / s). To produce a polarizing film. It was 2.0 micrometers when the film thickness of the polarizing film at this time was measured with the laser microscope (OLS3000 by Olympus Corporation).

2. Measurement of polarization degree, transmittance and color

The measurement results of visibility correction monolithic transmittance (Ty) and visibility correction polarization (Py) and chromaticity a *, chromaticity b *, orthogonal a *, and orthogonal b * of the prepared polarizing film were measured in the same manner as in Example 1. Indicates.

Example 7

1. Fabrication of Black Polarizing Film

A polarizing film was produced in the same manner as in Example 6 except that the wire width and the coating speed of the bar coater's bar were changed (# 5 50 mm / s). It was 2.2 micrometers when the film thickness of the polarizing film at this time was measured with the laser microscope (OLS3000 by Olympus Corporation).

2. Measurement of polarization degree, transmittance and color

The measurement results of visibility correction monolithic transmittance (Ty) and visibility correction polarization (Py) and chromaticity a *, chromaticity b *, orthogonal a *, and orthogonal b * of the prepared polarizing film were measured in the same manner as in Example 1. Indicates.

Comparative Example 1

1. Fabrication of Iodine-PVA Polarizer

Polyvinyl alcohol film having an average degree of polymerization of about 2,400 and a degree of saponification of 99.9 mol% or more and a thickness of 75 µm was uniaxially stretched by about 5 times in a dry manner and immersed in pure water at 60 ° C. for 1 minute while maintaining a tension state, followed by iodine It was immersed at 28 degreeC for 60 second in the aqueous solution which / mass ratio of potassium iodide / water is 0.1 / 5/100. Then, it was immersed for 300 second in 72 degreeC in the aqueous solution of the potassium iodide / boric acid / water mass ratio 810.5 / 7.5 / 100. Subsequently, the resultant was washed with pure water at 10 ° C. for 5 seconds, and then dried at 80 ° C. for 3 minutes to obtain a polarizer in which iodine was adsorbed and oriented on the polyvinyl alcohol resin film.

2. Measurement of polarization degree, transmittance and color

The measurement results of the visibility correction monolith transmittance (Ty) and the visibility correction polarization (Py) and chromaticity a *, chromaticity b *, orthogonal a *, and orthogonal b * of the produced polarizer were measured in the same manner as in Example 1. Indicates.

As can be seen from Table 4, all of the polarizing films of Examples 1 to 7 were thinner than conventional iodine-PVA polarizers. In addition, all the polarizing films of Examples 1-7 showed neutral color property.

Example 8

1. Preparation of optical alignment film on retardation film

Retardation film (uniaxially stretched film WRF-S (modified polycarbonate-based resin), retardation value 137.5 nm, thickness 50 µm, Teijin Chemical Co., Ltd.) ), The liquid obtained by dissolving the photo-alignment polymer represented by the formula (3) in 5% cyclopentanone was applied by a bar coat method, dried at 120 ° C to obtain a dry film. Polarized UV was irradiated on this dry film, and the photo-alignment film was obtained. The polarization UV treatment was performed under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ using a UV irradiation device (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.). In addition, at this time, the irradiation direction of polarization UV was implemented so that it might become 45 degrees with respect to the slow axis of a retardation film.

2. Fabrication of Circular Polarizer

After apply | coating the composition (C) for polarizing film formation by the bar coat method (# 7 20 mm / s) on the photo-alignment film of the retardation film which has the produced photo-alignment film, heat-dried for 1 minute in 120 degreeC drying oven, Cooled to room temperature. Subsequently, using a UV irradiation apparatus (SPOT CURE SP-7; manufactured by Ushio Denki Co., Ltd.), ultraviolet rays having an exposure dose of 2000 mJ / cm 2 (365 nm standard) were irradiated to the layer formed of the composition for forming a polarizing film, thereby drying the same. The circularly polarizing plate was produced by superposing | polymerizing the polymeric liquid crystal compound contained in a film, maintaining the liquid crystal state of the said polymeric liquid crystal composition, and forming a polarizing film with the dry film. It was 2.0 micrometers when the film thickness of the polarizing film at this time was measured with the laser microscope (OLS3000 by Olympus Corporation).

3. Confirmation of anti-reflection performance

When the retardation film side and the aluminum metal plate of the obtained circular polarizing plate were bonded together through the adhesive, the metallic gloss observed by the aluminum metal plate single body disappeared, and the uniform black display was obtained. Thus, it turns out that the circularly-polarizing plate produced by this polarizing film has favorable antireflection characteristic.

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

1: transparent base material 2: photo-alignment film
3: present polarizing film 4: retardation layer
100: present polarizer 210: first roll
210A: 220: second roll
220A: Core 230: Third Roll
230A: Attention 240: Fourth Roll
240A: winding cores 211A, 211B: coating device
212A and 212B: drying furnace 213A: polarized UV irradiation device
213B: light irradiation apparatus 300: auxiliary roll
10: liquid crystal display device 11: surface protective layer
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 (15)

When the polymer formed from the polymerizable liquid crystal compound and the polymer are dispersed in the polymer and the light absorption is measured, at least one dichroic dye (1) having an absorption maximum in the wavelength range of 380 to 550 nm, and the wavelength of 550 to A polarizing film comprising at least two dichroic dyes (2) having an absorption maximum in the range of 700 nm. The polarizing film of Claim 1 which has an absorption maximum in the range of 400-550 nm when the said dichroic dye (1) is disperse | distributed in the polymer formed from a polymeric liquid crystal compound, and light absorption is measured. The at least 2 dichroic dye (2) of Claim 1 or 2 which has an absorption maximum in the range of 550-700 nm when disperse | distributing in the said polymer and measuring light absorption,
In the case where the light absorption is measured by dispersing in the polymer,
Dichroic dye (2-1) which has an absorption maximum in the range of 550-600 nm of wavelengths,
The polarizing film containing the dichroic dye (2-2) which has an absorption maximum in the range of 600-700 nm of wavelengths. The polarizing film of any one of Claims 1-3 whose polymerizable liquid crystal compound is a compound which shows a smectic liquid crystal phase. The polarizing film of any one of Claims 1-4 in which a Bragg peak is obtained in X-ray diffraction measurement. The color coordinate a * value and b * value in an L * a * b * color system satisfy | fill the relationship of following formula (1F) and formula (2F) in any one of Claims 1-5. Polarizing film.
-3≤ chromaticity a * ≤3 (1F)
-3≤ chroma b * ≤3 (2F) The polarizing film of any one of Claims 1-6 whose dichroic dye (1) and dichroic dye (2) are azo compounds. The polarizing film of any one of Claims 1-7 in which the dichroic dye (2) consists of a compound represented by Formula (2).

[In formula (2), n is 1 or 2.
Ar ¹ and Ar ³ are each independently a group represented by any one of formulas (AR-1) to (AR-4).

Ar ² is a group represented by formula (AR2-1), formula (AR2-2) or formula (AR2-3).

A ₁ and A ₂ are each independently a group represented by any one of formulas (A-1) to (A-9), and * represents a bonding number.

(mc is an integer of 0-10, and when two mcs are in the same group, these two mcs are the same or different.) The polarizing film of any one of Claims 1-8 in which a dichroic dye (1) consists of a compound represented by 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 any ^one of formulas (R ¹ -1) to (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 the same or different from each other. * Represents a bond number.)
R ² is a group represented by any one of formulas (R ² -1) to (R ² -6).

(Wherein mb is an integer of 0 to 10).] The polarizer formed by forming the polarizing film of any one of Claims 1-9 on a transparent base material. As a manufacturing method of the polarizer of Claim 10,
Preparing a laminate having an alignment film on a transparent substrate;
Dichroic dye which has absorption maximum in the range of wavelength 380-550 nm when disperse | distributing in a polymerizable liquid crystal compound and the polymer formed from the said polymeric liquid crystal compound on the said oriented film of the said laminated body, and measuring light absorption. (1) 1 type, the process of apply | coating the composition containing 2 types of dichroic dyes (2) which have absorption maximum in the range of 550-700 nm, and a solvent,
Polymerizing the polymerizable liquid crystal compound contained in the composition
&Lt; / RTI &gt; The manufacturing method of Claim 11 whose transparent base material is a plastics base material, and the said oriented film is a photo-alignment film. The liquid crystal display device provided with the polarizing film of any one of Claims 1-9. The circularly-polarizing plate which has the polarizing film of any one of Claims 1-9, and (lambda) / 4 layer, 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 λ / 4 layer is 45 °;
(A2) The value of the front retardation of the said (lambda) / 4 layer measured with the light of wavelength 550nm shall be 100-150 nm. The organic electroluminescence display provided with the circularly-polarizing plate of Claim 14, and organic electroluminescent element.

Images