JP6493972B2 - Method of manufacturing a polarizing element with a very small amount of droplet - Google Patents

Description

The present invention relates to a method for producing a polarizing element with a very small amount of droplets when an aqueous solution containing a dichroic dye is applied to a substrate.

Polarizing elements used in liquid crystal display devices, sunglasses, goggles, etc., adsorb dichroic dyes such as iodine and dichroic dyes to polymer substances such as polyvinyl alcohol, stretch the film, and dichromatic It is manufactured by a method of arranging a sexual dye or a method of adsorbing a dichroic molecule on a stretched polymer film. However, the polarization axis of the polarizing element obtained by these methods can only provide the absorption axis of the polarizing plate in the stretched direction, can only produce a flat plate, and has a large dimensional change because it involves stretching. In addition, the manufacturing process requires many steps of swelling, dyeing, boric acid aqueous solution of polyvinyl alcohol film, stretching, washing treatment, drying treatment, and bonding with a protective film with an adhesive. there were. For this reason, it has been demanded to provide a polarizer more easily in a desired portion.

Conventionally, the technique of nonpatent literature 1 is indicated for this purpose. However, although a method for producing a polarizer by orienting a dye by rubbing treatment is disclosed, the polarization performance is poor, there are defects due to coating, and the surface property is poor, and the quality as a polarizing plate. Was regarded as low. Patent Document 1 discloses a technique for obtaining a polarizer having higher performance that can be oriented in an arbitrary direction using a photo-alignment film, but is inferior in the coating property and performance of the polarizing element. In addition, it is described that the polarization performance and the surface state do not meet sufficient requirements. In order to improve such uniformity and polarization performance, in Patent Document 2, the occurrence of a portion where there is almost no pigment and no orientation (crater) is reduced as much as possible, and the orientation of the dichroic compound is improved as a whole. A technique relating to a method of manufacturing a polarizing element at a practical level for use is disclosed. Further, in Patent Document 2, a liquid crystalline polymer thin film is used as an alignment film, the thin film is irradiated with linearly polarized light, and then irradiated with linearly polarized light having different polarization axes through another micropatterned mask. Although a manufacturing method is disclosed in which a dichroic molecular solution is applied on a thin film so that a specific range of pressure is applied in a direction perpendicular to the substrate, the alignment film used as a base material is special and very expensive. In addition, it is difficult to manufacture industrially, and it is necessary to apply a specific pressure between the rolls in the production of the polarizer. Therefore, the wider the coating surface, the more uneven the surface. There have been problems such as contact with the rolls, which became a defect due to the contact of the rolls, and extremely minute scratches on the substrate.

JP-A-7-261024 Japanese Patent No. 4175455

Toshiaki Nose, Rumiko Yamaguchi, Susumu Sato, IEICE Transactions, J71-C, 1188 (1988) Application of functional dyes, 1st printing edition, CMC Publishing Co., Ltd., supervised by Masahiro Irie, P102-104 Alexander, L.E.Diffraction Methods InPolymer Science, Wiley-Interscience: NewYork, 1969, Chapter 4, pp241-252

  So far, in the method of obtaining a polarizer by applying a dye, the required quality has not been achieved. The surface quality is poor, the level of coating in coating and the location where it is applied cannot be easily controlled, and scratches caused by rubbing caused by rubbing treatment, or electrical scratches caused by dust or static electricity As a result, it was difficult to obtain a high-quality polarizing element.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has dramatically improved the surface by improving the coating method, and can easily control the level of concentration in coating and the location where the coating is applied. High-quality polarizing element that dramatically improves polarization characteristics and does not cause scratches caused by rubbing caused by contact coating with rolls or electrical scratches caused by dust or static electricity Can be obtained. Further, it has been found that a polarizing element having a higher dichroic ratio can be obtained by making the stretching axis and the rubbing axis coaxial by applying a rubbing treatment to the substrate that has been further stretched. It was newly found that a polarizing element can be easily produced on an arbitrary axis different from the stretching axis by rubbing at a different angle. Furthermore, when applying the aqueous solution containing a dichroic dye to a base material, it came to develop the manufacturing method of the polarizing element characterized by the quantity of the droplet being 1 microliter or less.

That is, the present invention
“(1) When applying an aqueous solution containing a dichroic dye to a substrate, a discharge port for discharging a recording liquid in a predetermined direction, a liquid channel having a straight portion connected to the discharge port, A state change caused by liquid pressure or heat is caused to occur in the liquid containing the dichroic dye in the straight portion of the liquid passage and the inlet for supplying the recording liquid communicating with the liquid passage. And a recording liquid is ejected from the ejection port to form flying droplets, and the amount of the droplets is 1 picoliter to 1 microliter.
(2) The method for producing a polarizing element according to (1), wherein the method of applying droplets of 1 microliter or less is an ink jet method.
(3) The method according to (2), wherein when a droplet of 1 microliter or less is applied, the distance from the droplet discharge port to the substrate is within 3 mm.
(4) The manufacturing method of (1) to (3), wherein the ink jet method is a piezo method.
(5) In (4), the substrate is a film or sheet made of a resin selected from polyethylene terephthalate, polyethylene naphthalate, polycarbonate, cycloolefin, cellulose, triacetylcellulose, acrylic, polyimide, and polyamide. Description manufacturing method.
(6) The method according to any one of (1) to (4), wherein the substrate is rubbed.
(7) The method according to (1) to (6), wherein the aqueous solution containing the dichroic dye has a viscosity of 0.5 to 10 mPa · s.
(8) The method for producing a polarizing element according to any one of (1) to (5), wherein at least one of the dichroic dyes is a compound represented by the formula (1).
(In Formula (1), X ₁ is a phenyl group or a naphthyl group having one or two sulfonic acid groups, and further having a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and X ₂ and X ₃ are Phenylene having one or two substituents independently selected from an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, and a sulfonic acid group. A group or a naphthylene group, R ₁ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an acetyl group, a benzoyl group or a substituted or unsubstituted phenyl group, m is 0 or 1, n is 1 or 2 Represents.)
(9) The method for producing a polarizing element as described in (1) to (5), wherein at least one of the dichroic dyes is a compound represented by the formula (2).

(In Formula (2), Y ₁ represents a naphthyl group having one or two sulfonic acid groups and further having a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, Y ₂ or Y ₃ independently represents 1 or 2 substituents selected from an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, and a sulfonic acid group as substituents. A phenylene group or a naphthylene group, R ₂ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an acetyl group, a benzoyl group, or a substituted or unsubstituted phenyl group. A phenylazo group is substituted at any of the 6-position, 7-position or 8-position, and R ₃ and R ₄ are each independently a hydrogen atom, a hydroxyl group, a sulfonic acid group, or an alkyl having 1 to 3 carbon atoms. Group or An alkoxy group having 1 to 3 carbon atoms, q represents 0 or 1, and p represents 1 or 2. )
(10) The dichroic dye is a compound represented by the formula (3), wherein X ₁ of the formula (1) and / or Y ₁ of the formula (2) is the compound represented by the formula (3) The manufacturing method of the polarizing element as described in (4).
(In formula (3), j represents 1 or 2.)
(11) The method for producing a polarizing element according to any one of (1) to (10), wherein the dichroic dye layer contains polyoxyethylene polyoxypropylene alkyl ether or a derivative thereof. ".

When an aqueous solution containing a dichroic dye is applied to a substrate, a high-performance polarizing element can be obtained simply by a polarizing element manufacturing method characterized in that the amount of droplets is 1 microliter or less. To get.

FIG. 1 shows that the polarizing element obtained in Example 1 is placed on a blank sheet, and an iodine-based polarizing plate SKN-18242P manufactured by Polatechno Co., Ltd. is disposed on the polarizing element and has the polarization of the obtained polarizing element. It is a figure shown, and is the figure which has arrange | positioned the extending | stretching axis | shaft of an iodine type polarizing plate coaxially with respect to the rubbing axis | shaft applied to the OHP sheet. FIG. 2 is a diagram in which the stretching axis of the iodine polarizing plate is arranged on the orthogonal axis with respect to the rubbing axis applied to the OHP sheet.

"The present invention, ... the dichroic dye in the straight part of ... the fluid passage"

As the base material used in the present invention, glass plates such as silica glass and hard glass, quartz plates, polysiloxane resins, ABS resins, cycloolefin resins, acetal resins, (meth) acrylic resins, cellulose acetate, cellulose Acetate, chlorinated polyether, ethylene-vinyl acetate copolymer, fluorine resin, ionomer, methylpentene polymer, nylon, polyamide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, etc. polyester, polyimide, polyamide, polyphenylene oxide, polyphenylene sulfide, Polyallylsulfone, polyarylate, polyethylene, polypropylene, polystyrene, polysulfone, cycloolefin resin, vinyl acetate resin, vinylidene chloride resin, AS resin, vinyl chloride Plastic plates and sheets (films) of various materials such as resin, alkyd resin, allyl resin, amino resin, urea resin, melamine resin, epoxy resin, phenol resin, unsaturated polyester resin, silicone resin, polyurethane, Patent Document 1, Patent Photoactive molecules (commonly known as photoalignment films) as described in Document 2, or films or plates on which these resins are laminated or applied, or on the surface, silicon oxide, tin oxide, indium oxide, aluminum oxide Examples of the base material include metal oxides such as titanium oxide, chromium oxide, and zinc oxide, silicon nitride, silicon carbide, and the like. Alternatively, a substrate (film) whose surface is coated with a highly reflective metal thin film can also be used as a base material. These base materials may be not only planar but also curved. Furthermore, when the illustrated film or base material is stretched, molecular anisotropy is expressed on the surface, and the dichroic dye can be oriented. The stretched state of the film indicates that the film is anisotropically expressed in the molecular orientation of the film. The expression of this anisotropy can be measured by diffraction measurement by X-ray measurement, phase difference measurement, anisotropic IR absorption analysis, or the like. In particular, in the orientation coefficient obtained by the fc calculation method described in Non-Patent Document 3, fc should be 0.3 or more, preferably 0.5, more preferably 0.7, and 0.9 or more. Particularly preferred. The method of stretching the film is not particularly problematic as long as anisotropy develops. However, the use of a uniaxially stretched film gives a film having a high degree of polarization after the application of the dichroic dye. .

By performing corona discharge treatment or ultraviolet irradiation on the substrate, the dichroism of the dichroic dye is improved as will be described later, so that the polarization characteristics can be further enhanced. As an apparatus for performing the corona discharge treatment, various commercially available corona discharge treatment machines can be applied. In particular, a corona treatment machine having an aluminum head is preferable. The condition of the corona discharge treatment is 20 to 400 W · min / m ² , preferably about 50 to W · min / m ² as an energy density in one treatment. If one process is insufficient, the process may be performed twice or more. Similarly, various commercially available ultraviolet irradiation apparatuses can be applied to the ultraviolet irradiation. The wavelength of the ultraviolet rays to be used is not particularly limited, but for example, far ultraviolet rays having a wavelength of 300 nm or less are preferable. Moreover, it is preferable to perform ultraviolet irradiation under an oxygen stream. Even if the irradiation time is long, a few minutes is sufficient.

Examples of dichroic dyes include dye compounds such as azo dyes, stilbene dyes, pyrazolone dyes, triphenylmethane dyes, quinoline dyes, oxazine dyes, thiazine dyes, and anthraquinone dyes. . The dichroic dye used in the present invention is a compound that exhibits lyotropic liquid crystallinity under certain solvent composition, dye concentration, and temperature conditions, and examples thereof include the dyes described in Non-Patent Document 2. A water-soluble one is preferred, but not limited thereto. A compound having an aromatic ring structure is preferred. As the aromatic ring structure, in addition to benzene, naphthalene, anthracene, phenanthrene, a heterocyclic ring such as thiazole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, or a quaternary salt thereof, and these with benzene, naphthalene, etc. A fused ring is particularly preferred. Further, it is preferable that a hydrophilic substituent such as a sulfonic acid group, a carboxylic acid group, an amino group, or a hydroxyl group is introduced into these aromatic rings. Specific examples of such dichroic dyes include C.I. I. Direct Orange 39,
C. I. Direct Orange 41,
C. I. Direct Orange 49,
C. I. Direct Orange 72,
C. I. Direct Red 2,
C. I. Direct Red 28,
C. I. Direct Red 39,
C. I. Direct Red 79,
C. I. Direct Red 81,
C. I. Direct Red 83,
C. I. Direct Red 89,
C. I. Direct Violet 9,
C. I. Direct Violet 35,
C. I. Direct Violet 48,
C. I. Direct Violet 57,
C. I. Direct Blue 1,
C. I. Direct Blue 15,
C. I. Direct Blue 67,
C. I. Direct Blue 78,
C. I. Direct Blue 83,
C. I. Direct Blue 90,
C. I. Direct Blue 98,
C. I. Direct Blue 151,
C. I. Direct Blue 168,
C. I. Direct Blue 202,
C. I. Direct Green 42,
C. I. Direct Green 51,
C. I. Direct Green 59,
C. I. Direct Green 85,
C. I. Direct Yellow 4,
C. I. Direct Yellow 12,
C. I. Direct Yellow 26,
C. I. Direct Yellow 44,
C. I. Direct Yellow 50,
Moldant Yellow 26,
C. I. No. 27865,
C. I. No. 27915,
C. I. No. 27920,
C. I. No. 29058,
C. I. No. 29060
In addition, JP-A-1-161202, JP-A-1-172906, JP-A-1-172907, JP-A-1-183602, JP-A-1-248105, and JP-A-1-265205. And the described dyes. In particular, a dye having the structure of the formula (1) or (2) is preferably used. Further Oite _to X ₁ or Y ₁ of the formula (1) or (2), when having the structure of formula (3), it is possible to further improve the performance. Examples of such a pigment include dichroic dyes exemplified in Japanese Patent No. 3963379.

In Formula (1), X ₁ is a phenyl group or naphthyl group having one or two sulfonic acid groups, and further having a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and X ₂ and X ₃ are each A phenylene group having one or two substituents independently selected from an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group and a sulfonic acid group; Or a naphthylene group, R ₁ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an acetyl group, a benzoyl group or a substituted or unsubstituted phenyl group, m is 0 or 1, and n is 1 or 2. Represent.

In Formula (2), Y ₁ represents a naphthyl group having one or two sulfonic acid groups, and further having a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, Y ₂ or Y ₃ independently represents one or two substituents selected from an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, and a sulfonic acid group as substituents. Or a phenylene group or a naphthylene group, R ₂ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an acetyl group, a benzoyl group, or a substituted or unsubstituted phenyl group, the 5-position of the terminal naphthyl group , A phenylazo group is substituted at any of the 6-position, 7-position or 8-position, and R ₃ and R ₄ are each independently a hydrogen atom, a hydroxyl group, a sulfonic acid group, or an alkyl group having 1 to 3 carbon atoms. Or 1 An alkoxy group having 3 to 3 carbon atoms, q represents 0 or 1, and p represents 1 or 2.

In the formula (3), j represents 1 or 2.

These dichroic dyes are oriented on the substrate. The above dichroic molecule alone or a mixture of two or more thereof is mixed with water, alcohols, ethers, pyridine, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidinone (NMP), dimethylacetamide. It dissolves in a hydrophilic solvent such as an aprotic polar solvent such as (DMAC) -dimethylimidazoline (DMI) or a water-containing solvent thereof. Particularly preferred is a mixed solvent mainly composed of water. The mixing amount of the organic solvent in water is arbitrary, but 0 to 50% by weight, particularly 0 to 20% by weight, based on water is preferable. The concentration of the dichroic dye is preferably 0.1 to 25% by weight, more preferably 0.3 to 10% by weight, and still more preferably 0.5 to 5% by weight.

In the present invention, a general water-soluble surfactant can be used. Specifically, the additive described in Patent Document 2 can be used. More preferably, an additive which becomes polyoxyethylene polyoxypropylene alkyl ether or a derivative thereof is added. By adding this additive, it is necessary to reduce the shear stress parallel to the substrate described in Patent Document 2, and it is necessary to use a specific surfactant, particularly an anionic surfactant. However, a special processing method at the time of coating is not necessary according to the present invention. An additive and a dichroic dye that are polyoxyethylene polyoxypropylene alkyl ethers or their derivatives are added to a rubbed substrate, a photo-alignment film, a substrate scratched by friction, or a stretched substrate. The dye film of the present invention can be produced simply by applying or dripping the contained solution. The concentration of the additive that can be a surfactant is preferably 0.001 to 5% by weight, more preferably 0.01 to 2% by weight, based on the solution containing the dichroic dye. More preferably, it is 0.05 wt% to 1.0 wt%.

With the above, an aqueous solution containing a dichroic dye can be obtained. Although the viscosity of the liquid to be applied can be measured with a measuring instrument such as E-type viscosity measurement, the viscosity measurement is not limited to the E-type. The resulting viscosity is preferably 0.5 to 10.0 mPa · s, preferably 0.5 to 6.0 mPa · s, more preferably 0.9 to 5.0 mPa · s, and even more preferably 1. It is preferably 0 to 4.0 mPa · s. In the viscosity measurement, a value measured at 20 ° C. to 30 ° C., particularly preferably 25 ° C. may be used, but the temperature may be adjusted to a preferable viscosity at the time of coating.

"Next, ... dichroic dye in the straight part of ... the fluid passage"

The thickness of the dichroic dye layer is preferably thinner from the viewpoint of improving polarization characteristics, for example, 0.001 to 10 μm or less, preferably 0.03 μm to 2 μm, more preferably 0.05 μm to 1 μm. Is preferred. The coating film thickness for applying the solution containing the dichroic dye for forming the dichroic dye film is preferably 1 to 10 μm, more preferably 2 to 5 μm. Is preferred.

The substrate to which the dichroic dye solution is attached is dried to form a solid dichroic dye layer, whereby the polarizing element of the present invention is obtained. Although the drying conditions vary depending on the type of solvent, the type of dichroic dye, the amount of the applied dichroic dye solution, the concentration of the dichroic dye, etc., the temperature is 25 ° C to 100 ° C, preferably 25 ° C to The temperature is 50% and the humidity is 20% RH to 95% RH, preferably about 30% RH to 90% RH.

Further, the substrate to which the dichroic dye solution is attached may be further heated or humidified. Heating or humidifying is preferable because adhesion, polarization performance, dichroism and durability of the dichroic dye are improved. The temperature is 25 ° C. to 95 ° C., preferably 60 ° C. to 90 ° C., and the humidity is 40% RH to 95% RH, preferably about 50% RH to 90% RH.

The dichroic ratio (Rd) of the polarizing element thus obtained is calculated by the formula (4). If the dichroism is 5 or more, the polarizing function is exhibited, but it is preferably 10 or more, more preferably 15 or more, and more preferably 20 or more. In this case, Ky is the transmittance of the axis that transmits the most light when polarized light is incident, and Kz is the transmittance of the axis that absorbs the most light when polarized light is incident.

Further, as a method for further improving the dichroism, it is preferable to use a stretched film, and more preferably, with respect to the stretched film surface, in the same direction as the stretch axis of the film, In contrast, dichroism can be further improved by exhibiting greater molecular anisotropy. An example of a method for developing molecular dichroism greater than that of the stretched film is a method of rubbing the stretched film. The rubbing is exemplified by methods such as JP-A-06-10059 and JP-A-2002-90743. The measurement of the molecular anisotropy of the surface of the stretched film is measured by a measurement method used for anchoring measurement of the alignment film for liquid crystal, and the method is not limited. Examples of the apparatus for measuring the molecular anisotropy of the surface include, but are not limited to, Ray Scan manufactured by MARITEX SCOTT.

A polarizing element characterized by exhibiting molecular anisotropy in an arbitrary direction on the surface of a film having an axis having a phase difference at an angle different from the major axis direction of the film can be produced by the method of the present application. In the technique of the present application, the polarizing element having the absorption axis can be used for a stretched film having a phase difference axis, that is, a slow axis or a fast axis (hereinafter also referred to as a phase difference axis) at an arbitrary angle. By imparting molecular anisotropy to the surface by rubbing or the like, the axial angle of the polarizing plate can be arbitrarily controlled. Stretching as a base material by using a stretched film showing molecular anisotropy on the surface in the major axis direction on the surface of the film having a phase difference axis at an angle different from the angle with respect to the major axis direction of the film It becomes possible to produce a polarizing element in which the axis having the phase difference of the film is different from the absorption axis or parallel axis of the polarizing element. As a result, it exhibits molecular anisotropy in the major axis direction on the surface of the film having a slow axis or a fast axis of phase difference at an angle of 10 ° to 100 ° with respect to the major axis direction of the film. A polarizing element can be manufactured. On the surface of a film having a slow axis or a fast axis at any angle of 10 ° to 20 °, 40 ° to 50 °, 70 ° to 80 °, 80 ° to 100 ° with respect to the major axis direction of the film It is preferable to provide molecular anisotropy in the major axis direction and provide the absorption axis of the polarizing element, but the angle between the retardation axis of the stretched film and the absorption axis or parallel axis of the polarizing element is 15 °. , 45 °, 75 °, or 90 ° is most preferable. The reason why each axis is preferable is that, in general, when linearly polarized light is to be controlled to circularly polarized light, a film having a phase difference of 1/4 with respect to the length of the wavelength to be controlled is used as the absorption axis of the polarizing element. It is known to install at 45 °. On the other hand, as a method of reversing the axis of linearly polarized light, it is known to install a film having a phase difference of 1/2 with respect to the length of the wavelength to be controlled at 90 °. Alternatively, the reason for the installation at 75 ° is an axial angle used in a prescription (generally referred to as a broadband achromatic phase difference plate) that shows a phase difference of ¼ with respect to a wide range of wavelengths. In the present application, a polarizing element having an absorption axis of the polarizing film can be arbitrarily adjusted by giving molecular anisotropy to the surface of the stretched film having a phase difference at an arbitrary angle by rubbing or the like. The combination with a stretched film is very useful because it can be controlled.

The dye layer thus formed is in a solid state such as amorphous or crystal, but the layer of the dichroic dye is usually inferior in mechanical strength, so that the surface thereof is subjected to Lake treatment and crosslinking with a silane coupling agent. A treatment and a protective layer are provided. “Lake” is a water-soluble dye electrically coupled to a metal ion or the like. Making the dye into Lake is sometimes referred to as “Lake” or “insolubilization”. Examples of compounds suitable for Lake include aluminum chloride, iron chloride, calcium chloride, barium chloride, nickel chloride, magnesium chloride, copper chloride, barium acetate, nickel acetate, etc. If it couple | bonds and a dichroic dye can be insolubilized in water, it will not be limited. The crosslinking treatment with the silane coupling agent is not particularly limited, and the silane coupling agent as described in JP2011-53234A is treated and crosslinked by heat treatment to fix the dye film. I can do it. The protective layer is usually coated with a dichroic molecular layer coated with a transparent polymer film such as UV curable or thermosetting, or laminated with a transparent polymer film such as a polyester film or a cellulose acetate film. Provided by law. The protective layer can be provided as a polymer-coated layer or a film laminate layer. The transparent polymer or film forming the transparent protective layer is preferably a transparent polymer or film having high mechanical strength and good thermal stability. As a substance used as a transparent protective layer, for example, cellulose acetate resin such as triacetyl cellulose or diacetyl cellulose or film thereof, acrylic resin or film thereof, polyvinyl chloride resin or film thereof, nylon resin or film thereof, polyester resin or film thereof A film, a polyarylate resin or a film thereof, a cyclic polyolefin resin having a cyclic olefin such as norbornene or a film thereof, polyethylene, polypropylene, a polyolefin having a cyclo or norbornene skeleton or a copolymer thereof, a main chain or a side chain Examples include imide and / or amide resins or polymers or films thereof. In addition, a resin having liquid crystallinity or a film thereof can be provided as the transparent protective layer. The thickness of the protective film is, for example, about 0.5 to 200 μm. A polarizing plate is produced by providing one or more layers of the same or different types of resins or films on one side or both sides.

According to the present invention, polarizers such as polarized sunglasses and goggles can be created. Compared to the case of using a normal polyvinyl alcohol film, since it can be performed only by applying a pigment, there is no dimensional change, and thus a polarizing plate without shrinkage can be obtained. The absence of dimensional change is particularly effective for displays that require a polarizing element on one side, such as a flexible display or an organic electroluminescence display (commonly referred to as OLED). In addition, unlike conventional polarizing plates, difficult conditions are not required for dye coating, and it is easy to manufacture because it becomes a polarizing element simply by applying a dichroic dye to a stretched film. become.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these. In addition, the transmittance | permeability shown in an Example was performed as follows.

The single transmittance, polarization degree, and dichroic ratio (Rd) of the wavelength (hereinafter referred to as λmax) indicating the maximum degree of polarization of the obtained measurement sample were measured using V-7100 manufactured by JASCO Corporation. The value was taken as the measurement result.

Example 1
As a dichroic dye, C.I. I. A composition of 3 parts by weight of Direct Blue 67, 1.0 part by weight of polyoxyethylene polyoxypropylene alkyl ether (Emulgen MS-110 manufactured by Kao Corporation) and 100 parts by weight of water was prepared. When the viscosity of the ink was measured using an E-type viscometer VISCOMETER TVE-22H (manufactured by Toki Sangyo Co., Ltd.), the viscosity was 1.25 mPa · s. The obtained ink was filled into DCP-J540N manufactured by Canon as an inkjet printer. An OHP sheet (product name: LPCOHPS1) for a color laser printer manufactured by EPSON was rubbed with a velvet cloth, the filled ink was applied, and a polarizing element was produced while drawing a pattern pattern. The obtained polarizing element could be applied as shown in FIG. When the polarizing element obtained on white paper was installed and checked while rotating the iodine-based polarizing plate on it, it was enough that the light and darkness could be clearly confirmed by rotating the iodine-based polarizing plate by 90 ° A polarizing element oriented in the direction was obtained.

Example 2
As a dichroic dye, C.I. I. A composition of 3 parts by weight of Direct Blue 67, 1.0 part by weight of polyoxyethylene polyoxypropylene alkyl ether (Emulgen MS-110 manufactured by Kao Corporation) and 100 parts by weight of water was prepared. When the viscosity of the ink was measured using an E-type viscometer VISCOMETER TVE-22H (manufactured by Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was 1.25 mPa · s. The obtained ink was filled into DCP-J540N manufactured by Canon as an inkjet printer. An OHP sheet (product name: LPCOHPS1) manufactured by EPSON was rubbed with a velvet cloth, the filled ink was applied, and a uniform polarizing element was produced without drawing a pattern. When the polarization performance of the obtained polarizing element was confirmed, a polarizing element having Ys of 45.43%, ρ of 77.53%, and Rd of 10.6 was obtained.

Example 3
As a dichroic dye, C.I. I. A composition comprising 6 parts by weight of Direct Blue 67, 1.0 part by weight of polyoxyethylene polyoxypropylene alkyl ether (Emulgen MS-110 manufactured by Kao Corporation) and 100 parts by weight of water was prepared. When the viscosity of the ink was measured using an E-type viscometer VISCOMETER TVE-22H (manufactured by Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was 5.79 mPa · s. The obtained ink was filled into DCP-J540N manufactured by Canon as an inkjet printer. An OHP sheet (product name: LPCOHPS1) manufactured by EPSON was rubbed with a velvet cloth, the filled ink was applied, and a uniform polarizing element was produced without drawing a pattern. When the polarizing performance of the obtained polarizing element was confirmed, a polarizing element having Ys of 42.53%, ρ of 83.64%, and Rd of 10.8 was obtained.

Example 4
As a dichroic dye, C.I. I. A composition of 4 parts by weight of Direct Blue 67, 1.0 part by weight of polyoxyethylene polyoxypropylene alkyl ether (Emulgen MS-110 manufactured by Kao Corporation) and 100 parts by weight of water was prepared. When the viscosity of the ink was measured using an E-type viscometer VISCOMETER TVE-22H (manufactured by Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. was 1.275 mPa · s. The obtained ink was filled into PM-205 manufactured by EPSON as an ink jet printer. An OHP sheet (product name: LPCOHPS1) manufactured by EPSON was rubbed with a velvet cloth, the filled ink was applied, and a uniform polarizing element was produced without drawing a pattern. When the polarizing performance of the obtained polarizing element was confirmed, a polarizing element having Ys of 44.84%, ρ of 91.01%, and Rd of 20.7 was obtained.

Example 5
The same applies except that the OHP sheet for color laser printer (product name: LPCOHPS1) manufactured by EPSON was used as the PET substrate used in Example 4 and applied to the non-easy surface (PET surface) of A-4100 manufactured by Toyobo Co., Ltd. Thus, a polarizing element was produced. A uniform polarizing element was produced without drawing a pattern. When the polarizing performance of the obtained polarizing element was confirmed, it was found that a polarizing element having Y44.75%, ρ of 94.05%, and Rd of 25.7 was obtained.

Comparative Example 1
In Example 1, as an inkjet printer, without using DCP-J540N manufactured by Canon Inc., coating was performed with a spray having a droplet size of 10 microliters or more (Airbrush Series No.31 Spray Work Basic manufactured by Tamiya). A droplet was formed and a uniform surface could not be obtained.

As is apparent from the results of Examples 1 to 5 and Comparative Example 1 described above, when the aqueous solution containing the dichroic dye is applied to the substrate, the amount of the droplets is 1 microliter or less. The polarizing element manufacturing method characterized in that the patterning of the polarizing element can be easily manufactured, and the performance of the obtained polarizing element is a polarizing element having a dichroic ratio of 20 or more. It can be seen that the polarization performance is very high. Moreover, since the manufacturing method is possible also with household inkjet, it turns out that a polarizing element can be manufactured easily. From the above results, the polarizing element manufacturing method of the present invention has led to a polarizing element that can be easily manufactured and has a high degree of polarization and high quality.

Claims (10)

When an aqueous solution containing a dichroic dye is applied to a substrate, a discharge port for discharging a recording liquid in a predetermined direction, a liquid channel communicating with the discharge port and having a straight portion, and a liquid channel A liquid pressure or heat is applied to a liquid containing a water-soluble lyotropic liquid crystalline dichroic dye and a water-soluble surfactant located in a straight portion of the liquid channel, and an inlet for supplying the recording liquid. to rise to state changes caused by the recording liquid on the basis of the state change is applied to form a flying liquid droplet is discharged from the discharge port, the amount of the droplets is 1 picoliter to 1 microliter, the substrate is polyethylene terephthalate, polyethylene naphthalate, polycarbonate, cycloolefin, cellulose, triacetyl cellulose, made of a film or sheet made of a resin selected from acrylic Method of manufacturing a polarizing element, wherein the molecular anisotropy to the substrate surface is expressed film or sheet. The method for manufacturing a polarizing element according to claim 1, wherein the method of applying droplets of 1 microliter or less is an ink jet method. 3. The method for manufacturing a polarizing element according to claim 2, wherein when applying a droplet of 1 microliter or less, a distance from the droplet discharge port to the substrate is within 3 mm. 4. The method for manufacturing a polarizing element according to claim 1, wherein the inkjet method is a piezo method. 5. The method for manufacturing a polarizing element according to claim 1, wherein the base material is rubbed. Method of manufacturing a polarizing element according to claims 1 to 5 viscosity of the aqueous solution containing a dichroic dye, characterized in that from 0.5 to 10 mPa · s. At least one dichroic dye, method of manufacturing a polarizing element according to claim 1 to 4, characterized in that the formula (1).
(In Formula (1), X1 is a phenyl group or a naphthyl group having one or two sulfonic acid groups, and further having a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and X2 and X3 are each independently A phenylene group or naphthylene having one or two substituents selected from an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, and a sulfonic acid group R1 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an acetyl group, a benzoyl group, or a substituted or unsubstituted phenyl group, m represents 0 or 1, and n represents 1 or 2.) At least one dichroic dye, method of manufacturing a polarizing element according to claim 1 to 4, characterized in that the formula (2).
(In Formula (2), Y1 is a naphthyl group which has one or two sulfonic acid groups and may further have a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, Y2 or Y3 represents 1 or 2 of 1 or 2 kinds of substituents each independently selected from an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group, and a sulfonic acid group as a substituent. An phenylene group or a naphthylene group, R2 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an acetyl group, a benzoyl group, or a substituted or unsubstituted phenyl group, the 5-position, 6-position of the terminal naphthyl group, A phenylazo group is substituted at either the 7-position or the 8-position, and R3 and R4 are each independently a hydrogen atom, a hydroxyl group, a sulfonic acid group, an alkyl group having 1 to 3 carbon atoms, or 1 to Alkoxy group having a carbon number of a, q is 0 or 1, p is 1 or 2.) 5. The polarized light according to claim 3, wherein the dichroic dye is a compound represented by the formula (3), wherein X1 of the formula (1) and / or Y1 of the formula (2) is represented by the formula (3): Device manufacturing method.
(In formula (3), j represents 1 or 2.) Layer polyoxyethylene polyoxypropylene alkyl ethers of the dichroic dye, or a method of manufacturing a polarizing element according to claim 1 to 9, characterized in that it contains a derivative thereof.