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WO2011149020A1 - Matière polarisante, matière de revêtement contenant celle-ci pour la production d'un film polarisant et film polarisant - Google Patents

Matière polarisante, matière de revêtement contenant celle-ci pour la production d'un film polarisant et film polarisant Download PDF

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Publication number
WO2011149020A1
WO2011149020A1 PCT/JP2011/062100 JP2011062100W WO2011149020A1 WO 2011149020 A1 WO2011149020 A1 WO 2011149020A1 JP 2011062100 W JP2011062100 W JP 2011062100W WO 2011149020 A1 WO2011149020 A1 WO 2011149020A1
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Prior art keywords
polarizing
metal
coating
refractive index
film
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PCT/JP2011/062100
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English (en)
Japanese (ja)
Inventor
了一 宮本
晃一 久保
秀樹 林
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積水化学工業株式会社
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Priority to JP2011531277A priority Critical patent/JP4842412B1/ja
Priority to KR1020127001852A priority patent/KR101176400B1/ko
Publication of WO2011149020A1 publication Critical patent/WO2011149020A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3058—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state comprising electrically conductive elements, e.g. wire grids, conductive particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B2207/00—Coding scheme for general features or characteristics of optical elements and systems of subclass G02B, but not including elements and systems which would be classified in G02B6/00 and subgroups
    • G02B2207/101—Nanooptics

Definitions

  • the present invention relates to a polarizing material particularly useful for use as a polarizing plate and a polarizing plate for increasing brightness, a coating material for manufacturing a polarizing film, and a polarizing film including the polarizing material.
  • a polarizer used near room temperature a polarizing plate for liquid crystal display and a polarizing plate for increasing luminance (also referred to as a luminance increasing film) have been put into practical use.
  • a polarizer requiring heat resistance a polarizer for an optical isolator used for the purpose of noise removal at the connection interface of an optical fiber used for optical communication has been put into practical use.
  • the polarizing plate is obtained by orienting an anisotropic pigment on the film.
  • the water-absorbing polyvinyl alcohol (PVA) film is impregnated with water-soluble iodine or a water-soluble dye and then stretched. It is made by doing.
  • the polarizer for the optical isolator is required to have heat resistance that temporarily withstands about 260 ° C. for soldering and the like.
  • a so-called Lamipol is used as a polarizer for an optical isolator. Lamipol is manufactured by preparing a film in which aluminum having a thickness of about 10 nm is deposited on a silica film having a thickness of about 1 ⁇ m, laminating the film to form an alternating multilayer film of silica and aluminum, and then cutting it thin.
  • the conventional polarizer has the following problems.
  • Pigments such as iodine and dye used in conventional polarizing plates have low heat resistance.
  • the stretched PVA film as a base material also has a problem that the dimensions change due to wet heat, thereby causing a phase difference and lowering the degree of polarization.
  • the conventional polarizing plate for increasing brightness is stretched by alternately laminating 100 to 200 layers of the two kinds of polyester films, uniform stretching is difficult and productivity is poor. There is also a problem that the light transmittance in the non-stretching direction is low.
  • the Lamipol used in a polarizer for an optical isolator has a problem in that workability and productivity for production are poor, and it is easily broken during handling.
  • a polarizer made of another material has a problem that there is no substitute material because of low heat resistance.
  • the main object of the present invention is to provide a polarizing material having good heat resistance instead of a pigment, a coating material for manufacturing a polarizing film, and a polarizing film.
  • the present inventor can use a specific metal-plated nanowire as a polarizing material, has good heat resistance, and can be oriented on a substrate with high productivity. As a result, the present invention has been completed.
  • this invention relates to the following polarizing material, the coating material for polarizing film manufacture, and a polarizing film.
  • Polarizing material comprising metal-plated nanowires obtained by forming a metal plating layer having a thickness of 1 to 15 nm on the surface of nanowires comprising a dielectric having an average thickness of 20 to 300 nm and an average length of 0.4 ⁇ m or more .
  • the dielectric has a core layer and a coat layer formed on the surface thereof, and the refractive index of the core layer is 1.47 to 2.2, and the refractive index of the coat layer is equal to that of the core layer.
  • Item 2 The polarizing material according to Item 1, wherein the refractive index is nc, and the refractive index is within nc ⁇ 0.4. 4).
  • a paint for producing a polarizing film, comprising the polarizing material according to Item 1. 6).
  • the paint according to Item 5 wherein the paint contains a resin, and the refractive index of the resin is within nd ⁇ 0.4, where nd is the refractive index of the dielectric. 7). 4.
  • a coating material for producing a polarizing film comprising the polarizing material according to item 3 and a resin, wherein a refractive index of the resin is nc ⁇ 0.4, where nc is a refractive index of the core layer. 8).
  • the said coating material is a coating material of said claim
  • a polarizing film obtained by applying the coating material according to the above item 5 on the surface of the base film and then drying it. 10.
  • the coating is coating by a bar coating method using a coating bar, (1) The coating is performed under the condition that the contact length P between the circumferential portion of the coating bar and the substrate film is P ⁇ 1000 ⁇ L (L: average length of metal-plated nanowires). Coating, (2) The coating bar is provided with a groove evenly at least in a region where the coating bar and the base film are in contact, and the width W of the groove is 50 ⁇ ⁇ ⁇ W ⁇ 10000 ⁇ ⁇ . ( ⁇ : average thickness of metal-plated nanowires), Item 10. The polarizing film according to Item 9. 11. Item 10. The polarizing film according to Item 9, which is used as a polarizing plate or a luminance increasing polarizing plate.
  • the relationship between the metal nanowire and the polarizing property will be described first, and then the polarizing material (metal-plated nanowire), the coating material for manufacturing the polarizing film, and the polarizing film of the present invention will be described.
  • the relational light between the metal nanowire and the polarizing property can be divided into two polarized lights (referred to as p-polarized light and s-polarized light in this specification) that vibrate in directions perpendicular to each other in a plane perpendicular to the traveling direction.
  • the polarizing film has a function of transmitting one of the two polarized lights and blocking (absorbing or reflecting) the other polarized light.
  • a rod-shaped metal having a nanometer size in width and length exhibits anisotropy with respect to electromagnetic waves such as light.
  • a rod-shaped metal having a length of 1 ⁇ m or more is sometimes referred to as a metal nanowire, and a rod-shaped metal having a length of less than 1 ⁇ m is sometimes referred to as a metal nanorod.
  • both are collectively referred to as a rod-shaped metal having a length of 0.4 ⁇ m or more. Is called a metal nanowire.
  • the length of the metal nanowire is longer than the wavelength of light and the width is sufficiently narrower than the wavelength of light.
  • polarized light having an electric field vibration plane in the length direction of the metal nanowire is absorbed or reflected by vibrating the free electrons of the metal nanowire.
  • polarized light having an electric field vibration plane in the width direction of the metal nanowire is transmitted because the free electrons of the metal nanowire are less likely to oscillate in resonance with light (exactly speaking, the expression “scatter forward”) is correct. It is simply called “transmitting”.
  • metals absorb or reflect light is that light is electromagnetic waves, and free electrons in the metal vibrate in resonance with the electric field of light, and the light energy changes to kinetic energy. Therefore, in order for the metal to absorb or reflect light, a width of the metal that allows free electrons in the metal to vibrate in a direction perpendicular to the light traveling direction is necessary.
  • the width of the metal when the width of the metal is about 10 nm or less, free electrons can no longer vibrate, and light is not absorbed or reflected, and is transmitted. Conversely, if the width of the metal is equal to or greater than the wavelength of light, it is considered that the metal is efficiently absorbed or reflected. Therefore, in the case of metal nanowires, it is considered that a good polarizing material is obtained if the length is longer than the wavelength of light and the width is about 10 nm or less.
  • FIG. 1 shows the relationship between the vibration direction of the electric field of s-polarized light and p-polarized light, and the length direction, width direction, and thickness direction of the metal nanowire when square columnar metal nanowires are arranged perpendicular to the light traveling direction. It is shown.
  • P-polarized light does not vibrate free electrons of the metal nanowire if the width of the metal nanowire is about 10 nm or less. Therefore, regardless of the length and thickness of the metal nanowire, p-polarized light is transmitted without being absorbed or reflected.
  • S-polarized light vibrates free electrons of the metal nanowire if the length of the metal nanowire is longer than the wavelength of light. At this time, light is absorbed or reflected even if the width is 10 nm or less. Whether light is absorbed or reflected depends on the thickness of the metal nanowire.
  • ⁇ is approximately 4.8 ⁇ 10 ⁇ 9 and the metal conductivity ⁇ (S / m) is silver: 61 ⁇ 10 6 and aluminum: 40 ⁇ 10. 6 , nickel: 15 ⁇ 10 6 and tantalum: 8 ⁇ 10 6 , the skin depths are silver: 2.7 nm, aluminum: 3.5 nm, nickel: 4.1 nm, and tantalum: 5.3 nm, respectively. .
  • the thickness of the metal nanowire is about 5 nm, it is absorbed, and if the thickness is about 10 nm, it is reflected. This is the same even when the shape of the metal nanowire is changed from a quadrangular column to a polygonal column.
  • the depth of the metal skin it can be seen that when the length of the metal nanowire is 400 nm (0.4 ⁇ m) or more and the thickness is 5 nm or less, p-polarized light is transmitted and s-polarized light is absorbed. It can also be seen that when the length is 400 nm (0.4 ⁇ m) or more and the thickness is about 10 nm, p-polarized light is transmitted and s-polarized light is reflected. Therefore, if the metal nanowires of this size are oriented, a polarizing plate and a luminance increasing polarizing plate can be obtained.
  • the metal nanowires are required to be straight.
  • almost all methods for producing metal nanowires with a width of several nanometers and good linearity and good productivity are known. Absent.
  • the thinner the metal nanowires the more bent and agglomerated during handling, and there is a problem in production.
  • a metal plating layer having a thickness of 1 to 15 nm is formed on the surface of the nanowire made of a dielectric having an average thickness of 20 to 300 nm and an average length of 0.4 ⁇ m or more.
  • the metal plating nanowire obtained by this is used as a polarizing material.
  • a dielectric having an average thickness of 20 to 300 nm and an average length of 0.4 ⁇ m or more can be manufactured with good linearity with good productivity. Good metal-plated nanowires can be produced with high productivity.
  • a polarizing plate that transmits light in the thickness direction and absorbs light in the length direction, or transmits light in the thickness direction, It can be used as a polarizing plate for increasing brightness that reflects light in the length direction (including partial reflection), and can be used as a polarizing material.
  • the metal plating layer is a substitute for a conventional pigment (means for expressing polarization), and a polarizing plate or a brightness increasing polarizing plate excellent in heat resistance can be provided.
  • Polarizing material of the present invention comprises a metal plating layer having a thickness of 1 to 15 nm on the surface of a nanowire made of a dielectric material having an average thickness of 20 to 300 nm and an average length of 0.4 ⁇ m or more. It is a metal-plated nanowire obtained by forming.
  • a nanowire made of a dielectric material having an average thickness of 20 to 300 nm and an average length of 0.4 ⁇ m or more is used.
  • the “average” is an average value of thickness and length when 10 nanowires are arbitrarily selected from an electron microscope image.
  • the average thickness of the dielectric is 20 to 300 nm, preferably 50 to 200 nm.
  • the length of one side of the polygonal column is preferably sufficiently shorter than the wavelength of light.
  • the aspect ratio of the dielectric is not limited, but is preferably 10 or more.
  • the length of the dielectric exceeds 20 ⁇ m, the linearity of the dielectric may be easily lost.
  • the aspect ratio is less than 10, the polarization and orientation may be lowered.
  • nanowires made of dielectric nanowires of (meth) acrylic resin, nanowires of silica, etc. are synthesized as nanowires obtained by electrospinning.
  • nanowires, such as an alumina are synthesize
  • Langmuir, 2004, 20 (11), 44784-4786 and Crystal Growth and Design, 2006, 6 (6), 1504-1508 are nanowires obtained by hydrothermal method with a thickness of 30-120 nm Hydroxyapatite or fluoroapatite nanowires with a length of several ⁇ m to 50 ⁇ m (both have a refractive index of about 1.64) have been reported.
  • a method for synthesizing boehmite nanowires (refractive index of about 1.7) is reported.
  • Nanowires made of dielectrics nanowires made of oxides or hydroxides of silicon, aluminum, etc., magnesium, aluminum, calcium, zinc and potassium metal phosphates, sulfates, borates, Nanowires made of silicate or phenyl phosphate are also known.
  • the present invention is not limited to these dielectrics, and any nanowire having a dielectric refractive index (nd) of 1.47 to 2.2 can be suitably used.
  • the refractive index (nd) is more preferably 1.47 to 1.8.
  • (meth) acrylic resins such as poly (meth) methyl acrylate, calcium carbonate, fluoroapatite, potassium titanate, magnesium sulfate, and the like can be particularly preferably used.
  • the dielectric When the dielectric is made of a crystal, it usually has a polygonal column shape or a twisted shape. Therefore, if necessary, the surface of the dielectric may be coated with the same or different dielectric having the same refractive index, and may be used after forming a cylindrical or quasi-cylindrical nanowire with a curved surface. .
  • the nanowire after coating has an average thickness of 20 to 300 nm, an average length of 0.4 ⁇ m or more, and preferably an aspect ratio of 10 or more.
  • the dielectric has a core layer and a coat layer formed on the surface thereof, the core layer has a refractive index of 1.47 to 2.2, and the coat layer has a refractive index of the core layer.
  • the refractive index is nc, and is preferably within nc ⁇ 0.4.
  • the refractive index (nc) of the core layer is more preferably 1.47 to 1.8
  • the refractive index of the coat layer is more preferably within nc ⁇ 0.2.
  • Examples of the coating layer include, but are not limited to, those obtained by depositing the same compound as the core layer in the same precipitation reaction with a reduced time so as not to take crystallization time.
  • a core layer for example, (meth) acrylic resin, silicon resin and the like are preferable.
  • a core layer may be formed by adding a crosslinking agent (for example, a titanium-based crosslinking agent or a zirconium-based crosslinking agent) to (meth) acrylic resin, silicon resin, or the like.
  • a crosslinking agent for example, a titanium-based crosslinking agent or a zirconium-based crosslinking agent
  • J.Am.Chem.Soc., 2005 It is possible to form a nanowire with a curved surface by forming a coating layer with an amorphous resin such as (meth) acrylic resin or silicon resin on the surface of the core layer. , 127 (46), 16040-16041, Crystal Growth and Design, 2006, 611 (11), 2422-2426, J.Phys.Chem.B, 2006, 110 (2), 807-811 etc. It is described in. In addition, it is possible to form a coating layer using silica in J. Phys. Chem. B, 2005, 109 (1), 151-154 and J.Phys.Chem.B, 2006, 110 (2). Pp. 807-811.
  • an amorphous resin such as (meth) acrylic resin or silicon resin
  • the metal plating layer formed on the surface of the nanowire made of dielectric is preferably formed by electroless plating.
  • Metals to be electrolessly plated are: 1) those that are likely to precipitate due to reactions in the liquid layer, 2) those that are difficult to corrode, and 3) those that are difficult to corrode by forming a passive layer or a protective layer equivalent thereto on the surface. Preferably there is.
  • the metal used for the metal plating layer is preferably at least one of nickel, chromium, zinc, tantalum, niobium, silver, iron and aluminum.
  • at least one of nickel, chromium, zinc, tantalum, niobium, and aluminum is more preferable from the viewpoint of ensuring the non-coloring property of the metal plating layer.
  • aluminum plating it is reported in Chem. ⁇ Mater. 2006, 18, 1634 that cyclopentadienylaluminum is precipitated in mesitylene, and aluminum plating may be performed in this reaction solution.
  • the thickness of the metal plating layer may be 1 to 15 nm, preferably 1 to 10 nm.
  • the thickness of the passive film is preferably thinner than the thickness of the metal plating layer.
  • the total thickness of the metal plating layer and the passive film is preferably not more than twice the thickness of the metal plating layer.
  • it can form by heating metal plating nanowire in a solvent, or surface-treating with an oxidizing agent.
  • the surface of the metal-plated nanowire may be further coated with a dielectric film of 50 nm or less.
  • the dielectric used for the coating preferably has a refractive index within ⁇ 0.4 with respect to nd, more preferably within nd ⁇ 0.2.
  • the coating material for example, a copolymer obtained by hydrolyzing alkoxysilane and alkoxyzirconium with acid or alkali, and a copolymer obtained by hydrolyzing alkoxysilane and alkoxyzirconium with acid or alkali. Examples thereof include a copolymer of alkoxysilane and alkoxyzirconium obtained.
  • the refractive index of the polarizing material can be adjusted and the orientation of the polarizing material can be further improved.
  • the polarizing material of the present invention can be used as a polarizer for a polarizing plate, a luminance increasing polarizing plate, or an optical isolator by dispersing and orienting it in a resin having a refractive index (nr) within nd ⁇ 0.4. it can.
  • the refractive index (nr) is more preferably within nd ⁇ 0.2.
  • the content of the polarizing material when dispersed in the resin is preferably about 10 to 70% by weight, more preferably about 30% to 50% by weight, with the total amount of the resin and the polarizing material being 100% by weight. Moreover, in order to orient efficiently after making it disperse
  • optical behavior of the polarizing material of the present invention is as follows.
  • S-polarized light is absorbed or reflected by vibrations of free electrons in the metal plating layer and does not transmit if the length of the polarizing material is equal to or greater than the wavelength of light.
  • the polarizing material (metal plated nanowire) of the present invention is dispersed and oriented in the resin, and the polarizing material is composed of a dielectric layer (one dielectric layer) and a metal plated layer.
  • Direction wave direction normal direction (unit vector is represented by s) is confirmed with reference to FIG.
  • light proceeds in the order of resin layer (1) ⁇ boundary a ⁇ metal plating layer (2) ⁇ boundary b ⁇ dielectric layer (3), and the magnetic field in the resin layer (1) is changed to H 1 .
  • the velocity is v 1
  • the refractive index is n 1
  • the wavefront normal unit vector is s 1
  • the magnetic field in the metal plating layer (2) is H 2
  • the speed of light is v 2
  • the refractive index is n 2
  • the wavefront normal is S 2
  • the magnetic field in the dielectric layer (3) is H 3
  • the speed of light is v 3
  • the refractive index is n 3
  • the wavefront normal unit vector is s 3
  • the time is t
  • the boundary a Assume that the position vector is r a and the position vector of the boundary b is r b .
  • the light incident on the metal-plated nanowire does not change the light intensity or the light traveling direction before and after the metal plating layer (2).
  • the light that exits in the order of the dielectric layer (3) ⁇ the metal plating layer (2) ⁇ the resin layer (1) does not change in intensity or traveling direction. Accordingly, the p-polarized light is transmitted through the metal-plated nanowire while maintaining the traveling direction. This is based on the fact that forward scattering occurs because no reflection occurs.
  • the thickness of the film can be regarded as constant. If the refractive index of the resin layer and that of the dielectric layer are the same, the amplitude and traveling direction of the light will not change, and p-polarized light will be transmitted. That is, s-polarized light is absorbed or reflected, and p-polarized light is transmitted.
  • w is preferably 100 nm or less.
  • the metal plating layer is thin and the side surface of the nanowire faces in all directions, the thickness of the nanowire is 200 nm or less, the average value of w is sufficiently shorter than 100 nm, and the degree of polarization required as a polarizing film is achieved. I think that.
  • the coating material for manufacturing a polarizing film and the polarizing film includes a coating material for manufacturing a polarizing film containing the polarizing material.
  • the coating material for producing a polarizing film contains the above polarizing material and contains at least one of a resin binder, a solvent and the like for use as a coating material.
  • Japanese Patent Application Laid-Open No. 2008-279434 discloses an alignment coating method for metal nanowires.
  • a coating material is applied using this coating method, and a polarizing material is applied. It is preferable to orient on the substrate.
  • a coating material containing a polarizing material is applied with a coating bar, and in order to orient the polarizing material, the Brownian motion of the polarizing material during coating needs to be gentle. It is. Here, the Brownian motion is gentler as the polarizing material is heavier and longer.
  • the polarizing material of the present invention is small in size and specific gravity. Therefore, for efficient orientation, it is preferable to use a paint having a viscosity of at least several hundreds mPa ⁇ s in which a thickening resin is dissolved for the purpose of suppressing Brownian motion.
  • the resin for thickening becomes a resin layer surrounding the polarizing material in the coating film after the coating film is dried.
  • the refractive index of this resin layer is preferably within ⁇ 0.4, and within ⁇ 0.2, as described above, with respect to the refractive index nd of the nanowire. Is more preferable.
  • the refractive index of the resin layer is, for example, 1.47 by using a (meth) acrylic resin or an acrylamide resin as a main component and using a crosslinking agent (for example, a titanium-based crosslinking agent, a zirconium-based crosslinking agent, etc.) as necessary. It can be adjusted to ⁇ 2.2.
  • a crosslinking agent for example, a titanium-based crosslinking agent, a zirconium-based crosslinking agent, etc.
  • a viscosity of 300 mPa ⁇ s or more is obtained by adding a (meth) acrylic resin or an acrylamide resin to a solvent having a boiling point of 150 ° C. or less and, if necessary, a crosslinking agent (for example, a titanium-based crosslinking agent, a zirconium-based crosslinking agent).
  • a crosslinking agent for example, a titanium-based crosslinking agent, a zirconium-based crosslinking agent.
  • a polarizing material is dispersed in the obtained resin solution to obtain a paint.
  • the coating is performed under the condition that the contact length P between the circumferential portion of the coating bar and the substrate film is P ⁇ 1000 ⁇ L (L: average length of metal-plated nanowires).
  • the coating bar is provided with a groove evenly at least in a region where the coating bar and the base film are in contact, and the width W of the groove is 50 ⁇ ⁇ ⁇ W ⁇ 10000 ⁇ ⁇ . ( ⁇ : average thickness of metal-plated nanowires) is preferable.
  • the groove width W needs to be sufficiently wider than the average thickness of the metal-plated nanowires, but if the groove width is too wide or the contact length P is short, the orientation becomes insufficient.
  • a wire having a certain diameter is tightly wound around the surface of the coating bar (so-called “wire bar”), or on the surface of the coating bar itself.
  • a groove in which grooves having a certain width and depth are provided at a certain pitch is used.
  • the clearance gap between adjacent wires turns into a groove
  • the groove is set so that the groove width W is 50 ⁇ ⁇ ⁇ W ⁇ 10000 ⁇ ⁇ ( ⁇ : average thickness of metal-plated nanowires). If 50 ⁇ ⁇ > W, the average thickness ⁇ ⁇ 50 of the metal-plated nanowires becomes larger than the width W of the groove, and the short axis of the metal-plated nanowires does not enter the groove, so that it cannot be oriented. Further, when W> 10000 ⁇ ⁇ , the short axis of the metal-plated nanowire is difficult to be oriented. When the width W of the groove satisfies the above condition, a shear flow occurs in the metal plated nanowire in each groove, and the metal plated nanowire is oriented in the coating direction.
  • the depth of the groove is not particularly limited as long as it is larger than the average thickness ⁇ of the metal-plated nanowire.
  • the contact length P between the circumferential portion of the coating bar and the base film is set so as to satisfy the condition of P ⁇ 1000 ⁇ L (L: average length of metal-plated nanowires). If the contact length P does not satisfy the above conditions, a sufficient shear flow does not occur, and it is difficult to orient the metal-plated nanowires with an orientation ratio of 80% or more.
  • the contact length P is set so as to satisfy the above condition by adjusting the holding angle ⁇ according to the diameter R of the coating bar to be used. That is, each adjustment may be made so as to satisfy ⁇ R ⁇ ⁇ / 360 ⁇ 150 ⁇ L.
  • the diameter R of the coating bar is preferably 15 to 200 mm. If the diameter of the coating bar is made thinner than 15 mm, the adhesion between the coating bar and the substrate film tends to be poor due to the influence of the bending elasticity of the substrate. On the other hand, if it is 200 mm or more, the coating bar becomes heavy, and a load is applied to the motor of the coating machine.
  • the holding angle ⁇ is not particularly limited as long as ⁇ R ⁇ ⁇ / 360 ⁇ 150 ⁇ L can be satisfied, and may be appropriately determined according to a coating apparatus or the like.
  • the thickness of the dry coating film is not limited, but is preferably about 0.1 ⁇ m to 10 ⁇ m in order to exhibit desirable polarization characteristics.
  • the aligned polarizing material is preferably such that the gap between adjacent polarizing materials is less than the wavelength of light.
  • the solvent used for the paint preferably has a boiling point lower than 150 ° C., aliphatic alcohol, aliphatic ether, aliphatic ketone, fatty acid ester, aliphatic halide, aromatic alcohol, aromatic ether, aromatic ketone, Of the aromatic esters and aromatic halides, those having a boiling point of 150 ° C. or lower are preferred.
  • the substrate film to which the paint is applied is not particularly limited as long as it can exhibit the polarization characteristics of the polarizing material of the present invention, and examples thereof include glass and resin films. Moreover, in order to improve orientation, you may extend
  • the film used as the base material has high visible light permeability and is preferably a water and heat resistant film.
  • Polyester film such as polyethylene terephthalate, cellulose ester film such as unsaponified cellulose acetate, cyclic polyolefin resin film, polycarbonate resin film
  • Polysulfone resin films, polyethersulfone resin films, and the like are preferable.
  • a polyester film using a resin adhesive a film such as a cellulose ester film, a cyclic polyolefin resin film, a polycarbonate resin film, a polysulfone resin film, or a polyether sulfone resin film may be bonded and protected.
  • a gas barrier film by laminating
  • a dielectric having an average thickness of 20 to 300 nm and an average length of 0.4 ⁇ m or more can be produced with good linearity with good productivity.
  • a metal-plated nanowire with good properties can be produced with good productivity.
  • a metal plating layer having a thickness of 1 to 15 nm a polarizing plate that transmits light in the thickness direction and absorbs light in the length direction, or transmits light in the thickness direction, It can be used as a polarizing plate for increasing brightness that reflects light in the length direction (including partial reflection), and can be used as a polarizing material.
  • the metal plating layer is a substitute for a conventional pigment (means for expressing polarization), and a polarizing plate or a brightness increasing polarizing plate excellent in heat resistance can be provided.
  • Example 1 A metal-plated nanowire in which a metal plating layer is formed on the surface of a cylindrical polymethyl methacrylate (PMMA) nanowire having an average thickness of 100 nm and an average length of 2 ⁇ m is placed in an acrylic resin (refractive index 1.49) coating film. It was dispersed and oriented (see FIG. 3). The refractive index of the PMMA nanowire is 1.49. The coating film was dried to obtain a polarizing film. Hereinafter, it is abbreviated as “coating film”.
  • PMMA polymethyl methacrylate
  • Table 1 shows the results of calculating the polarization performance of the coating film using commercially available finite difference time domain method software.
  • the calculation when a large amount of nickel-plated nanowires overlaps in the coating film is enormous, so as shown in FIG. 3, nanowires with an average thickness of 100 nm are 200 nm
  • Examples 2 to 4 and Comparative Examples 1 to 2 A metal-plated nanowire in which a chromium plating layer is formed as a metal plating layer on the surface of a columnar fluoroapatite (refractive index: 1.635) nanowire having an average thickness of 100 nm and an average length of 20 ⁇ m is coated with an acrylic resin (refractive index). 1.49, thickness 0.2 ⁇ m). The thickness of the chromium plating layer was changed for each example and comparative example. Table 2 shows the results of evaluating the polarization performance of the coating film using a polarization analyzer (custom product) manufactured by Sigma Koki Co., Ltd.
  • the thickness of the metal plating layer is preferably set to 2 to 15 nm.
  • Examples 5 to 6 and Comparative Examples 3 to 4 A metal-plated nanowire in which an aluminum plating layer having a thickness of 7.5 ⁇ m is formed on a cylindrical PMMA (refractive index 1.49) nanowire having an average length of 20 ⁇ m with a changed average thickness is coated with an acrylic resin coating film (refractive index 1). 49) was dispersed and oriented.
  • Table 3 shows the results of evaluating the polarization performance of the coating film using the above ellipsometer.
  • the thickness of the coating film was basically 0.2 ⁇ m, 0.3 ⁇ m when the average nanowire thickness was 200 nm, and 0.35 ⁇ m when 300 nm.
  • Examples 7 to 8 and Comparative Example 5 A metal-plated nanowire having a 10 nm-thick chromium plating layer formed on the surface of a columnar fluoroapatite (refractive index: 1.635) nanowire having an average thickness of 100 nm and varying the average length is coated with an acrylic resin coating (refractive In a ratio of 1.49 and a thickness of 0.2 ⁇ m).
  • Table 4 shows the results of evaluating the polarization performance of the coating film using the above ellipsometer.
  • the transmittance is higher than the reflectance of s-polarized light, and polarization separation cannot be obtained sufficiently.
  • the average length of the nanowire is 2 ⁇ m or more, the polarization separation function is exhibited. However, from the viewpoint of easy handling of nanowires, 20 ⁇ m or less is preferable.
  • Examples 9 to 11 and Comparative Example 6 Metal plated nanowires in which an aluminum plating layer having a thickness of 7.5 ⁇ m was formed on cylindrical nanowires having an average thickness of 100 nm and an average length of 20 ⁇ m were dispersed and oriented in a resin coating film.
  • Table 5 shows the results of evaluating the polarization performance of the coating film using the above-described ellipsometer.
  • Each Example and Comparative Example have different refractive index differences, and combinations (nanowire / resin) are as follows.
  • Example 9 Magnesium sulfate (refractive index 1.53) / acrylic (refractive index 1.49)
  • Example 10 Potassium titanate (refractive index 2.2) / episulfide system (refractive index 1.8)
  • Example 11 Potassium titanate (refractive index 2.2) coated with 10 nm thick episulfide system (refractive index 1.8) / thiourethane system (refractive index 1.65)
  • Comparative Example 6 Potassium titanate (refractive index 2.2) / acrylic (refractive index 1.49)
  • the polarization separation function is sufficiently exerted even if the refractive index difference between the nanowire and the coating film is somewhat large.
  • the refractive index difference is too large as in the comparative example, the transmittance of s-polarized light increases and the luminance is increased. The performance when the rising polarizing plate is used is lowered.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Optics & Photonics (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

L'invention concerne une matière polarisante qui présente une bonne résistance à la chaleur et peut remplacer un colorant; une matière de revêtement destinée à la production d'un film polarisant et qui contient cette matière polarisante; et un film polarisant. L'invention concerne spécifiquement: une matière polarisante, constituée de nanofils à placage métallique qui sont obtenus par la formation de couches de placage métallique d'une épaisseur de 1-15 nm sur les surfaces des nanofils, lesquels sont constitués de corps diélectriques présentant un diamètre moyen de 20-300 nm et une longueur moyenne supérieure ou égale à 0,4 μm; une matière de revêtement pour la production d'un film polarisant et qui contient cette matière polarisante; et un film polarisant.
PCT/JP2011/062100 2010-05-28 2011-05-26 Matière polarisante, matière de revêtement contenant celle-ci pour la production d'un film polarisant et film polarisant WO2011149020A1 (fr)

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KR1020127001852A KR101176400B1 (ko) 2010-05-28 2011-05-26 편광성 재료 및 그것을 포함하는 편광막 제조용 도료 그리고 편광막

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KR101176400B1 (ko) 2012-08-23
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