WO2016167060A1 - Polarizer, polarizing plate, and method for producing polarizer - Google Patents
Polarizer, polarizing plate, and method for producing polarizer Download PDFInfo
- Publication number
- WO2016167060A1 WO2016167060A1 PCT/JP2016/057495 JP2016057495W WO2016167060A1 WO 2016167060 A1 WO2016167060 A1 WO 2016167060A1 JP 2016057495 W JP2016057495 W JP 2016057495W WO 2016167060 A1 WO2016167060 A1 WO 2016167060A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polarizer
- boric acid
- resin film
- concentration
- polarizing plate
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Definitions
- the present invention relates to a polarizer, a polarizing plate, and a method for producing a polarizer.
- Polarizers are used in image display devices (for example, liquid crystal display devices) such as mobile phones and notebook personal computers.
- image display devices for example, liquid crystal display devices
- a polarizer for a meter display unit of an automobile, a smart watch, and the like, and it is desired to make the shape of the polarizer other than a rectangle and to form a through hole in the polarizer.
- a problem of durability is likely to occur.
- a polarizing plate formed by bonding a pair of polarizer protective films to both main surfaces of the polarizer and melting the outer peripheral end surfaces and then solidifying them.
- Patent Document 1 further improvement in durability is demanded.
- the present invention has been made to solve the above-mentioned problems, and a main object thereof is to provide a polarizer having excellent durability.
- the polarizer of this invention is comprised from the resin film containing a boric acid, and the low density
- the said low concentration part has a density
- the said low concentration part is formed over the position of 50 micrometers or more in the surface direction inward from the end surface of the said resin film.
- the said low concentration part is formed in the absorption-axis direction edge part.
- a through hole is formed, and the low-concentration portion is formed at the peripheral edge of the through hole.
- the said low concentration part is formed in the outer edge part.
- the said outer edge contains the site
- a polarizing plate is provided. This polarizing plate has the said polarizer and the protective film arrange
- a method for producing a polarizer is provided. This manufacturing method includes a step of bringing a treatment liquid into contact with a resin film containing boric acid to form a low concentration portion having a lower concentration of boric acid than other portions at the end of the resin film.
- the treatment liquid includes water.
- the treatment liquid is a solution in which a compound containing a substance that forms a counter ion of iodine is dissolved in a solvent.
- the compound comprises potassium iodide and / or sodium chloride.
- the liquid temperature of the said processing liquid is 50 degreeC or more.
- it includes a step of forming the resin film containing boric acid into a desired shape by cutting and / or punching.
- the cutting and / or punching process is performed by irradiating a laser beam.
- the laser is a CO 2 laser.
- a polarizer having extremely excellent durability can be obtained by forming a low concentration portion having a lower concentration of boric acid than other portions at the end.
- FIG. 1 is a plan view of a polarizing plate according to one embodiment of the present invention. It is a partial expanded sectional view of the polarizing plate shown in FIG. It is an expanded sectional view of the edge part of the polarizing plate by one Embodiment of this invention.
- (A) is a photograph which shows the external appearance of the polarizing plate of the comparative example 3 after a heat cycle test
- (b) is a photograph which shows the external appearance of the polarizing plate of Example 3 after a heat cycle test.
- A) is the observation photograph by the optical microscope after the heat resistance test of the edge part of the polarizing plate of Example 1
- (b) is a graph which shows the analysis result by the micro Raman spectroscopic analysis.
- (A) is a graph which shows the boric acid concentration distribution in the surface direction of the edge part of the polarizer of Example 1
- (b) shows the boric acid concentration distribution in the surface direction of the edge part of the polarizer of Comparative Example 1. It is a graph.
- (A) is a graph which shows the potassium concentration distribution in the surface direction of the edge part of the polarizer of Example 4,
- (b) shows the potassium concentration distribution in the surface direction of the edge part of the polarizer of Comparative Example 1.
- It is a graph and (c) is a graph which shows the density
- FIG. (A) is the observation photograph by the optical microscope of the edge part of the polarizing plate of Example 1
- (b) is the observation photograph by the optical microscope of the edge part of the polarizing plate of the comparative example 1.
- FIG. 1 is a plan view of a polarizing plate according to one embodiment of the present invention
- FIG. 2 is a partially enlarged sectional view of the polarizing plate shown in FIG.
- the polarizing plate 100 is suitably used for an automobile meter panel.
- the polarizing plate 100 is configured by connecting a first display unit 50 and a second display unit 60, and through holes 51 and 61 for fixing various meter needles are provided near the center of each display unit. Each is formed.
- the diameter of the through hole is, for example, 0.5 mm to 100 mm.
- the outer edges of the display units 50 and 60 are formed in an arc shape along the rotation direction of the meter needle.
- a polarizer is used in a state where a protective film is laminated (made as a polarizing plate).
- the polarizing plate 100 in the illustrated example includes a polarizer 10 and a pair of protective films 21 and 22 disposed on both main surfaces of the polarizer 10.
- the protective film is disposed on both main surfaces of the polarizer, but the protective film may be disposed only on one surface.
- the polarizer is composed of a resin film. Any appropriate resin can be used as the resin for forming the resin film.
- polyvinyl alcohol resin (hereinafter referred to as “PVA resin”) is used.
- PVA resin include polyvinyl alcohol and ethylene-vinyl alcohol copolymer.
- Polyvinyl alcohol is obtained by saponifying polyvinyl acetate.
- the ethylene-vinyl alcohol copolymer can be obtained by saponifying an ethylene-vinyl acetate copolymer.
- the degree of saponification of the PVA-based resin is usually 85 to 100 mol%, preferably 95.0 mol% or more, more preferably 99.0 mol% or more, and particularly preferably 99.93 mol% or more. .
- the degree of saponification can be determined according to JIS K 6726-1994. By using a PVA-based resin having such a saponification degree, a polarizer having excellent durability can be obtained.
- the average degree of polymerization of the PVA resin can be appropriately selected according to the purpose.
- the average degree of polymerization is usually 1000 to 10000, preferably 1200 to 6000, more preferably 2000 to 5000.
- the average degree of polymerization can be determined according to JIS K 6726-1994.
- the polarizer (resin film) 10 contains boric acid, and its end portions (specifically, the outer edge portion 101 and the peripheral portions 51a and 61a of the through holes 51 and 61) have other concentrations of boric acid in other parts. A lower concentration portion is formed. The durability can be improved by forming the low concentration portion. Specifically, the generation of cracks can be suppressed.
- a polarizer has a contraction force larger than that of a protective film, and a stress may be generated at the interface between the polarizer and the protective film due to a change in temperature and humidity, thereby generating a crack.
- the low-concentration part can be less rigid than the other parts by releasing the cross-linking structure with boric acid.
- the low concentration portion As a result, in the low concentration portion, the stress due to the polarizer contraction is relaxed, and the generation of cracks can be suppressed. Therefore, the formation of cracks can be effectively suppressed by forming the low concentration portion in a portion where stress tends to concentrate, such as a peripheral edge of a through hole to be described later or a V-shaped portion. Moreover, according to such a form, there is very little influence which it has on external appearance and bonding with another member.
- the low concentration portion has, for example, a concentration gradient in which the boric acid-containing concentration decreases as going outward in the plane direction.
- concentration gradient By having the concentration gradient, it is possible to suppress a rapid decrease in the polarization performance at the end while suppressing the occurrence of the cracks.
- the boric acid content in the other part is, for example, 20% by weight to 30% by weight.
- the low concentration portion is preferably formed from the end face of the polarizer (resin film) to the position of 50 ⁇ m or more inward in the plane direction, more preferably from the end face of the polarizer to a position of 80 ⁇ m or more. If it is such a range, the effect of the said durability improvement can fully be acquired.
- the low concentration portion is preferably formed from the end face of the polarizer to the inner side in the plane direction at a position of 1000 ⁇ m or less, more preferably at a position of 500 ⁇ m or less.
- the position of the through hole can be appropriately set according to the use of the polarizer, for example.
- the crack is likely to be generated starting from the peripheral edge of the through hole, and the tendency of the crack becomes more prominent as the position of the through hole is away from the outer edge of the polarizer.
- the effect of improving the durability due to the formation of the low concentration portion can be obtained remarkably.
- the low concentration portion is preferably formed at least at the boundary portions 41 and 42 of each display portion. Specifically, it is preferable that the low concentration portion is formed at a site where the outer edge has a V shape (including a round shape) convex inward in the surface direction. This is because the portion where the outer edge has a V-shape projecting inwardly in the surface direction is likely to be the starting point of a crack, similar to the periphery of the through hole.
- the low concentration portion is preferably formed at the end of the polarizer in the absorption axis direction.
- the cracks tend to occur along the absorption axis direction of the polarizer, and the occurrence of cracks can be effectively suppressed by forming the low concentration portion at the end portion in the absorption axis direction.
- the polarizer typically contains a dichroic substance.
- the dichroic substance include iodine and organic dyes. These may be used alone or in combination of two or more. Preferably, iodine is used.
- the content concentration of the components contained in the polarizer including the dichroic material can be lower in the low concentration part than in the other parts.
- components contained in the polarizer other than boric acid and dichroic materials, for example, solutions used for various treatments for obtaining a polarizer described later (specifically, iodides such as potassium iodide are dissolved) Components contained in the solution).
- the polarizer (resin film) 10 includes a substance that forms a counter ion of iodine, and the end portions thereof (specifically, the peripheral edge portions 51 a and 61 a of the outer edge portion 101 and the through holes 51 and 61). ) Is formed with a high-concentration part in which the concentration of the substance is higher than other parts.
- the substance that forms the counter ion of iodine include metals that can form halides such as potassium, sodium, lithium, zinc, aluminum, lead, copper, barium, calcium, tin, and titanium. Of these, potassium and sodium are preferably used.
- the substance that forms the counter ion of iodine can be in any appropriate state. Specifically, it may be in an ionic state, a bond with another substance, or a mixture of these states. Examples of other substances include iodine ion (I ⁇ ) and iodine complex (I 3 ⁇ ).
- the high-concentration portion has a concentration gradient in which the content concentration of the substance that forms the counter ion of iodine increases toward the outside in the plane direction, for example.
- the content of the substance that forms the counter ion of iodine in the other part is, for example, 0.3 wt% to 5 wt%.
- part may be mainly introduce
- the high concentration portion is preferably formed from the end face of the polarizer (resin film) to the position of 100 ⁇ m or more inward in the plane direction, more preferably from the end face of the polarizer to a position of 500 ⁇ m or more.
- the high concentration portion is preferably formed over a position of 2000 ⁇ m or less from the end face of the polarizer inward in the plane direction, and more preferably over a position of 1000 ⁇ m or less.
- the high concentration region includes the low concentration region of boric acid.
- the high concentration region is formed corresponding to the boric acid low concentration region. More preferably, the high concentration portion is formed in a region including the entire region of the low concentration portion of boric acid.
- the low concentration part of boric acid is formed from the end face of the resin film to a predetermined position inward in the plane direction, the high concentration part extends from the low concentration part of boric acid inward in the plane direction by 100 ⁇ m or more. Preferably it is formed. According to such a form, heat resistance can be improved reliably.
- the rigidity can be lower than other parts, so that the occurrence of cracks is suppressed, while the heat resistance is reduced. obtain.
- One of the causes is that the content of iodine complexes (eg, I 3 ⁇ , I 5 ⁇ ) is low and the content of iodine ions (eg, I ⁇ , I 3 ⁇ ) is low in the low concentration part of boric acid. It can be expensive.
- the iodine complex can be oriented in the resin film, while iodine ions can be present in the resin film in an unstable state.
- iodine ions are stabilized by forming the high-concentration part and introducing counter ions, thereby contributing to improvement of the heat resistance of the resin film (for example, suppression of coloring of the resin film due to suppression of polyene formation).
- the content of iodine (I 2 ) is high in the low concentration part of boric acid, and iodine may be present in the resin film in an unstable state.
- the polarizer preferably exhibits absorption dichroism in the wavelength range of 380 nm to 780 nm.
- the single transmittance (Ts) of the polarizer is preferably 40% or more, more preferably 41% or more, still more preferably 42% or more, and particularly preferably 43% or more.
- the theoretical upper limit of the single transmittance is 50%, and the practical upper limit is 46%.
- the single transmittance (Ts) is a Y value measured with a 2 degree visual field (C light source) of JIS Z8701 and corrected for visibility, for example, using a spectrophotometer (manufactured by JASCO, V7100). Can be measured.
- the polarization degree of the polarizer is preferably 99.8% or more, more preferably 99.9% or more, and further preferably 99.95% or more.
- the thickness of the polarizer can be set to any appropriate value.
- the thickness is typically 1 ⁇ m to 80 ⁇ m, preferably 3 ⁇ m to 40 ⁇ m.
- Examples of the material for forming the protective film include cellulose resins such as diacetyl cellulose and triacetyl cellulose (TAC), (meth) acrylic resins, cycloolefin resins, olefin resins such as polypropylene, and polyethylene terephthalate resins. Ester resins, polyamide resins, polycarbonate resins, copolymer resins thereof, and the like.
- the “(meth) acrylic resin” refers to an acrylic resin and / or a methacrylic resin.
- the thickness of the protective film is preferably 10 ⁇ m to 200 ⁇ m.
- a surface treatment layer may be formed on one side of the protective film (side where the polarizer is not disposed). Specifically, a hard coat treatment, an antireflection treatment, or treatment for diffusion or antiglare may be performed.
- the same structure may be sufficient as the structure (formation material, thickness, etc.) of a pair of said protective film, and a different structure may be sufficient as it.
- the protective film is typically laminated on the polarizer surface via an adhesive layer.
- Any appropriate adhesive is used as the adhesive.
- a water-based adhesive, a solvent-based adhesive, an active energy ray curable adhesive, or the like is used as the water-based adhesive.
- an adhesive containing a PVA-based resin is preferably used as the water-based adhesive.
- the polarizer (polarizing plate) of the present invention is not limited to the configuration of the illustrated example, and can be changed as appropriate.
- the shape of the polarizer (polarizing plate), the presence / absence of the through hole, the shape and size of the through hole, and the number and formation positions of the through holes can be changed as appropriate.
- the low concentration portion is preferably formed by bringing a treatment liquid into contact with a resin film containing boric acid. According to such a form, a low concentration part can be easily formed in a desired part. Specifically, boric acid can be eluted into the treatment liquid to form the low concentration portion satisfactorily. Any appropriate method can be adopted as a method for contacting the treatment liquid. Specifically, a method of immersing the resin film in the treatment liquid, a method of applying the treatment liquid to the resin film, a method of spraying the treatment liquid on the resin film, and the like can be given. Preferably, a method of immersing a resin film in the treatment liquid is employed.
- the treatment liquid examples include water, alcohols such as methanol and ethanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, ethylenediamine, and diethylenetriamine. Amines are used. These may be used alone or in combination of two or more. Among these, water is preferably used.
- the treatment liquid may contain a substance that forms a counter ion of iodine.
- the treatment liquid is typically a solution in which a compound containing a substance that forms a counter ion of iodine is dissolved in the solvent.
- Examples of the compound containing a substance that forms the counter ion of iodine include halides such as potassium, sodium, lithium, zinc, aluminum, lead, copper, barium, calcium, tin, titanium (preferably iodide, chloride). Product). Among these, potassium iodide and sodium chloride are preferably used.
- the compounding amount of such a compound is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the solvent.
- the treatment liquid is a basic solution.
- the treatment liquid can be obtained by blending a basic compound with the solvent.
- the basic compound include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, and inorganic alkali metal salts such as sodium carbonate. And organic alkali metal salts such as sodium acetate. These may be used alone or in combination of two or more.
- the concentration of the basic solution is, for example, 1N to 10N.
- the treatment liquid is an acidic solution.
- the treatment liquid can be obtained by blending an acidic compound with the solvent.
- the acidic compound include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrogen fluoride, and organic acids such as formic acid, oxalic acid, citric acid, acetic acid, and benzoic acid. These may be used alone or in combination of two or more.
- the concentration of the acidic solution is, for example, 1N to 10N.
- the treatment liquid may contain an additive.
- the liquid temperature (at the time of contact) of the treatment liquid is preferably 50 ° C. or higher, more preferably 60 ° C. or higher. This is because the low concentration portion can be formed satisfactorily.
- the liquid temperature (at the time of contact) of the treatment liquid is preferably 90 ° C. or lower.
- the treatment liquid in a state where the treatment liquid is in contact with the resin film, the treatment liquid is heated so that the treatment liquid reaches a predetermined temperature (so that the treatment liquid is maintained at the predetermined temperature). .
- the immersion time is, for example, 3 minutes to 20 minutes.
- the treatment liquid When the treatment liquid is brought into contact with the resin film, the treatment liquid may be subjected to ultrasonic treatment. Specifically, the resin film is immersed in an ultrasonic bath. According to such a form, a low concentration part can be formed efficiently. Sonication can be performed under any suitable conditions.
- the output is 40 W to 1000 W, for example.
- the frequency is, for example, 15 kHz to 100 kHz.
- the resin film When the treatment liquid is brought into contact, the resin film is subjected to various treatments such as swelling treatment, stretching treatment, dyeing treatment with the dichroic substance, crosslinking treatment, washing treatment, and drying treatment, and can be used as a polarizer. It is preferable that The resin film containing boric acid can be obtained, for example, by bringing a boric acid solution (for example, boric acid aqueous solution) into contact with the resin film during the stretching treatment and the crosslinking treatment.
- the resin film may be a resin layer formed on a substrate.
- the stretching direction in the stretching process may correspond to the absorption axis direction of the obtained polarizer. From the viewpoint of obtaining excellent polarization characteristics, the resin film is usually uniaxially stretched 3 to 7 times.
- a resin film containing boric acid is covered with a coating film, and a treatment solution is selectively brought into contact with a desired site.
- a film that can be used as it is as the protective film after contact with the treatment liquid is preferably used.
- stacking a protective film on each main surface of the resin film (polarizer) containing a boric acid is immersed in a process liquid, and a low concentration part is formed. According to such a method, the low concentration portion and / or the high concentration portion having the concentration gradient can be formed satisfactorily.
- the end face 10 a of the polarizer 10 can be positioned inward in the plane direction with respect to the end faces 21 a and 22 a of the protective films 21 and 22. Can be formed. The durability can be further improved by forming the polarizer gap.
- molding into a desired shape is typically performed by cutting and / or punching.
- the cutting and / or punching process is preferably performed before the low-concentration portion is formed.
- the cutting and / or punching may be performed on the polarizer (resin film) alone, but is preferably performed on the laminate of the polarizer and the protective film.
- the laminate of the polarizer and the protective film is formed into a desired shape by cutting and / or punching, and then the low concentration portion is formed.
- any appropriate method can be adopted as the cutting (punching) method.
- Examples thereof include a method using a cutting blade (punching die) such as a Thomson blade and a picnal blade, and a method of irradiating a laser beam.
- a cutting blade punching die
- a method of irradiating a laser beam Preferably, cutting by laser light irradiation is employed. According to the laser light irradiation, a smooth cut surface can be obtained, and the occurrence of crack starting points (initial cracks) can be suppressed.
- any appropriate laser can be adopted as the laser.
- a laser capable of emitting light having a wavelength in the range of 150 nm to 11 ⁇ m is used.
- a gas laser such as a CO 2 laser
- a solid laser such as a YAG laser
- a semiconductor laser Preferably, a CO 2 laser is used.
- the irradiation condition of the laser beam can be set to any appropriate condition depending on, for example, the laser to be used.
- the output condition is preferably 10 W to 1000 W, and more preferably 100 W to 400 W.
- the resin film (laminate) After the contact with the treatment liquid, the resin film (laminate) can be subjected to a drying treatment.
- the drying temperature is, for example, 50 ° C. to 120 ° C.
- Example 1 (Production of polarizer) A polymer film containing a PVA resin as a main component was immersed and stretched in the following five baths [1] to [5] while applying tension in the longitudinal direction of the film. This stretched film was dried to obtain a polarizer having a thickness of 28 ⁇ m.
- Swelling bath pure water at 30 ° C.
- Dyeing bath 30 ° C. aqueous solution containing iodine and potassium iodide
- First cross-linking bath containing potassium iodide and boric acid
- 40 Second cross-linking bath: 60 ° C. aqueous solution containing potassium iodide and boric acid
- Washing bath 25 ° C. aqueous solution containing potassium iodide
- the obtained polarizing plate sheet was cut using a CO 2 laser (wavelength: 9.35 ⁇ m, output: 150 W), and cut with a size of 54 mm ⁇ 54 mm in which a through hole having a diameter of 4 mm was formed at a site 25 mm from the outer edge. I got a piece. The obtained cut piece was dipped in warm water kept at 74 ° C. for 16 minutes to obtain a polarizing plate.
- Example 2 A polarizing plate was obtained in the same manner as in Example 1 except that the size of the cut piece was 94 mm ⁇ 94 mm and the through hole was formed at a position 45 mm from the outer edge.
- Example 3 A polarizing plate was obtained in the same manner as in Example 1 except that the size of the cut piece was 114 mm ⁇ 114 mm and the through hole was formed at a site 55 mm from the outer edge.
- Example 4 A polarizing plate was obtained in the same manner as in Example 1 except that the cut piece was immersed in a 3% by weight aqueous potassium iodide solution maintained at 74 ° C. instead of warm water maintained at 74 ° C.
- Example 1 A polarizing plate was obtained in the same manner as in Example 1 except that the cut piece was not immersed in warm water.
- Example 2 A polarizing plate was obtained in the same manner as in Example 2 except that the cut piece was not immersed in warm water.
- Example 3 A polarizing plate was obtained in the same manner as in Example 3 except that the cut piece was not immersed in warm water.
- a heat cycle (HS) test was performed on the obtained polarizing plate. Specifically, the obtained polarizing plate was bonded to a glass plate using an acrylic pressure-sensitive adhesive (thickness 20 ⁇ m) to obtain a test sample. This was left for 30 minutes in an atmosphere at ⁇ 40 ° C. and then left for 30 minutes in an atmosphere at 85 ° C. After repeating this operation as 100 cycles for 100 cycles, it was confirmed whether or not cracks occurred in the polarizing plate.
- the heat resistance test was performed on the polarizing plates of Example 1 and Example 4. Specifically, the polarizing plate was bonded to a glass plate using an acrylic pressure-sensitive adhesive (thickness 20 ⁇ m) to obtain a test sample. This was left in an atmosphere of 105 ° C. for 140 hours, and it was observed whether or not the polarizing plate was colored after the heat resistance test.
- Example 4 coloring was not confirmed after the heat resistance test, whereas in Example 1, as shown in the observation photograph by the optical microscope (manufactured by OLYMPUS, MX61, magnification: 5 times) in FIG. A colored portion having a width of about 300 ⁇ m was observed along the edge of the plate.
- the analysis result by micro-Raman spectroscopy analysis of the edge part of the polarizing plate of Example 1 after a heat test is shown in FIG.5 (b), and it is estimated that it is coloring by polyeneization.
- the content of iodine complex (I 3 ⁇ ) is markedly lower in the colored part than in the non-colored part. Note that the measurement conditions of the microscopic Raman spectroscopic analysis are as follows.
- Example 1 The concentration distribution of boric acid in the plane direction of the polarizer edge was measured.
- a time-of-flight secondary ion mass spectrometer TOF-SIMS
- ION-TOF product name: TOF-SIMS 5
- TOF-SIMS 5 The concentration distribution of boric acid in the plane direction of the polarizer edge was measured.
- TOF-SIMS time-of-flight secondary ion mass spectrometer
- the obtained polarizing plate was embedded with a resin and the cross-section was prepared using a microtome.
- the measurement conditions are as follows.
- Irradiated primary ions Bi 3 2+ ⁇ Primary ion acceleration voltage: 25 kV ⁇ Measurement area: 300 ⁇ m square x 2 fields of view * Use a charge correction electron gun for measurement. Observation with Optical Microscope A polarizing plate having an end embedded with a resin was cut in the thickness direction, and the cut surface was observed with an optical microscope (Nikon, ECLIPSE LV100, magnification: 50 times).
- FIG. 6A is a graph showing the boric acid concentration distribution in the surface direction of the end portion of the polarizer of Example 1
- FIG. 6B is the boric acid in the surface direction of the end portion of the polarizer of Comparative Example 1. It is a graph which shows concentration distribution. It was confirmed that a low-concentration portion having a concentration gradient in which the boric acid-containing concentration decreases toward the outside is formed at the end portion of the polarizer of Example 1. It was confirmed that a low concentration portion of boric acid was also formed at the end portion of the polarizer of Example 4.
- FIG. 7A is a graph showing a potassium concentration distribution in the surface direction of the end portion of the polarizer of Example 4, and FIG. 7B is a graph showing potassium concentration in the surface direction of the end portion of the polarizer of Comparative Example 1.
- FIG. 7C is a graph showing the concentration distribution of potassium in the surface direction of the end portion of the polarizer of Example 1.
- the potassium concentration in the high concentration part was about 10 times at maximum with respect to the potassium content in the central part of the polarizer.
- FIG. 8A and 8B are photographs taken with an optical microscope.
- FIG. 8A is a photograph showing the end of the polarizing plate of Example 1
- FIG. 8B is a photograph showing the end of the polarizing plate of Comparative Example 1.
- FIG. It was confirmed that a polarizer gap was formed at the end of the polarizing plate of Example 1.
- Example 4 the same results as in Example 1 were obtained.
- the polarizer of the present invention can be suitably used for, for example, a rectangular image display device (liquid crystal display device, organic EL device), for example, an odd-shaped image display unit typified by an automobile meter display unit or a smart watch. obtain.
- a rectangular image display device liquid crystal display device, organic EL device
- an odd-shaped image display unit typified by an automobile meter display unit or a smart watch.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Polarising Elements (AREA)
Abstract
Description
1つの実施形態においては、上記低濃度部は、面方向外方にいくほどホウ酸含有濃度が少ない濃度傾斜を有する。
1つの実施形態においては、上記低濃度部は、上記樹脂フィルムの端面から面方向内方に50μm以上の位置にかけて形成されている。
1つの実施形態においては、上記低濃度部は、吸収軸方向端部に形成されている。
1つの実施形態においては、貫通穴が形成され、この貫通穴の周縁部に上記低濃度部が形成されている。
1つの実施形態においては、上記低濃度部が外縁部に形成されている。
1つの実施形態においては、上記外縁は、面方向内方に凸の略V字形状をなす部位を含む。
本発明の別の局面によれば、偏光板が提供される。この偏光板は、上記偏光子と、この偏光子の少なくとも片面に配置された保護フィルムとを有する。
本発明のさらに別の局面によれば、偏光子の製造方法が提供される。この製造方法は、ホウ酸を含む樹脂フィルムに処理液を接触させて、この樹脂フィルムの端部に、ホウ酸の含有濃度が他の部位よりも低い低濃度部を形成する工程を含む。
1つの実施形態においては、上記処理液は水を含む。
1つの実施形態においては、上記処理液は、溶媒に、ヨウ素の対イオンを形成する物質を含む化合物を溶解させた溶液である。
1つの実施形態においては、上記化合物は、ヨウ化カリウムおよび/または塩化ナトリウムを含む。
1つの実施形態においては、上記処理液の液温は50℃以上である。
1つの実施形態においては、上記ホウ酸を含む樹脂フィルムを、切断および/または打ち抜き加工により所望の形状に成形する工程を含む。
1つの実施形態においては、上記切断および/または打ち抜き加工を、レーザー光を照射することにより行う。
1つの実施形態においては、上記レーザーはCO2レーザーである。 The polarizer of this invention is comprised from the resin film containing a boric acid, and the low density | concentration part whose content concentration of boric acid is lower than another site | part is formed in the edge part of this resin film.
In one embodiment, the said low concentration part has a density | concentration inclination with a boric acid containing density | concentration few, so that it goes to a surface direction outward.
In one embodiment, the said low concentration part is formed over the position of 50 micrometers or more in the surface direction inward from the end surface of the said resin film.
In one embodiment, the said low concentration part is formed in the absorption-axis direction edge part.
In one embodiment, a through hole is formed, and the low-concentration portion is formed at the peripheral edge of the through hole.
In one embodiment, the said low concentration part is formed in the outer edge part.
In one embodiment, the said outer edge contains the site | part which makes a substantially V shape convex in the surface direction inward.
According to another aspect of the present invention, a polarizing plate is provided. This polarizing plate has the said polarizer and the protective film arrange | positioned at least on one side of this polarizer.
According to still another aspect of the present invention, a method for producing a polarizer is provided. This manufacturing method includes a step of bringing a treatment liquid into contact with a resin film containing boric acid to form a low concentration portion having a lower concentration of boric acid than other portions at the end of the resin film.
In one embodiment, the treatment liquid includes water.
In one embodiment, the treatment liquid is a solution in which a compound containing a substance that forms a counter ion of iodine is dissolved in a solvent.
In one embodiment, the compound comprises potassium iodide and / or sodium chloride.
In one embodiment, the liquid temperature of the said processing liquid is 50 degreeC or more.
In one embodiment, it includes a step of forming the resin film containing boric acid into a desired shape by cutting and / or punching.
In one embodiment, the cutting and / or punching process is performed by irradiating a laser beam.
In one embodiment, the laser is a CO 2 laser.
図1は本発明の1つの実施形態による偏光板の平面図であり、図2は図1に示す偏光板の部分拡大断面図である。偏光板100は、自動車のメータパネルに好適に用いられる。偏光板100は、第1の表示部50と第2の表示部60とが連設されて構成され、各表示部の中心付近には、各種メータ針を固定するための貫通穴51,61がそれぞれ形成されている。貫通穴の直径は、例えば0.5mm~100mmである。表示部50,60の外縁は、メータ針の回転方向に沿った円弧状に形成されている。 A. Polarizer (polarizing plate)
FIG. 1 is a plan view of a polarizing plate according to one embodiment of the present invention, and FIG. 2 is a partially enlarged sectional view of the polarizing plate shown in FIG. The polarizing
上記低濃度部は、好ましくは、ホウ酸を含む樹脂フィルムに処理液を接触させることにより形成される。このような形態によれば、所望の部位に低濃度部を簡便に形成することができる。具体的には、ホウ酸を処理液に溶出させて、良好に低濃度部を形成することができる。処理液の接触方法としては、任意の適切な方法が採用され得る。具体的には、処理液に樹脂フィルムを浸漬する方法、樹脂フィルムに処理液を塗布する方法、樹脂フィルムに処理液を噴霧する方法等が挙げられる。好ましくは、処理液に樹脂フィルムを浸漬する方法が採用される。 B. Method for Producing Polarizer (Polarizing Plate) The low concentration portion is preferably formed by bringing a treatment liquid into contact with a resin film containing boric acid. According to such a form, a low concentration part can be easily formed in a desired part. Specifically, boric acid can be eluted into the treatment liquid to form the low concentration portion satisfactorily. Any appropriate method can be adopted as a method for contacting the treatment liquid. Specifically, a method of immersing the resin film in the treatment liquid, a method of applying the treatment liquid to the resin film, a method of spraying the treatment liquid on the resin film, and the like can be given. Preferably, a method of immersing a resin film in the treatment liquid is employed.
(偏光子の作製)
PVA系樹脂を主成分とする高分子フィルムを下記[1]~[5]の5浴に順次、フィルム長手方向に張力を付与しながら浸漬し、延伸した。この延伸フィルムを乾燥させて、厚み28μmの偏光子を得た。
<条件>
[1]膨潤浴:30℃の純水
[2]染色浴:ヨウ素とヨウ化カリウムとを含む、30℃の水溶液
[3]第1の架橋浴:ヨウ化カリウムとホウ酸とを含む、40℃の水溶液
[4]第2の架橋浴:ヨウ化カリウムとホウ酸とを含む、60℃の水溶液
[5]洗浄浴:ヨウ化カリウムを含む、25℃の水溶液 [Example 1]
(Production of polarizer)
A polymer film containing a PVA resin as a main component was immersed and stretched in the following five baths [1] to [5] while applying tension in the longitudinal direction of the film. This stretched film was dried to obtain a polarizer having a thickness of 28 μm.
<Conditions>
[1] Swelling bath: pure water at 30 ° C. [2] Dyeing bath: 30 ° C. aqueous solution containing iodine and potassium iodide [3] First cross-linking bath: containing potassium iodide and boric acid, 40 [4] Second cross-linking bath: 60 ° C. aqueous solution containing potassium iodide and boric acid [5] Washing bath: 25 ° C. aqueous solution containing potassium iodide
上記偏光子の片側にPVA系接着剤を乾燥後の厚みが100nmとなるように塗布し、長尺状で厚み40μmのTACフィルムを互いの長手方向を揃えるように貼り合わせた。
続いて、上記偏光子のもう片側にPVA系接着剤を乾燥後の厚みが100nmとなるように塗布し、長尺状で厚み30μmのアクリルフィルムを互いの長手方向を揃えるように貼り合わせた。
こうして、TACフィルム/偏光子/アクリルフィルムの構成を有する偏光板シートを得た。 (Preparation of polarizing plate sheet)
A PVA adhesive was applied to one side of the polarizer so that the thickness after drying was 100 nm, and a long TAC film having a thickness of 40 μm was bonded so that the longitudinal directions thereof were aligned.
Subsequently, a PVA adhesive was applied to the other side of the polarizer so that the thickness after drying was 100 nm, and a long acrylic film having a thickness of 30 μm was bonded so that the longitudinal directions thereof were aligned.
Thus, a polarizing plate sheet having a TAC film / polarizer / acrylic film structure was obtained.
得られた切断片を74℃に保たれた温水に16分間浸漬し、偏光板を得た。 The obtained polarizing plate sheet was cut using a CO 2 laser (wavelength: 9.35 μm, output: 150 W), and cut with a size of 54 mm × 54 mm in which a through hole having a diameter of 4 mm was formed at a site 25 mm from the outer edge. I got a piece.
The obtained cut piece was dipped in warm water kept at 74 ° C. for 16 minutes to obtain a polarizing plate.
切断片のサイズを94mm×94mmとし、貫通穴を外縁から45mmの部位に形成したこと以外は実施例1と同様にして、偏光板を得た。 [Example 2]
A polarizing plate was obtained in the same manner as in Example 1 except that the size of the cut piece was 94 mm × 94 mm and the through hole was formed at a position 45 mm from the outer edge.
切断片のサイズを114mm×114mmとし、貫通穴を外縁から55mmの部位に形成したこと以外は実施例1と同様にして、偏光板を得た。 [Example 3]
A polarizing plate was obtained in the same manner as in Example 1 except that the size of the cut piece was 114 mm × 114 mm and the through hole was formed at a site 55 mm from the outer edge.
74℃に保たれた温水のかわりに、切断片を74℃に保たれた3重量%のヨウ化カリウム水溶液に浸漬したこと以外は実施例1と同様にして、偏光板を得た。 [Example 4]
A polarizing plate was obtained in the same manner as in Example 1 except that the cut piece was immersed in a 3% by weight aqueous potassium iodide solution maintained at 74 ° C. instead of warm water maintained at 74 ° C.
切断片を温水に浸漬しなかったこと以外は実施例1と同様にして、偏光板を得た。 [Comparative Example 1]
A polarizing plate was obtained in the same manner as in Example 1 except that the cut piece was not immersed in warm water.
切断片を温水に浸漬しなかったこと以外は実施例2と同様にして、偏光板を得た。 [Comparative Example 2]
A polarizing plate was obtained in the same manner as in Example 2 except that the cut piece was not immersed in warm water.
切断片を温水に浸漬しなかったこと以外は実施例3と同様にして、偏光板を得た。 [Comparative Example 3]
A polarizing plate was obtained in the same manner as in Example 3 except that the cut piece was not immersed in warm water.
・装置:顕微鏡レーザーラマン(Jobin Yvon S.A.S, LabRAM HR800)
・励起波長:514nm
・測定波長範囲:80~1800cm-1付近
・Grating:600gr/mm
・対物レンズ:×100
・積算時間:2sec
・積算回数:2回
・フィルター:D3
・Hole:300
・検出器:CCD In Example 4, coloring was not confirmed after the heat resistance test, whereas in Example 1, as shown in the observation photograph by the optical microscope (manufactured by OLYMPUS, MX61, magnification: 5 times) in FIG. A colored portion having a width of about 300 μm was observed along the edge of the plate. The analysis result by micro-Raman spectroscopy analysis of the edge part of the polarizing plate of Example 1 after a heat test is shown in FIG.5 (b), and it is estimated that it is coloring by polyeneization. The content of iodine complex (I 3 − ) is markedly lower in the colored part than in the non-colored part. Note that the measurement conditions of the microscopic Raman spectroscopic analysis are as follows.
・ Device: Microscope Laser Raman (Jobin Yvon SA, LabRAM HR800)
Excitation wavelength: 514 nm
・ Measurement wavelength range: around 80 to 1800 cm −1・ Grating: 600 gr / mm
・ Objective lens: x100
・ Integrated time: 2 sec
・ Number of integration: 2 times ・ Filter: D3
-Hole: 300
・ Detector: CCD
1.濃度分布測定
偏光子端部の面方向におけるホウ酸の濃度分布を測定した。測定は、飛行時間型二次イオン質量分析計(TOF-SIMS)(ION-TOF製、製品名:TOF-SIMS 5)を用いた。測定サンプルとしては、得られた偏光板を樹脂で包埋し、ミクロトームを用いて断面調製したものを用いた。測定条件は以下のとおりである。
・照射した一次イオン:Bi3 2+
・一次イオン加速電圧:25kV
・測定面積:300μm角×2視野
※測定には、帯電補正用電子銃を使用
2.光学顕微鏡観察
端部を樹脂で包埋した偏光板をその厚み方向に切断し、切断面を光学顕微鏡(Nikon製、ECLIPSE LV100、倍率:50倍)で観察した。 The following evaluation was performed on the polarizing plates of Example 1, Example 4, and Comparative Example 1.
1. Concentration distribution measurement The concentration distribution of boric acid in the plane direction of the polarizer edge was measured. For the measurement, a time-of-flight secondary ion mass spectrometer (TOF-SIMS) (manufactured by ION-TOF, product name: TOF-SIMS 5) was used. As a measurement sample, the obtained polarizing plate was embedded with a resin and the cross-section was prepared using a microtome. The measurement conditions are as follows.
Irradiated primary ions: Bi 3 2+
・ Primary ion acceleration voltage: 25 kV
・ Measurement area: 300μm square x 2 fields of view * Use a charge correction electron gun for measurement. Observation with Optical Microscope A polarizing plate having an end embedded with a resin was cut in the thickness direction, and the cut surface was observed with an optical microscope (Nikon, ECLIPSE LV100, magnification: 50 times).
21,22 保護フィルム
100 偏光板 10
Claims (16)
- ホウ酸を含む樹脂フィルムから構成され、
前記樹脂フィルムの端部に、前記ホウ酸の含有濃度が他の部位よりも低い低濃度部が形成されている、
偏光子。 Consists of a resin film containing boric acid,
The low concentration part where the content concentration of the boric acid is lower than other parts is formed at the end of the resin film,
Polarizer. - 前記低濃度部が、面方向外方にいくほどホウ酸含有濃度が少ない濃度傾斜を有する、請求項1に記載の偏光子。 The polarizer according to claim 1, wherein the low concentration portion has a concentration gradient in which the boric acid content concentration decreases toward the outside in the plane direction.
- 前記低濃度部が、前記樹脂フィルムの端面から面方向内方に50μm以上の位置にかけて形成されている、請求項1または2に記載の偏光子。 The polarizer according to claim 1 or 2, wherein the low-concentration portion is formed from the end face of the resin film to a position of 50 µm or more inward in the plane direction.
- 前記低濃度部が、吸収軸方向端部に形成されている、請求項1から3のいずれかに記載の偏光子。 The polarizer according to any one of claims 1 to 3, wherein the low concentration portion is formed at an end portion in an absorption axis direction.
- 貫通穴が形成され、該貫通穴の周縁部に前記低濃度部が形成されている、請求項1から4のいずれかに記載の偏光子。 The polarizer according to any one of claims 1 to 4, wherein a through hole is formed, and the low concentration portion is formed at a peripheral portion of the through hole.
- 前記低濃度部が外縁部に形成されている、請求項1から5のいずれかに記載の偏光子。 The polarizer according to any one of claims 1 to 5, wherein the low concentration portion is formed at an outer edge portion.
- 前記外縁が、面方向内方に凸の略V字形状をなす部位を含む、請求項6に記載の偏光子。 The polarizer according to claim 6, wherein the outer edge includes a substantially V-shaped portion that is convex inward in the plane direction.
- 請求項1から7のいずれかに記載の偏光子と、該偏光子の少なくとも片面に配置された保護フィルムとを有する、偏光板。 A polarizing plate comprising the polarizer according to any one of claims 1 to 7 and a protective film disposed on at least one side of the polarizer.
- ホウ酸を含む樹脂フィルムに処理液を接触させて、該樹脂フィルムの端部に、該ホウ酸の含有濃度が他の部位よりも低い低濃度部を形成する工程を含む、
偏光子の製造方法。 Including a step of bringing a treatment liquid into contact with a resin film containing boric acid, and forming a low-concentration part having a lower concentration of boric acid than other parts at the end of the resin film,
A method for producing a polarizer. - 前記処理液が水を含む、請求項9に記載の製造方法。 The manufacturing method according to claim 9, wherein the treatment liquid contains water.
- 前記処理液が、溶媒に、ヨウ素の対イオンを形成する物質を含む化合物を溶解させた溶液である、請求項9または10に記載の製造方法。 The method according to claim 9 or 10, wherein the treatment liquid is a solution in which a compound containing a substance that forms a counter ion of iodine is dissolved in a solvent.
- 前記化合物が、ヨウ化カリウムおよび/または塩化ナトリウムを含む、請求項11に記載の製造方法。 The production method according to claim 11, wherein the compound contains potassium iodide and / or sodium chloride.
- 前記処理液の液温が50℃以上である、請求項9から12のいずれかに記載の製造方法。 The manufacturing method according to any one of claims 9 to 12, wherein a temperature of the treatment liquid is 50 ° C or higher.
- 前記ホウ酸を含む樹脂フィルムを、切断および/または打ち抜き加工により所望の形状に成形する工程を含む、請求項9から13のいずれかに記載の製造方法。 The manufacturing method according to any one of claims 9 to 13, including a step of forming the resin film containing boric acid into a desired shape by cutting and / or punching.
- 前記切断および/または打ち抜き加工を、レーザー光を照射することにより行う、請求項14に記載の製造方法。 The manufacturing method according to claim 14, wherein the cutting and / or punching is performed by irradiating a laser beam.
- 前記レーザーがCO2レーザーである、請求項15に記載の製造方法。 The manufacturing method according to claim 15, wherein the laser is a CO 2 laser.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16779852.9A EP3285098A4 (en) | 2015-04-17 | 2016-03-10 | Polarizer, polarizing plate, and method for producing polarizer |
KR1020177026550A KR102027048B1 (en) | 2015-04-17 | 2016-03-10 | Polarizer, polarizing plate, and method for producing polarizer |
CN201680016655.5A CN107430235B (en) | 2015-04-17 | 2016-03-10 | Polarizer, polarizing plate and method for producing polarizer |
US15/545,766 US10107947B2 (en) | 2015-04-17 | 2016-03-10 | Polarizer, polarizing plate, and method for producing polarizer |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015085107 | 2015-04-17 | ||
JP2015-085107 | 2015-04-17 | ||
JP2015-227540 | 2015-11-20 | ||
JP2015227540A JP6420747B2 (en) | 2015-04-17 | 2015-11-20 | Polarizer, polarizing plate, and method for producing polarizer |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016167060A1 true WO2016167060A1 (en) | 2016-10-20 |
Family
ID=57126791
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/057495 WO2016167060A1 (en) | 2015-04-17 | 2016-03-10 | Polarizer, polarizing plate, and method for producing polarizer |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2016167060A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018139358A1 (en) * | 2017-01-27 | 2018-08-02 | 住友化学株式会社 | Polarizing plate and image display device |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005084507A (en) * | 2003-09-10 | 2005-03-31 | Sumitomo Chemical Co Ltd | Manufacturing method of polarizing film, manufacturing method of polarizing plate and manufacturing method of optical laminated body |
JP2013011837A (en) * | 2010-09-03 | 2013-01-17 | Nitto Denko Corp | Thin polarizing film, optical laminate with thin polarizing film, and production method for thin polarizing film |
JP2013254072A (en) * | 2012-06-06 | 2013-12-19 | Nitto Denko Corp | Polarizing plate, optical film, and image display device |
JP2014167654A (en) * | 2014-06-03 | 2014-09-11 | Kuraray Co Ltd | Production method of polarizing film |
-
2016
- 2016-03-10 WO PCT/JP2016/057495 patent/WO2016167060A1/en active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005084507A (en) * | 2003-09-10 | 2005-03-31 | Sumitomo Chemical Co Ltd | Manufacturing method of polarizing film, manufacturing method of polarizing plate and manufacturing method of optical laminated body |
JP2013011837A (en) * | 2010-09-03 | 2013-01-17 | Nitto Denko Corp | Thin polarizing film, optical laminate with thin polarizing film, and production method for thin polarizing film |
JP2013254072A (en) * | 2012-06-06 | 2013-12-19 | Nitto Denko Corp | Polarizing plate, optical film, and image display device |
JP2014167654A (en) * | 2014-06-03 | 2014-09-11 | Kuraray Co Ltd | Production method of polarizing film |
Non-Patent Citations (1)
Title |
---|
See also references of EP3285098A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018139358A1 (en) * | 2017-01-27 | 2018-08-02 | 住友化学株式会社 | Polarizing plate and image display device |
JP2018159911A (en) * | 2017-01-27 | 2018-10-11 | 住友化学株式会社 | Polarizing plate and image display device |
CN110192131A (en) * | 2017-01-27 | 2019-08-30 | 住友化学株式会社 | Polarization plates and image display device |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6420747B2 (en) | Polarizer, polarizing plate, and method for producing polarizer | |
JP6215262B2 (en) | Manufacturing method of long polarizer | |
JP6215261B2 (en) | Long polarizer, long polarizing plate and image display device | |
JP6823705B2 (en) | Polarizer | |
JP6619619B2 (en) | Polarizer, polarizing plate, and method for producing polarizer | |
TW201706640A (en) | Polarizer | |
TW201728704A (en) | Polarizer, polarizing plate, and image display apparatus | |
JP2016027393A (en) | Long polarizing film laminate | |
WO2016167059A1 (en) | Polarizing plate and method for producing same | |
WO2016167060A1 (en) | Polarizer, polarizing plate, and method for producing polarizer | |
JP2020106834A (en) | Polarizer and method for manufacturing the same | |
JP7369237B2 (en) | Manufacturing method of polarizing plate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16779852 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15545766 Country of ref document: US |
|
REEP | Request for entry into the european phase |
Ref document number: 2016779852 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20177026550 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |