Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B45/00—Complex metal compounds of azo dyes
  • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
  • C09B45/24—Disazo or polyazo compounds
  • C09B45/28—Disazo or polyazo compounds containing copper
• • 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
  • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
• • G—PHYSICS
  • G02—OPTICS
  • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
  • G02C7/00—Optical parts
  • G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
• • G—PHYSICS
  • G02—OPTICS
  • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
  • G02C7/00—Optical parts
  • G02C7/12—Polarisers

Definitions

• the present invention relates to a dye-based polarizing element or a dye-based polarizing plate that does not elute or precipitate an azo compound even if it is subjected to a humidification treatment or a water immersion treatment, etc., and a water-containing treatment.
• a polarizing element is generally produced by adsorbing and orienting iodine or dichroic dye, which is a dichroic dye, on a polyvinyl alcohol resin film.
• a protective film made of triacetyl cellulose or the like is bonded to at least one surface of the polarizing element via an adhesive layer to form a polarizing plate, which is used for a liquid crystal display device or the like.
• a polarizing plate using iodine as a dichroic dye is called an iodine polarizing plate, while a polarizing plate using a dichroic dye as a dichroic dye is called a dye polarizing plate.
• dye-based polarizing plates have high heat resistance, high humidity heat durability, high stability, and are characterized by high color selectivity by blending, while having the same degree of polarization.
• the transmittance is low compared to the plate, that is, the contrast is low. Therefore, it is desired to maintain high durability, to have various color selectivity, to have higher transmittance and to have high polarization characteristics.
• the dye-based polarizing plate has high durability, since the polarizing element itself is a polyvinyl alcohol resin film, it swells when it contains water, and the azo compound is re-dissolved by the water contained in the film, so At the same time, there was a problem that the azo compound was eluted and discolored or decolored.
• the cause is that amine compounds such as monoethanolamine and diethanolamine are used as described in Examples described in Patent Documents 1 to 6. Since amine compounds can improve the solubility of azo compounds in water, they can be used as auxiliary agents during dye synthesis, dye water solubility improvers during the dyeing process, and dye solution dissolution stabilizers.
• Such discoloration or discoloration occurs when, for example, a polarizing element or a polarizing plate using the same is subjected to a humidification treatment or a water immersion treatment, so that the azo compound is eluted from the polarizing element.
• a polarizing element or a polarizing plate using the same is subjected to a humidification treatment or a water immersion treatment, so that the azo compound is eluted from the polarizing element.
• There was a problem of discoloration and discoloration No decolorization or discoloration when used for products that require reworking of polarizing elements, such as lenses and filters that require bending or curved surfaces of polarizing elements, especially sunglasses and glasses.
• a polarizing element has been desired.
• the inventor is a polyvinyl alcohol-based resin film that has been subjected to a stretching treatment containing at least one azo compound, and the content of the amine compound contained in the film is 70 ppm.
• Dye-type polarizing element or dye-type polarizing plate in which azo compound does not elute or precipitate even when it is moistened by water treatment or dipping treatment in water. It was found that it can provide.
• a polarizing element comprising a stretched polyvinyl alcohol-based resin film containing at least one azo compound, characterized in that the content of the amine compound contained in the film is 70 ppm or less.
• the polarizing element (2) The polarizing element according to (1), wherein the amine compound has a hydroxyl group, (3) The polarizing element according to (1) or (2), wherein the polyvinyl alcohol-based resin film is stretched 3 to 7 times, (4) The polarizing element according to any one of (1) to (3), wherein at least one of the azo compounds is a copperated azo compound, (5) The polarizing element according to any one of (1) to (4), wherein at least one of the azo compounds is a copperated azo compound having a structure of formula (1), (In the formula, A 1 represents an azo group and / or a phenyl group or naphthyl group having a substituent, and R 1 represents a hydrogen atom, a lower alkyl group, a lower
• X 1 represents an amino group which may have a substituent, a benzoylamino group which may have a substituent, a phenylamino group which may have a substituent, a phenylazo group which may have a substituent Or a naphthotriazole group which may have a substituent.
• a polarizing plate comprising a transparent protective layer provided on at least one surface of the polarizing element according to any one of (1) to (5), (7) A polarizing lens using the polarizing element according to any one of (1) to (5) or the polarizing plate according to (6), (8) A polarizing filter using the polarizing element according to any one of (1) to (5) or the polarizing plate according to (6), (9) The polarizing element according to any one of (1) to (5), the polarizing plate according to (6), the polarizing lens according to (7), or the polarizing filter according to (8).
• Used polarized sunglasses (10) The polarizing element according to any one of (1) to (5), the polarizing plate according to (6), the polarizing lens according to (7), or the polarizing filter according to (8).
• Used polarized glasses (11) A method for producing a polarizing element, wherein the polarizing element according to any one of (1) to (5) is wetted or humidified, and then stretched or rolled again.
• a method for producing a polarizing element by impregnating a polyvinyl alcohol-based resin film into a dye solution containing an azo compound and subjecting it to stretching treatment, wherein the content of the amine compound in the dye solution is azo compound
• the manufacturing method is characterized by being 400 parts by weight or less with respect to 1000 parts by weight.
• the present invention relates to a dye-based polarizing element or a dye-based polarizing plate that does not elute or precipitate an azo compound even when it is water-containing by humidification treatment or water immersion treatment.
• the present invention is a polarizing element comprising a polyvinyl alcohol-based resin film subjected to stretching treatment containing at least one azo compound, wherein the content of the amine compound contained in the film is 70 ppm or less, and
• the present invention relates to a polarizing plate including the polarizing element.
• a polarizing element or polarized light is obtained by forming a resin comprising a polyvinyl alcohol-based resin and a derivative thereof as a base material, containing the azo compound of the present invention and a blend thereof in the film, and applying an orientation treatment such as stretching.
• a plate can be made.
• the manufacturing method of a polyvinyl alcohol-type resin is not specifically limited, It can produce with a well-known method. As a production method, for example, it can be obtained by saponifying a polyvinyl acetate resin.
• the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith.
• Examples of other monomers copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids.
• the degree of saponification of the polyvinyl alcohol resin is usually about 85 to 100 mol%, preferably 95 mol% or more.
• This polyvinyl alcohol-based resin may be further modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used.
• the polymerization degree of a polyvinyl alcohol-type resin means a viscosity average polymerization degree, and can be calculated
• the degree of polymerization of the polyvinyl alcohol resin is usually about 1,000 to 10,000, and preferably about 1,500 to 6,000.
• a film formed from such a polyvinyl alcohol resin is used as a raw film.
• the method for forming a polyvinyl alcohol-based resin is not particularly limited, and can be formed by a known method.
• the polyvinyl alcohol-based resin film may contain glycerin, ethylene glycol, propylene glycol, low molecular weight polyethylene glycol or the like as a plasticizer.
• the amount of plasticizer is 5 to 20% by weight, preferably 8 to 15% by weight.
• the film thickness of the raw film made of polyvinyl alcohol resin is not particularly limited, but for example, about 5 ⁇ m to 150 ⁇ m, preferably about 10 ⁇ m to 100 ⁇ m is preferable.
• a swelling process is performed on the polyvinyl alcohol-based resin film obtained as described above.
• the swelling treatment is applied by immersing in a solution at 20 to 50 ° C. for 30 seconds to 10 minutes.
• the solution is preferably water.
• the draw ratio may be adjusted to 1.00 to 1.50 times, preferably 1.10 to 1.35 times.
• the swelling process may be omitted because it swells even during the dyeing process.
• the dyeing process can be performed by immersing the polyvinyl alcohol resin film in a solution containing an azo compound. Done.
• the solution temperature in this step is preferably 5 to 60 ° C, more preferably 20 to 50 ° C, and particularly preferably 35 to 50 ° C.
• the time for dipping in the solution can be adjusted moderately, but is preferably adjusted from 30 seconds to 20 minutes, more preferably from 1 to 10 minutes.
• the dyeing method is preferably immersed in the solution, but can also be performed by applying the solution to a polyvinyl alcohol-based resin film.
• the solution containing the azo compound can contain sodium carbonate, sodium hydrogen carbonate, sodium chloride, sodium sulfate, anhydrous sodium sulfate, sodium tripolyphosphate, and the like as a dyeing assistant.
• Their content can be adjusted at any concentration depending on the time and temperature depending on the dyeability of the dye, but the respective content is preferably 0 to 5% by weight, more preferably 0.1 to 2% by weight.
• the azo compound is used as a free acid and may be a salt of the compound.
• Such salts can also be used as alkali metal salts such as lithium salts, sodium salts, and potassium salts, or organic salts such as ammonium salts and alkylamine salts.
• it is a sodium salt.
• Examples of the azo compound include compounds described in Non-Patent Document 1, and dichroic dyes can be used, and those having high dichroism are more preferable. Further, as the azo compound, in addition to the azo compound as shown in Non-Patent Document 1, C.I. Ai. direct. Yellow 12, sea. Ai. direct. Yellow 28, Sea. Ai. direct. Yellow 44, Sea. Ai. direct. Orange 26, Sea. Ai. direct. Orange 39, sea. Ai. direct. Orange 107, sea. Ai. direct. Red 2, sea. Ai. direct. Red 31, sea. Ai. direct. Red 79, Sea. Ai. direct. Red 81, Sea. Ai. direct. Red 247, Sea. Ai. direct. Green 80, Sea. Ai. direct.
• Examples thereof include Green 59, and organic dyes described in JP-A Nos. 2001-33627, 2002-296417, and 60-156759.
• these dichroic dyes may be alkali metal salts (for example, Na salt, K salt, Li salt), ammonium salts, or salts of amines.
• a dye-based polarizing element that does not elute or precipitate an azo compound even when it is moistened by water treatment, particularly by humidification treatment, or dye-based polarization.
• a plate can be produced.
• Examples of the copperated azo compound include C.I. Ai. direct. Blue 199, Sea. Ai. direct. Blue 202, Sea. Ai.
• the copperized azo compounds is a copperated azo compound having the structure of the formula (1)
• a humidification treatment or water is used for reprocessing.
• the azo compound is eluted, and discoloration and decoloration are remarkable.
• the elution of the azo compound is remarkably suppressed when the amine compound in the polarizing element is 70 ppm or less.
• a 1 represents an azo group and / or a phenyl group or naphthyl group having a substituent
• R 1 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfo group, or a lower alkoxy group having a sulfo group
• X 1 represents an amino group which may have a substituent, a benzoylamino group which may have a substituent, a phenylamino group which may have a substituent, a phenylazo group which may have a substituent Or a naphthotriazole group which may have a substituent.
• Examples of the amine compound of the present invention include ethylamines, isopropylamines, ethylenediamines, ethanolamines, isopropanolamines, and the like, and examples include amine compounds that exhibit water solubility. Specifically, monoethylamine, diethylamine, triethylamine, isopropylamine, ethylenediamine, monoethanolamine, 2-aminoethanol, methylaminoethanol, dimethylaminoethanol, diethanolamine, triethanolamine, pyridine, N, N-dimethylformamide, aniline 2-pyrrolidone, N-methyl-2-pyrrolidone, formalin, N-methyl formalin, monoisopropanolamine and the like.
• an amine compound having a hydroxyl group such as monoethanolamine, 2-aminoethanol, methylaminoethanol, dimethylaminoethanol, or diethanolamine is used in the synthesis of the azo compound.
• the polarizing element contains more than 70 ppm of the compound
• the azo compound is eluted, and discoloration and decoloration become remarkable. Therefore, attention must be paid to the content of the amine compound in the polarizing element.
• content of the amine compound in a polarizing element it is required that it is 70 ppm or less, More preferably, it is 40 ppm or less, More preferably, 10 ppm or less is good.
• a method using a standard method in a gas chromatograph can be mentioned.
• a freeze-pulverized polarizing element is added to a known amount of an internal standard substance (for example, trimethylolpropane), N, O-bis (trimethylsilyl) trifluoroacetamide, and pyridine, and heated at 80 ° C. for 10 minutes.
• the amine compound can be quantified from the area value obtained by measurement with a gas chromatograph.
• the method of quantification is not limited to this, and can be quantified by a known method.
• a method for controlling the content of the amine compound in the polarizing element As a method for controlling the content of the amine compound in the polarizing element, a method in which the polarizing element containing the amine compound is brought into contact with a solvent in which the amine compound is dissolved, an aqueous solution or a solution used in the manufacturing process of the polarizing element contains the amine compound. The method of manufacturing while immersing in the aqueous solution or solution with little quantity is illustrated.
• a polarizing element comprising a polyvinyl alcohol-based resin film having an amine compound of 70 ppm or less, in order to avoid impregnation of the amine compound into the polyvinyl alcohol-based resin film, an aqueous solution containing little amine compound or a polarizing element with a solution Is preferable.
• the content of the amine compound in each step in the aqueous solution or solution needs to be adjusted depending on the method of containing the azo compound in the polyvinyl alcohol resin film, the draw ratio of the polyvinyl alcohol resin film, and the dyeing state of the azo compound. It is necessary to adjust arbitrarily.
• a method of adjusting the content of the amine compound it is necessary to reduce the content of the amine compound in an aqueous solution or solution in which the azo compound is immersed in the polyvinyl alcohol resin film.
• Management of amine compounds in each process is important.
• the method include a method of removing the amine compound from the aqueous solution or solution in the dyeing step, a method of removing the amine compound contained in the azo compound, and the like.
• the temperature of the cleaning solution in the cleaning step 1 needs to be a temperature at which the hydrophilic polymer does not dissolve. Generally, it is washed at 5 to 40 ° C. However, since there is no problem in performance even without the cleaning step 1, this step can be omitted.
• a step of adding a crosslinking agent and / or a water resistance agent can be performed.
• the crosslinking agent include boron compounds such as boric acid, borax or ammonium borate, polyhydric aldehydes such as glyoxal or glutaraldehyde, polyisocyanate compounds such as biuret type, isocyanurate type or block type, titanium oxy Titanium compounds such as sulfate can be used, but ethylene glycol glycidyl ether, polyamide epichlorohydrin, and the like can also be used.
• water-resistant agent examples include succinic peroxide, ammonium persulfate, calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, ammonium chloride or magnesium chloride, preferably boric acid.
• succinic peroxide ammonium persulfate
• calcium perchlorate benzoin ethyl ether
• ethylene glycol diglycidyl ether glycerin diglycidyl ether
• ammonium chloride or magnesium chloride preferably boric acid.
• the step of containing a crosslinking agent and / or a water-resistant agent is performed using at least one kind of crosslinking agent and / or a water-resistant agent shown above.
• water is preferable, but it is not limited.
• the concentration of the cross-linking agent and / or the water-proofing agent in the solvent in the step of adding the cross-linking agent and / or the water-proofing agent is 0.1 to 6.0 when boric acid is used as an example. % By weight is preferable, and 1.0 to 4.0% by weight is more preferable.
• the solvent temperature in this step is preferably 5 to 70 ° C, more preferably 5 to 50 ° C. Although it is preferable to immerse the polyvinyl alcohol-based resin film in the solution with a crosslinking agent and / or a waterproofing agent, the solution may be applied to or applied to the polyvinyl alcohol-based resin film.
• the treatment time in this step is preferably 30 seconds to 6 minutes, more preferably 1 to 5 minutes.
• this processing step may be omitted if a cross-linking treatment or a water-resistant treatment is unnecessary. .
• the stretching step is a step of stretching the polyvinyl alcohol resin film uniaxially.
• the stretching method may be either a wet stretching method or a dry stretching method, and the effect of the present invention can be achieved by stretching the stretching ratio by 3 times or more.
• the draw ratio is 3 times or more, preferably 5 to 7 times.
• the stretching heating medium is an air medium
• the temperature of the air medium is preferably stretched at a room temperature to 180 ° C.
• the treatment is preferably performed in an atmosphere of 20 to 95% RH.
• the stretching method include, but are not limited to, an inter-roll zone stretching method, a roll heating stretching method, a pressure stretching method, and an infrared heating stretching method.
• the stretching step can be performed in one step, but can also be performed by two or more multi-step stretching.
• stretching is performed in water, a water-soluble organic solvent, or a mixed solution thereof. It is preferable to perform the stretching treatment while being immersed in a solution containing a crosslinking agent and / or a water resistance agent.
• a crosslinking agent include boron compounds such as boric acid, borax or ammonium borate, polyhydric aldehydes such as glyoxal or glutaraldehyde, polyisocyanate compounds such as biuret type, isocyanurate type or block type, titanium oxy Titanium compounds such as sulfate can be used, but ethylene glycol glycidyl ether, polyamide epichlorohydrin, and the like can also be used.
• water-proofing agents include succinic peroxide, ammonium persulfate, calcium perchlorate, benzoin ethyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, ammonium chloride, and magnesium chloride.
• Stretching is performed in a solution containing at least one or more crosslinking agents and / or waterproofing agents as described above.
• the crosslinking agent is preferably boric acid.
• the concentration of the crosslinking agent and / or waterproofing agent in the stretching step is preferably, for example, 0.5 to 15% by weight, more preferably 2.0 to 8.0% by weight.
• the stretching temperature is preferably 40 to 60 ° C, more preferably 45 to 58 ° C.
• the film surface may be subjected to a cleaning step (hereinafter referred to as “cleaning step 2”) because precipitation of the crosslinking agent and / or waterproofing agent or foreign matter may adhere to the film surface.
• cleaning step 2 a cleaning step
• the washing time is preferably 1 second to 5 minutes.
• the washing method is preferably immersed in a washing solution, but the solution can be washed on the polyvinyl alcohol resin film by coating or coating.
• the cleaning process can be performed in one stage, and the multi-stage process of two or more stages can be performed.
• the solution temperature in the washing step is not particularly limited, but is usually 5 to 50 ° C., preferably 10 to 40 ° C.
• the solvent used in the treatment steps so far, for example, water, dimethyl sulfoxide, N-methylpyrrolidone, methanol, ethanol, propanol, isopropyl alcohol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or triethylene glycol
• the solvent include, but are not limited to, alcohols such as methylolpropane, and amines such as ethylenediamine or diethylenetriamine. A mixture of one or more of these solvents can also be used.
• the most preferred solvent is water.
• a film drying process is performed.
• the drying process can be performed by natural drying, but in order to further improve the drying efficiency, the surface can be removed by compression with a roll, an air knife, a water absorption roll, etc., and / or blow drying is performed. You can also.
• the drying treatment temperature is preferably 20 to 100 ° C., more preferably 60 to 100 ° C.
• a drying treatment time of 30 seconds to 20 minutes can be applied, but 5 to 10 minutes is preferable.
• a polarizing element can be obtained.
• the obtained polarizing element is made into a polarizing plate by providing a transparent protective layer on one side or both sides.
• the transparent protective layer can be provided as a polymer-coated layer or a film laminate layer.
• the transparent polymer or film forming the transparent protective layer is preferably a transparent polymer or film having high mechanical strength and good thermal stability.
• cellulose acetate resin such as triacetyl cellulose or diacetyl cellulose or film thereof, acrylic resin or film thereof, polyvinyl chloride resin or film thereof, nylon resin or film thereof, polyester resin or film thereof
• imide and / or amide resins or polymers or films thereof include imide and / or amide resins or polymers or films thereof.
• An adhesive is required to bond the transparent protective layer to the polarizing element.
• a polyvinyl alcohol adhesive agent is preferable.
• the polyvinyl alcohol adhesive include, but are not limited to, GOHSENOL NH-26 (manufactured by Nihon Gosei Co., Ltd.) and EXEVAL RS-2117 (manufactured by Kuraray Co., Ltd.).
• a cross-linking agent and / or a waterproofing agent can be added to the adhesive.
• As the polyvinyl alcohol adhesive a maleic anhydride-isobutylene copolymer is used, but if necessary, an adhesive mixed with a crosslinking agent can be used.
• maleic anhydride-isobutylene copolymers for example, isoban # 18 (manufactured by Kuraray), isoban # 04 (manufactured by Kuraray), ammonia-modified isoban # 104 (manufactured by Kuraray), ammonia-modified isoban # 110 (manufactured by Kuraray) ), Imidized isoban # 304 (manufactured by Kuraray), imidized isoban # 310 (manufactured by Kuraray), and the like.
• a water-soluble polyvalent epoxy compound can be used as the crosslinking agent at that time.
• the water-soluble polyvalent epoxy compound examples include Denacol EX-521 (manufactured by Nagase Chemtech) and Tetrat-C (manufactured by Mitsubishi Gas Chemical).
• adhesives other than polyvinyl alcohol resin well-known adhesives, such as urethane type, an acrylic type, and an epoxy type, can also be used.
• additives such as zinc compounds, chlorides, iodides and the like can be simultaneously contained at a concentration of about 0.1 to 10% by weight. The additive is not limited. After laminating the transparent protective layer with an adhesive, the polarizing plate is obtained by drying or heat treatment at a suitable temperature.
• This polarizing plate may have various known functional layers such as an antireflection layer, an antiglare layer, and a hard coat layer on the other surface, that is, the exposed surface of the protective layer or film.
• a coating method is preferable for producing the layer having various functions, but a film having the function can be bonded through an adhesive or a pressure-sensitive adhesive.
• the various functional layers can be a layer or a film for controlling the phase difference.
• a polarizing element or a polarizing plate can be obtained.
• the polarizing element or polarizing plate of the present invention can reduce the discoloration or decoloration without any elution of the azo compound from the polarizing element even when a humidification process or a dipping process in water is applied, the polarizing element For re-stretching or rolling treatment, a polarizing element or a polarizing plate free from elution or precipitation of an azo compound can be produced even if a humidification treatment or a water immersion treatment is applied for reprocessing.
• the polarizing element or polarizing plate of the present invention thus obtained is used as a polarizing lens or a polarizing filter by providing a protective layer or a functional layer and a support as necessary.
• Such polarizing lenses and polarizing filters are suitable for polarized sunglasses or polarized glasses by being installed on a frame or the like.
• the transmittance when the polarizing element or polarizing plate is measured with one sheet is the transmittance Ts, and the two polarizing elements or polarizing plates are stacked so that their absorption axis directions are the same.
• the parallel transmittance Tp was defined as the orthogonal transmittance Tc.
• the single transmittance Ys was calculated by the following formula (I) by obtaining the spectral transmittance ⁇ at predetermined wavelength intervals d ⁇ (here, 5 nm) in the wavelength region of 400 to 700 nm.
• P ⁇ represents a spectral distribution of standard light (C light source)
• y ⁇ represents a 2 ° visual field color matching function.
• the spectral transmittance ⁇ was measured using a spectrophotometer (“U-4100” manufactured by Hitachi, Ltd.).
• ⁇ Production of polarizing element> A polyvinyl alcohol film (VF-XS, manufactured by Kuraray Co., Ltd.) having an average polymerization degree of 2400 having a saponification degree of 99% or more was immersed in warm water at 40 ° C. for 2 minutes, and a swelling treatment was applied to make the draw ratio 1.30 times.
• the swollen film was immersed in an aqueous solution at 45 ° C. containing 3000 parts by weight of water, 3.0 parts by weight of sodium tripolyphosphate, and 4.6 parts by weight of powder 1 of a copper azo compound, followed by dyeing.
• the film obtained by dyeing was stretched for 5 minutes in a 50 ° C.
• aqueous solution containing 30.0 g / liter of boric acid while being stretched 5.0 times.
• water washing treatment is performed for 20 seconds in water at 30 ° C., and the obtained film is subjected to drying treatment at 70 ° C. for 9 minutes, whereby the polarizing element of the present invention Got. 50 mg of the polarizing element of the present invention was weighed, and 0.1% by weight of trimethylolpropane was added as a known amount of internal standard substance.
• a treatment liquid heated by adding 10 ⁇ l of O-bis (trimethylsilyl) trifluoroacetamide and 300 ⁇ l of pyridine and heated at 80 ° C. for 10 minutes was measured with a gas chromatograph (Agilent 6890N). It was 8 ppm when content of the monoethanolamine in it was confirmed.
• Example 2 In the preparation of the dye of Example 1, in the dye drying step after redissolving in a 20% by weight aqueous solution, drying was carried out while spraying in an atmosphere of 105 ° C. to obtain a powder 2 of a copperated azo compound.
• the polarizing element of the present invention was produced.
• the content of monoethanolamine in the powdered copper azo compound powder 2 was 398 parts by weight of monoethanolamine with respect to 1000 parts by weight of the powdered copper azo compound powder 2.
• content of the monoethanolamine in the obtained polarizing element was confirmed, it was 61 ppm.
• Example 3 The powder 1 of the copperated azo compound of Example 1 was a sheet containing 0.8% by weight of methylaminoethanol and 9.7% by weight of diethanolamine. Ai. direct. A polarizing element of the present invention was obtained in the same manner except that it was changed to Blue 199. Methylaminoethanol in the obtained polarizing element was not detected because it was below the measurement limit value, and diethanolamine was 8 ppm.
• Example 4 The powder 1 of the copperated azo compound of Example 1 was a sheet containing 6.9% by weight of monoethanolamine. Ai. direct. A polarizing element of the present invention was obtained in the same manner except that the color was changed to Blue 237. It was 53 ppm when content of the monoethanolamine in the obtained polarizing element was confirmed.
• Example 5 In the manufacturing process of the polarizing element of Example 1, the same as that except that the draw ratio in a boric acid aqueous solution at 50 ° C. was 2.3 times and the draw ratio of the polarizing element was changed to 3 times the original material. Thus, the polarizing element of the present invention was obtained. When the content of monoethanolamine in the obtained polarizing element was confirmed, it was 10 ppm.
• the polarizing element of the present invention was produced in the same manner except that the powder 3 of the copperated azo compound was obtained by drying at 60 ° C. without spraying a 20 wt% aqueous solution. .
• the content of monoethanolamine in the powdered copper azo compound powder 3 was 455 parts by weight of monoethanolamine with respect to 1000 parts by weight of the powdered copper azo compound powder 3.
• the content of monoethanolamine in the obtained polarizing element was confirmed to be 78 ppm.
• Example 3 C.I. containing 12% by weight of methylaminoethanol and 33.5% by weight of diethanolamine.
• a polarizing element of the present invention was obtained in the same manner except that it was changed to Direct Blue 199. Methylaminoethanol in the obtained polarizing element was 4 ppm, and diethanolamine was 72 ppm.
• Comparative Example 4 In the same manner as in Comparative Example 1 except that the film stretched in a 55 ° C. boric acid aqueous solution was kept in a tension state, and was washed with water at 30 ° C. containing 10% by weight of sodium sulfate for 20 seconds. A polarizing element having a large content was obtained. Moreover, when content of the monoethanolamine in the obtained polarizing element was confirmed, it did not change at 78 ppm.
• Comparative Example 5 In Comparative Example 1, the swollen film was added to a 45 ° C. aqueous solution containing 3000 parts by weight of water, 3.0 parts by weight of sodium tripolyphosphate, and 4.6 parts by weight of powder 1 of a copperated azo compound, and a dye. A polarizing element containing a dye fixing agent was obtained in the same manner except that 1.0 part by weight of Kayafix M (manufactured by Nippon Kayaku Co., Ltd.) as a fixing agent was added.
• Kayafix M manufactured by Nippon Kayaku Co., Ltd.
• Table 1 shows the initial transmittance before the humidification and immersion treatment, the transmittance after the treatment, the degree of decolorization at the end of the polarizing element after the treatment, and the degree of elution of the dye in 50 ° C. warm water. The result confirmed visually is described.
• the polyvinyl alcohol-based resin film subjected to stretching treatment containing at least one kind of azo compound in the present application The polarizing element characterized in that the content of the amine compound contained in the film is 70 ppm or less, and the azo compound is not eluted from the polarizing element even when a humidification treatment or a water immersion treatment is applied.
• Discoloration and decoloration can be reduced as much as possible, so even if a humidification treatment or immersion treatment in water is applied to rework the polarizing element for re-stretching or rolling treatment, It can be seen that a polarizing element or a polarizing plate without precipitation can be produced.
• the polarizing element or polarizing plate of the present invention thus obtained is provided with a protective layer or functional layer and a support as necessary, and is subjected to humidification treatment or re-stretching or rolling treatment for curved surface processing or frame processing. Even when an immersion treatment in water or the like is applied, since the transmittance change of the polarizing element is small, such a polarizing element can be used as a polarizing lens or a polarizing filter.
• the obtained polarizing lens and polarizing filter are suitable for polarized sunglasses or polarized glasses by being installed on a frame or the like.

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• Physics & Mathematics (AREA)
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• Ophthalmology & Optometry (AREA)
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• Optics & Photonics (AREA)
• General Health & Medical Sciences (AREA)
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• Organic Chemistry (AREA)
• Polarising Elements (AREA)
• Eyeglasses (AREA)
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• 2014
  • 2014-09-24 JP JP2015539261A patent/JP6769711B2/ja active Active
  • 2014-09-24 CN CN201480048537.3A patent/CN105518495B/zh active Active
  • 2014-09-24 WO PCT/JP2014/075286 patent/WO2015046249A1/ja active Application Filing
  • 2014-09-24 KR KR1020167001189A patent/KR20160061956A/ko not_active Application Discontinuation
  • 2014-09-26 TW TW103133635A patent/TWI608257B/zh active
• 2016
  • 2016-09-03 HK HK16110520.0A patent/HK1222458A1/zh not_active IP Right Cessation
• 2020
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