WO2017030144A1 - 偏光板及びその製造方法 - Google Patents

偏光板及びその製造方法 Download PDF

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Publication number
WO2017030144A1
WO2017030144A1 PCT/JP2016/074000 JP2016074000W WO2017030144A1 WO 2017030144 A1 WO2017030144 A1 WO 2017030144A1 JP 2016074000 W JP2016074000 W JP 2016074000W WO 2017030144 A1 WO2017030144 A1 WO 2017030144A1
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WIPO (PCT)
Prior art keywords
polarizer
polarizing plate
polyvinyl alcohol
film
adhesive layer
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PCT/JP2016/074000
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English (en)
French (fr)
Japanese (ja)
Inventor
天煕 趙
重萬 朴
正寧 崔
容鉉 權
智康 竹内
Original Assignee
住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to KR1020187007371A priority Critical patent/KR20180031801A/ko
Priority to CN201680045107.5A priority patent/CN107850723B/zh
Priority to JP2017535549A priority patent/JP6878281B2/ja
Publication of WO2017030144A1 publication Critical patent/WO2017030144A1/ja

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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
    • G02B5/3033—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
    • G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—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 comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • 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
    • B32B2329/00—Polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals
    • B32B2329/04—Polyvinylalcohol

Definitions

  • the present invention relates to a polarizing plate excellent in both optical characteristics and appearance characteristics, a manufacturing method thereof, and an image display device including the polarizing plate.
  • Image display devices are universally used electronic products such as watches, mobile phones, PDAs, notebooks, PC monitors, DVD players, and TVs.
  • a polarizing plate is used as a basic component of the image display device.
  • Patent Document 1 Korean Published Patent No. 2014-0114923 discloses an adhesive composition manufactured by adding a leveling agent of an acetylene skeleton, improving the contact angle and improving the appearance defect. ing.
  • An object of the present invention is to provide a polarizing plate and an image display apparatus including the same that can prevent appearance defects without deteriorating optical characteristics such as transmittance and degree of polarization.
  • the present invention provides a polarizing plate excellent in physical properties such as adhesiveness, water resistance, moisture resistance, and heat resistance (hereinafter referred to as moisture resistance and heat resistance together) and an image display apparatus including the same.
  • the purpose is to provide.
  • a polarizer having an uneven average interval (RSm) of 500 to 5000 ⁇ m and a maximum height roughness (Rt) of 100 to 1000 nm; an adhesive layer having a thickness of 250 to 850 nm formed on at least one surface of the polarizer; and A polarizing plate comprising: a protective film laminated on the adhesive layer.
  • RSm uneven average interval
  • Rt maximum height roughness
  • the said contact bonding layer is a polarizing plate formed with the adhesive composition containing the polyvinyl alcohol-type resin containing an acetoacetyl group, and a glyoxylate crosslinking agent.
  • a polarizing plate comprising: applying an adhesive composition on any one surface to form an adhesive layer having a thickness of 250 to 850 nm; and (iii) bonding the polarizer and a protective film through the adhesive layer.
  • the adhesive composition includes a polyvinyl alcohol-based resin containing an acetoacetyl group and a glyoxylate crosslinking agent.
  • the polyvinyl alcohol-based resin containing an acetoacetyl group and the glyoxylate cross-linking agent are 2.5 to 6% by weight in total with respect to the total weight of the adhesive composition based on the solid content. Manufacturing method of polarizing plate contained.
  • the polarizing plate according to the present invention has remarkably few appearance defects such as uneven stripes without deteriorating optical properties such as transmittance and polarization degree.
  • the polarizing plate according to the present invention can have excellent adhesion, water resistance, and heat and moisture resistance.
  • the method for manufacturing a polarizing plate according to the present invention it is possible to widen the range in which the polarizer can be used, and to reduce the defect rate, and an additional process for removing defects is unnecessary. Convenience, efficiency and economy can be secured.
  • FIG. 1 is a photograph of analyzing the surface of a polarizer manufactured in a manufacturing example of the present invention.
  • FIG. 2 is a drawing schematically showing a water resistance evaluation test method for a polarizing plate according to the present invention.
  • a polarizer having an average unevenness interval (RSm) of 500 to 5000 ⁇ m and a maximum height roughness (Rt) of 100 to 1000 nm; a thickness 250 formed on at least one surface of the polarizer. It is related with the polarizing plate which was excellent in the optical characteristic and the external appearance characteristic by including the protective film laminated
  • the polarizing plate according to the present invention includes a polarizer having an uneven average interval (RSm) of 500 to 5000 ⁇ m and a maximum height roughness (Rt) of 100 to 1000 nm.
  • RSm uneven average interval
  • Rt maximum height roughness
  • the irregularity average interval (RSm) is a value specified by ISO 4287-1997, and the roughness curve is extracted from the reference length in the direction of the average line, and corresponds to one mountain and one valley adjacent to it. Means the value obtained by calculating the sum of the lengths of the average lines and averaging them within the reference length.
  • interval (RSm) is corresponded to the average length (RSm) of a roughness curve element prescribed
  • the maximum height roughness (Rt) is a value specified by ISO 4287-1997, and means the sum of the maximum value of the peak height of the roughness curve and the maximum value of the valley depth in the standard length.
  • the maximum height roughness (Rt) corresponds to the maximum cross-sectional height (Rt) of the roughness curve defined by JIS B 0601: 2013.
  • the polarizer according to the present invention can produce a polarizing plate excellent in both optical characteristics and appearance characteristics by having the above-mentioned specific ranges of RSm and Rt.
  • RSm is less than 500 ⁇ m, there is a problem that optical characteristics are deteriorated, and when it exceeds 5000 ⁇ m, there is a problem that appearance defects cannot be improved.
  • Rt is less than 100 nm, there is a problem that the optical characteristics are deteriorated, and when it exceeds 1000 nm, there is a problem that appearance defects cannot be improved.
  • RSm is 750 to 5000 ⁇ m and Rt is 120 to 970 nm.
  • the polarizing plate according to the present invention includes an adhesive layer having a thickness of 250 to 850 nm on at least one surface of the polarizer.
  • the polarizer having the RSm and Rt ranges of the present invention is used in the production of a polarizing plate by a usual method, striped pattern unevenness occurs. Therefore, in the present invention, by introducing an adhesive layer having a thickness in the above specific range, the unevenness of the striped pattern of the polarizing plate is remarkably reduced without deterioration of optical characteristics such as the degree of polarization or transparency.
  • the thickness of the adhesive layer is less than 250 nm, the appearance defect cannot be improved, and when it exceeds 850 nm, there is a problem that the optical characteristics are deteriorated.
  • the thickness of the adhesive layer is more preferably 300 to 800 nm from the viewpoint of further reducing the unevenness of the striped pattern of the polarizing plate without lowering the optical characteristics.
  • the method for increasing the thickness of the adhesive layer is not particularly limited.
  • a method for increasing the solid content concentration in the adhesive composition or increasing the bonding speed for bonding the polarizer and the protective film via the adhesive layer. Can be used.
  • the protective film according to the present invention is not particularly limited as long as it is a film excellent in transparency, mechanical strength, thermal stability, moisture shielding property, isotropy, etc.
  • Specific examples include polyethylene terephthalate, polyethylene Polyester resins such as isophthalate and polybutylene terephthalate; Cellulosic resins such as diacetyl cellulose, triacetyl cellulose and cellulose acetate propionate; Polycarbonate resins; Polyacrylic resins such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrenic resins such as polystyrene and acrylonitrile-styrene copolymers; Polyolefin resins such as polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, and ethylene propylene copolymers; Polyamide resins such as nylon and aromatic polyamide; imide resins; polyethersulfone resins;
  • a cycloolefin resin known in the field can be used without particular limitation.
  • the cycloolefin resin may be a thermoplastic resin having a cycloolefin monomer unit such as norbornene or a polycyclic norbornene monomer, and the cycloolefin ring-opening polymer or 2
  • a hydrogenated product of a ring-opening copolymer using more than one kind of cycloolefin may be used, or an addition copolymer of a cycloolefin and an aromatic compound having a chain olefin or a vinyl group may be used.
  • the polar group may be introduce
  • a film composed of a cellulose resin, a polyolefin resin, or a polyacrylic resin is preferable in consideration of polarization characteristics or durability.
  • RSm uneven average interval
  • Rt maximum height roughness
  • a polarizer having an uneven average interval (RSm) of 500 to 5000 ⁇ m and a maximum height roughness (Rt) of 100 to 1000 nm is manufactured (i).
  • the manufacturing process conditions of the polarizer can be adjusted.
  • the stretching ratio, drying time, etc. can be adjusted.
  • an example of the manufacturing method of the polarizer by this invention is demonstrated concretely.
  • the polymer film for manufacturing a polarizer is a polymer film used for manufacturing a polarizing plate
  • a film that can be dyed with a dichroic substance (for example, iodine) that is known in the art is used without particular limitation.
  • a dichroic substance for example, iodine
  • polyvinyl alcohol film partially saponified polyvinyl alcohol film; polyethylene terephthalate film, ethylene-vinyl acetate copolymer film, ethylene-vinyl alcohol copolymer film, cellulose film, these partially saponified Or a hydrophilic polymer film such as a dry film; or a polyene oriented film such as a dehydrated polyvinyl alcohol film, a dehydrochlorinated polyvinyl chloride film, or the like.
  • a polyvinyl alcohol film is preferable because it not only has an excellent effect of enhancing the uniformity of the degree of polarization in the plane, but also has an excellent dyeing affinity for io
  • the manufacturing method of the polarizer may include a swelling step, a dyeing step, a crosslinking step, a complementary color step, a stretching step, a water washing step, and a drying step, and can be classified according to a stretching method.
  • a dry stretching method, a wet stretching method, or a hybrid stretching method in which the above-mentioned two kinds of stretching methods are mixed can be used.
  • the manufacturing method of the polarizer of this invention is demonstrated taking the wet extending
  • the remaining steps except the drying step are performed by immersing the polyvinyl alcohol film in a constant temperature bath filled with at least one solution selected from various types of solutions. It can be carried out.
  • ⁇ Swelling step> In the swelling step, before dyeing the unstretched polyvinyl alcohol film, it is immersed in a swelling tank filled with an aqueous solution for swelling to remove impurities such as dust or anti-blocking agent deposited on the surface of the polyvinyl alcohol film. This is a step for swelling the polyvinyl alcohol film, improving the stretching efficiency, preventing nonuniform dyeing, and improving the physical properties of the polarizer.
  • an aqueous solution for swelling known in the art can be used without particular limitation.
  • water pure water, deionized water
  • glycerin or potassium iodide may be used alone, and a small amount of glycerin or potassium iodide may be used.
  • processability can be improved along with swelling of the polymer film.
  • the glycerin content may be 5% by weight or less and the potassium iodide content may be 10% by weight or less with respect to 100% by weight of the swelling aqueous solution, but is not limited thereto.
  • the temperature of the swelling tank is not particularly limited, but may be 20 to 45 ° C, for example, 25 to 40 ° C.
  • a performance time known in the art can be applied without particular limitation, and may be, for example, 180 seconds or less, preferably 90 seconds or less. .
  • immersion time is in the above range, it is possible to suppress the swelling from becoming excessively saturated, the breakage due to softening of the polyvinyl alcohol film is prevented, and the adsorption of iodine becomes uniform in the dyeing step, The degree of polarization can be improved.
  • the stretching step can be performed together with the swelling step.
  • the stretching ratio may be about 1.1 to 3.5 times, but is not limited, and preferably 1.5 to 3.0 times. Good. If the draw ratio is less than 1.1 times, wrinkles may occur. If it exceeds 3.5 times, the initial optical characteristics may be weakened.
  • the dyeing step is a step of immersing the polyvinyl alcohol film in a dyeing tank filled with a dichroic substance, for example, an aqueous dyeing solution containing iodine, and adsorbing iodine to the polyvinyl alcohol film.
  • a dichroic substance for example, an aqueous dyeing solution containing iodine, and adsorbing iodine to the polyvinyl alcohol film.
  • an aqueous dye solution known in the art can be used without particular limitation, and it can contain water, a water-soluble organic solvent or a mixed solvent thereof and iodine.
  • the iodine content may be 0.4 to 400 mmol / L with respect to the aqueous dyeing solution, but is not limited thereto, and is preferably 0.8 to 275 mmol / L, and most preferably 1 to 200 mmol / L. May be.
  • iodide may be further contained as a solubilizing agent.
  • an iodide known in the art can be used without limitation.
  • iodide At least one selected from the group consisting of barium iodide, calcium iodide, tin iodide, and titanium iodide can be included, and among these, potassium iodide is preferable because of its high solubility in water.
  • the iodide content may be 0.01 to 10% by weight with respect to 100% by weight of the aqueous dyeing solution, but is not limited, and may preferably be 0.1 to 5% by weight.
  • boric acid may be added to the dyeing tank at 0.3 to 5% by weight with respect to 100% by weight of the aqueous dyeing solution. It is not limited. When boric acid dyeing tank is less than 0.3 wt%, PVA-I 3 - complex and PVA-I 5 - it may not be effective in increasing the complex content, boric acid dyeing tank 5 If the concentration is higher than% by weight, the risk of film breakage may increase.
  • the temperature of the dyeing tank may be 5 to 42 ° C, but is not limited thereto, and may preferably be 10 to 35 ° C.
  • the immersion time of the polyvinyl alcohol film in the dyeing tank is not particularly limited, and may be 1 to 20 minutes, preferably 2 to 10 minutes.
  • the stretching step can be performed together with the dyeing step.
  • the stretching ratio may be 1.01 to 2.0 times, but is not limited thereto, and preferably 1. It may be 1 to 1.8 times.
  • the cumulative stretching ratio up to the dyeing step including the swelling and dyeing step may be 1.2 to 4.0 times. If the cumulative stretch ratio is less than 1.2 times, wrinkles of the film may occur and appearance defects may occur, and if it exceeds 4.0 times, the initial optical characteristics may be fragile.
  • the cross-linking step is a step of fixing the adsorbed iodine molecules by immersing the dyed polyvinyl alcohol film in an aqueous solution for cross-linking so that the dyeability by physically adsorbed iodine molecules is not deteriorated by the external environment. is there.
  • iodine which is a dichroic dye
  • iodine molecules may be detached by a moist heat environment, and sufficient crosslinking reaction is required.
  • the method for producing a polarizer can perform a crosslinking step known in the art without particular limitation, for example, can perform a crosslinking step constituted by a first and a second crosslinking step, One or more of the first and second cross-linking steps can use an aqueous cross-linking solution containing a boron compound. This can improve the optical properties and color durability of the polarizer.
  • crosslinking aqueous solution a crosslinking aqueous solution known in the art can be used without particular limitation, and may contain, for example, water as a solvent and a boron compound such as boric acid or sodium borate, together with water. It may further contain a soluble organic solvent and iodide.
  • Boron compounds impart short crosslinks and stiffness to the polarizer, and can suppress wrinkling of the film during the process, improving the handleability of the film and forming the iodine orientation of the polarizer Can play a role.
  • a content of the boron compound may be a content known in the art, and may be, for example, 1 to 10% by weight, preferably 2 to 6% by weight with respect to 100% by weight of the aqueous crosslinking solution. Also good. When the content is less than 1% by weight, the crosslinking effect of the boron compound is reduced, and it may be difficult to impart rigidity to the polarizer. When the content exceeds 10% by weight, the crosslinking reaction of the inorganic crosslinking agent is excessive. When activated, the crosslinking reaction of the organic crosslinking agent may not proceed effectively.
  • iodide can be used to maintain the uniformity of the degree of polarization in the plane of the polarizer and to prevent desorption of dyed iodine.
  • the iodide may be the same as that used in the dyeing step, and its content may be 0.05 to 15% by weight with respect to 100% by weight of the aqueous crosslinking solution, but is not limited, Preferably, it may be 0.5 to 14% by weight. If the content is less than 0.05% by weight, iodine ions in the film may escape and increase the transmittance of the polarizer. If the content exceeds 15% by weight, iodine ions in the aqueous solution may be added to the film. It can penetrate and reduce the transmittance of the polarizer.
  • the temperature of the crosslinking tank may be 20 to 70 ° C., but is not limited thereto.
  • the immersion time of the polyvinyl alcohol film in the crosslinking tank may be 1 second to 15 minutes, but is not limited thereto, and may preferably be 5 seconds to 10 minutes.
  • the stretching step can be performed together with the crosslinking step.
  • the stretching ratio of the first crosslinking step may be 1.4 to 3.0 times, but is not limited thereto, preferably 1.5. Or it may be 2.5 times.
  • the stretching ratio of the second crosslinking step may be 1.01 to 2.0 times, but is not limited thereto, and may preferably be 1.2 to 1.8 times.
  • the cumulative draw ratio of the first and second crosslinking steps may be 1.5 to 5.0 times, but is not limited thereto, and preferably 1.7 to 4.5 times. Good. If the cumulative stretching ratio is less than 1.5 times, the orientation effect of iodine may be insufficient, and if it exceeds 5.0 times, the film may break due to excessive stretching. Yes, production efficiency can be reduced.
  • ⁇ Complementary color step> the iodine complex positioned between the molecules in the polyvinyl alcohol film on which the iodine complex is physically adsorbed is oriented near the boric acid bridge to stabilize the iodine complex. May be.
  • it may be a step of correcting the color with respect to the polyvinyl alcohol film in which the iodine complex is insufficiently dyed in the crosslinking step.
  • an aqueous solution known in the art can be used without particular limitation, and includes, for example, water as a solvent and a boron compound such as boric acid, and an organic solvent and iodide that are mutually soluble with water. May further be included.
  • the boron compound imparts short crosslinks and rigidity to the polarizer, and suppresses wrinkling of the film during the process, thereby improving the handleability of the film and improving the iodine orientation of the polarizer. Can play a role to form.
  • the content of the boron compound may be 1 to 10% by weight with respect to 100% by weight of the aqueous solution in the complementary color step, but is not limited thereto, and may preferably be 2 to 6% by weight.
  • the content is less than 1% by weight, the crosslinking effect of the boron compound is reduced, and it may be difficult to impart rigidity to the polarizer.
  • the content exceeds 10% by weight, the crosslinking reaction of the inorganic crosslinking agent is excessive. When activated, the crosslinking reaction of the organic crosslinking agent may not proceed effectively.
  • iodide can be used to maintain the uniformity of the degree of polarization in the plane of the polarizer and to prevent desorption of dyed iodine.
  • the iodide may be the same as that used in the dyeing step, and the content thereof may be 0.05 to 15% by weight with respect to 100% by weight of the aqueous solution in the complementary color step. However, it may be 0.5 to 11% by weight. If the content is less than 0.05% by weight, iodine ions in the film may escape and increase the transmittance of the polarizer. If the content exceeds 15% by weight, iodine ions in the aqueous solution may be added to the film. It can penetrate and reduce the transmittance of the polarizer.
  • the temperature of the complementary color tank may be 20 to 70 ° C.
  • the immersion time of the polyvinyl alcohol film in the complementary color bath may be 1 second to 15 minutes, but is not limited thereto, and may preferably be 5 seconds to 10 minutes.
  • the stretching step can be performed together with the complementary color step.
  • the stretching ratio of the complementary color step may be 1.01 to 1.1 times, but is not limited thereto, and preferably 1.01 to 1. It may be 08 times.
  • the stabilization effect of the iodine complex may be insufficient, and if it exceeds 1.1 times, the film may be broken by excessive stretching. Production efficiency can be reduced.
  • the stretching step may be performed simultaneously with other steps as described above, or may be performed separately.
  • the stretching step may be performed at least once or may be performed a plurality of times. When it is performed a plurality of times, it may be performed separately at any step in the manufacturing process of the polarizer.
  • the stretch ratio in order to increase Rt, the stretch ratio can be increased, and in order to decrease Rt, it can be adjusted by decreasing the stretch ratio. Moreover, in order to enlarge RSm, it can adjust by enlarging a draw ratio, and in order to make RSm small, it can adjust by making a draw ratio small.
  • the total cumulative draw ratio of the polarizer is preferably 4.0 to 7.0 times, and more preferably 5.3 to 6.5 times.
  • the “cumulative stretch ratio” may include a product of stretch ratios in each step.
  • ⁇ Washing step> The polyvinyl alcohol-based film that has been crosslinked and stretched is immersed in a water-washing tank filled with an aqueous washing solution, and unnecessary residues such as boric acid adhered to the polyvinyl alcohol-based film in the steps up to the water washing step.
  • a rinsing step can be performed.
  • the aqueous washing solution may be an aqueous washing aqueous solution known in the art without particular limitation, and may be, for example, water, to which an iodide may be further added. Not.
  • the temperature of the washing tank may be 10 to 60 ° C, but is not limited thereto, and may preferably be 15 to 40 ° C.
  • the water washing step can be omitted, and can be performed each time a step before the water washing step such as the dyeing step or the crosslinking step is completed. Further, it may be repeated one or more times, and the number of repetitions is not particularly limited.
  • the drying step of the method for producing a polarizer is to dry the washed polyvinyl alcohol film, improve the orientation of dyed iodine molecules by neck-in by drying, and have excellent optical properties.
  • This is a step of obtaining a polarizer.
  • Neck-in means that the width of the film is narrowed.
  • a drying method known in the art can be used without limitation, and methods such as natural drying, air drying, heat drying, far-infrared drying, microwave drying, and hot air drying can be used.
  • Hot air drying can be performed at 20 to 100 ° C. for 1 to 10 minutes.
  • drying temperature can be made low in order to prevent deterioration of a polarizer, it is not restrict
  • the drying time in order to increase Rt, the drying time can be lengthened, and in order to reduce Rt, the drying time can be shortened.
  • it can adjust by lengthening drying time and shortening drying time in order to make RSm small.
  • an adhesive composition is applied on at least one of the polarizer and the protective film to form an adhesive layer of 250 to 850 nm (ii).
  • the adhesive layer can be formed using any adhesive composition known in the art without any particular limitation.
  • a water-based adhesive composition can be used, and the water-based adhesive composition has an aspect of improving water resistance. Therefore, an adhesive composition containing a polyvinyl alcohol-based resin containing an acetoacetyl group and a glyoxylate cross-linking agent can be used.
  • the acetoacetyl group-modified polyvinyl alcohol (PVA) resin can improve the adhesive force between a polyvinyl alcohol (PVA) polarizer and a protective film such as a cellulose film or an olefin film.
  • the acetoacetyl group-modified polyvinyl alcohol (PVA) resin contains a functional group having a higher reactivity than modified polyvinyl alcohol resins such as carboxyl group modification, methylol group modification, amino group modification and the like. Excellent in terms of durability.
  • the acetoacetyl group-modified polyvinyl alcohol resin can be used without particular limitation as long as it is a method known in the art, and can be produced by, for example, reacting a polyvinyl alcohol resin with diketene by a known method.
  • An acetyl group-modified polyvinyl alcohol resin can be obtained.
  • diketene is added here.
  • diketene is added here.
  • An acetoacetyl group-modified polyvinyl alcohol-based resin can be produced by a method in which the diketene gas or liquid diketene is brought into direct contact with the polyvinyl alcohol-based resin.
  • the acetoacetyl group-modified polyvinyl alcohol resin is not particularly limited as long as the degree of acetoacetyl group modification is 0.1 mol% or more, and may be, for example, 0.1 to 40 mol%, preferably 1 to 20 mol. %, Most preferably 2 to 7 mol%.
  • the degree of modification of the acetoacetyl group is less than 0.1 mol%, the adhesive layer may have insufficient water resistance, resulting in incompatibility.
  • the degree of modification of the acetoacetyl group exceeds 40 mol% May have insufficient water resistance improvement effect.
  • the saponification degree of the acetoacetyl group-modified polyvinyl alcohol resin is not particularly limited, but may be 80 mol% or more, and preferably 85 mol% or more.
  • the saponification degree of the polyvinyl alcohol-based resin contained in the adhesive composition is low, it becomes difficult for the adhesive composition to exhibit sufficient water solubility, and thus the adhesiveness may be insufficient.
  • Polyvinyl alcohol used in producing the acetoacetyl group-modified polyvinyl alcohol resin is not particularly limited, but in order to develop high adhesion between the polarizer and the protective film in the polarizing plate, the average degree of polymerization is The average saponification degree may be in the range of 80 to 100 mol%.
  • Examples of the product of the acetoacetyl group-modified polyvinyl alcohol resin include Z-100, Z-200, Z-200H, Z-210, Z-220, and Z-320 (Nippon Synthetic Chemical Co., Ltd.). Can do.
  • the glyoxylate crosslinking agent contained in the adhesive composition of the method for producing a polarizer includes an acetoacetyl group-modified polyvinyl alcohol (PVA) resin, a polyvinyl alcohol (PVA) polarizer, and cellulose. Adhesive force with a protective film such as a film or an olefin film can be improved.
  • PVA polyvinyl alcohol
  • the glyoxylate may be an alkali metal salt or alkaline earth metal salt of glyoxylic acid.
  • the same effect can be obtained when either an alkali metal salt or alkaline earth metal salt of glyoxylic acid is used.
  • alkali metals and alkaline earth metals are elements with low electronegativity, and their carboxylates have similar chemical properties and crosslinks of acetoacetyl-modified polyvinyl alcohol. It functions because it is the aldehyde part of glyoxylate.
  • glyoxylate a glyoxylate known in the art can be used without particular limitation.
  • an alkali metal salt lithium glyoxylate, sodium glyoxylate, potassium glyoxylate and the like may be used.
  • the metal salt may be magnesium glyoxylate, calcium glyoxylate, strontium glyoxylate, barium glyoxylate and the like.
  • an alkali metal salt is preferable because it is easily dissolved in water, and sodium glyoxylate is particularly preferable.
  • the glyoxylate may be in the range of 3 to 25 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin containing an acetoacetyl group.
  • weight ratio of glyoxylate to 3 parts by weight or less with respect to 100 parts by weight of the polyvinyl alcohol resin is less than 3 parts by weight, the water resistance of the adhesive layer when it is made into a polarizing plate is not sufficiently expressed.
  • weight ratio of glyoxylate to 100 parts by weight of the resin exceeds 25 parts by weight, the optical characteristics of the polarizing plate can be deteriorated.
  • the thickness of the adhesive layer according to the present invention can be adjusted, for example, by adjusting the concentration of the solid content in the adhesive composition.
  • the total of the polyvinyl alcohol-based resin containing an acetoacetyl group and the glyoxylate crosslinking agent may be included in an amount of 2.5 to 6% by weight based on the solid content with respect to the total weight of the adhesive composition. However, it may be contained preferably 3 to 5% by weight. If it is in said range, the thickness of an adhesive layer can be adjusted to the range of the thickness of the adhesive layer in the polarizing plate of this invention mentioned above.
  • the adhesive composition can be used in a pH range of 4 to 10.
  • the pH of this aqueous solution is less than 4, when the polarizing plate is produced using this, the water resistance cannot be sufficiently expressed.
  • the agent composition can be gelled.
  • the viscosity of the adhesive composition at 20 ° C. may be in the range of 3 to 25 mPa ⁇ sec.
  • the viscosity of the adhesive composition is less than 3 mPa ⁇ sec, when the polarizing plate is produced using the adhesive composition, the water resistance cannot be sufficiently exhibited, and the viscosity exceeds 25 mPa ⁇ sec. In some cases, the optical characteristics of the polarizing plate may be deteriorated.
  • the adhesive composition is an appropriate addition known in the art, such as a plasticizer, a silane coupling agent, an antistatic agent, fine particles, an alcohol that improves diffusibility, and a metal salt, as long as the effect is not impaired. It may be formed by adding at least one selected from the group consisting of agents.
  • a form known in the art can be applied without particular limitation.
  • a liquid for forming a uniform adhesive layer on the surface of a polarizer or a protective film as an adherend is used. It may be a mold.
  • Such a liquid type adhesive may be a solution type or a dispersion type of various solvents, and is preferably a solution type in consideration of the coatability of the substrate, and water in consideration of the stability. Solution type or dispersion type as solvent may be compatible.
  • a water / alcohol mixed solvent in which an alcohol solvent having a boiling point lower than that of water and mixed with water can be used in the adhesive solution.
  • the boiling point of the alcohol solvent is not particularly limited, and the boiling point may be 100 ° C. or lower and 80 ° C. or lower, but preferably 70 ° C. or lower.
  • the adhesive composition can be applied to the adhesive surface of the polarizer and / or the protective film, and both can be superimposed.
  • bonding means that the polarizer and the protective film are indirectly brought into contact with each other via an adhesive layer to be bonded.
  • the polarizer and the protective film can be sandwiched by nip rolls and joined.
  • the joining speed can be applied without limitation as long as the joining speed can increase the thickness of the adhesive layer.
  • the joining speed for joining the protective film to the adhesive layer is 10 to 35 m / min. However, it may be 20 to 30 m / min. If it is in said range, the thickness of an adhesive layer can be adjusted to the range of the thickness of the adhesive layer in the polarizing plate of this invention mentioned above.
  • the bonding speed refers to the length of the polarizer and the protective film bonded via the adhesive layer per unit time.
  • area can be applied without a restriction
  • Surface treatment such as saponification treatment may be performed.
  • the saponification treatment may include a method of immersing in an aqueous solution of an alkali such as sodium hydroxide or potassium hydroxide.
  • the drying treatment can be carried out after the polarizer, the adhesive layer and the protective film are laminated.
  • a drying treatment known in the art can be applied without particular limitation.
  • the drying treatment can be performed by spraying hot air, and the temperature at that time may be in the range of 50 to 100 ° C., The drying time may be 30 to 1,000 seconds, but is not limited thereto.
  • this invention provides the image display apparatus containing the said polarizing plate.
  • the polarizing plate according to the present invention can be applied to an image display device further including a configuration known in the art in addition to the polarizing plate.
  • the image display device to which the polarizing plate according to the present invention can be applied is not particularly limited as long as the polarizing plate can be applied.
  • a normal liquid crystal display device, an electroluminescence display device, a plasma display device can be used.
  • Various image display devices such as a field emission display device may be used.
  • the film was stretched at stretch ratios of 1.56 times and 1.64 times, respectively, and stretched so that the cumulative stretch ratio up to the dyeing tank was 2.56 times.
  • the film was immersed in an aqueous solution for crosslinking at 56 ° C. containing 13.9% by weight of potassium iodide and 3% by weight of boric acid for 26 seconds (first crosslinking step) and crosslinked at a stretching ratio of 1.7 times. Stretched. Thereafter, the film was immersed in an aqueous solution for crosslinking at 56 ° C. containing 13.9% by weight of potassium iodide and 3% by weight of boric acid for 20 seconds (second crosslinking step), and crosslinked at a ratio of 1.34 times.
  • the film was stretched 1.01 times while immersed for 10 seconds in a complementary color aqueous solution containing 5% by weight of potassium iodide and 2% by weight of boric acid (complementary color step). At this time, the total cumulative draw ratio of swelling, dyeing and crosslinking, and complementary color steps was set to 6 times.
  • the measuring method of RSm and Rt is as follows. After preparing the polarizer manufactured in the manufacturing example so as to have a size of 10 mm in width and 10 mm in length, it is bent on the X / Y stage of a Bruker interferometer microscope (model Contour GT-I) on the surface of the sample. Secure with tape to keep it from happening.
  • the measurement method is: AccurityXR PSI Mode, Object 10X, Multiplier 1.0X, Measurement area 10mm x 10mm, After setting the conditions with illumination Green, the surface of the polarizer is measured, and RSm and Rt are calculated based on ISO 4287-1997. Calculated.
  • FIG. 1 For reference, a photograph of the surface of the manufactured polarizer is shown in FIG.
  • the fluorescent lamp reflection method is an evaluation method in which light from a fluorescent lamp is incident from an oblique direction of about 45 °, and unevenness of a polarizing plate is visually confirmed with reflected light.
  • Lv1. Unevenness of striped pattern cannot be confirmed
  • Lv2. In the fluorescent lamp reflection method, striped pattern unevenness can be visually recognized, but cannot be visually confirmed.
  • Lv3. Stripe pattern irregularity is visible with fluorescent lamp reflection method and visual inspection
  • ⁇ Production Example 5 Production of polarizer> The immersion time of the swelling step is changed from 1 minute 20 seconds to 50 seconds, the immersion time of the dyeing step is changed from 2 minutes 30 seconds to 2 minutes, and the cumulative stretch ratio until the dyeing step is increased from 2.56 times to 3 times.
  • This aqueous solution of acetoacetyl group-modified polyvinyl alcohol resin and sodium glyoxylate (10% aqueous solution) as a cross-linking agent are combined with 100 parts by weight of acetoacetyl group-modified polyvinyl alcohol resin solid content of solid content of sodium glyoxylate.
  • the pH of the adhesive composition was 6.1 and the viscosity was 7.5 mPa ⁇ sec.
  • the plate was dried at a temperature of 80 ° C. for 5 minutes to produce a polarizing plate (adhesive layer thickness: 300 nm).
  • Example 2-9 and Comparative Example 1-4> As shown in Table 1, a polarizing plate was produced in the same manner as in Example 1 except that the concentration of the adhesive solid and the bonding speed were changed in order to adjust the thickness of the adhesive layer. However, as the cross-linking agent in the adhesive composition of Example 7, methylol melamine manufactured by Aldrich was used.
  • Example 10 and 11 A polarizing plate was produced in the same manner as in Example 1 (Example 10) and Example 2 (Example 11), respectively, except that the polarizer of Production Example 2 was used.
  • Example 12 A polarizing plate was produced in the same manner as in Example 1 (Example 12) and Example 2 (Example 13), respectively, except that the polarizer of Production Example 3 was used.
  • Example 14 A polarizing plate was produced in the same manner as in Example 1 except that the polarizer of Production Example 5 was used.
  • Adhesiveness After leaving each polarizing plate at room temperature for 1 hour, insert a cutter blade between each film of the polarizing plate (between the polarizer and one protective film and between the polarizer and the other protective film).
  • the method of inserting the blade when pushing forward was evaluated according to the following criteria.
  • ⁇ When the blade is pushed forward, it stops when the blade enters between at least one film and greater than 2 mm and 5 mm or less.
  • FIG. 2 is a drawing schematically showing a water resistance evaluation test method.
  • FIG. 2 (A) shows a sample (1) before immersion in warm water
  • FIG. 2 (B) shows a sample (2) before immersion in warm water
  • FIG. 2 (B) shows a sample (1 after immersion in warm water). ). As shown in FIG. 2 (A), one short side of the sample was gripped by the gripping part (5), and about 80% of the length direction was immersed in a 60 ° C. water bath and maintained for 4 hours. Then, the sample (1) was taken out from the water tank and the moisture was wiped off.
  • the polarizer (4) of the polarizing plate contracts by immersion in hot water.
  • the degree of contraction of the polarizer (4) was measured by measuring the distance from the end (1a) (end of the protective film) of the sample (1) at the center of the short side of the sample (1) to the end of the contracted polarizer (4).
  • the shrinkage length was evaluated.
  • the polarizer (4) located in the middle of the polarizing plate is contracted by immersion in warm water, so that a region (2) where the polarizer (4) does not exist between the protective films. It is formed.
  • iodine elutes from the peripheral part of the polarizer (4) in contact with the hot water by immersion in the hot water, and a part (3) where the color is lost is generated in the peripheral part of the sample (1).
  • the degree of decolorization is evaluated by measuring the distance from the end of the contracted polarizer (4) at the center of the short side of the sample (1) to the region (6) where the specific color of the polarizing plate remains, and iodine. I made it a missing length. Further, the total of the shrinkage length and iodine removal length was defined as the total erosion length (X).
  • the total erosion length (X) is an area where the characteristic color of the polarizing plate remains from the end (1a) (end of the protective film) of the sample (1) at the center of the short side of the sample (1) (6 ). It can be judged that the adhesiveness (water resistance) in the presence of water is higher as the shrinkage length, iodine loss length and total erosion length (X) are smaller.
  • ⁇ Total erosion length X is less than 2 mm
  • ⁇ Total erosion length X is 2 mm or more and less than 3 mm
  • Total erosion length X is 3 mm or more and less than 5 mm
  • Total erosion length X is 5 mm or more
  • Polarization degree (P) [(T1-T2) / (T1 + T2)] 1/2 (In the formula, T1 is a parallel transmittance obtained when a pair of polarizers are arranged with the absorption axes parallel to each other, and T2 is obtained when a pair of polarizers are arranged with the absorption axes orthogonal to each other. Orthogonal transmission).
  • the polarizing plates of the examples are superior in both optical characteristics (polarization degree) and appearance characteristics (level of stripe pattern unevenness) as compared with the comparative examples.
  • Example 1 using sodium glyoxylate as a crosslinking agent is superior in water resistance to Example 7 using methylol melamine as a crosslinking agent.
  • Sample 1a Edge of the protective film 2: Area where the polarizer is not present 3: Area where the color is missing in the peripheral part of the sample 4: Polarizer 5: Holding part 6: Area where the characteristic color of the polarizing plate remains

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Liquid Crystal (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2016/074000 2015-08-18 2016-08-17 偏光板及びその製造方法 WO2017030144A1 (ja)

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KR20180031801A (ko) 2018-03-28
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