WO2020090196A1 - Plaque de polarisation avec couche d'adhésif - Google Patents

Plaque de polarisation avec couche d'adhésif Download PDF

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Publication number
WO2020090196A1
WO2020090196A1 PCT/JP2019/032973 JP2019032973W WO2020090196A1 WO 2020090196 A1 WO2020090196 A1 WO 2020090196A1 JP 2019032973 W JP2019032973 W JP 2019032973W WO 2020090196 A1 WO2020090196 A1 WO 2020090196A1
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Prior art keywords
adhesive layer
polarizer
sensitive adhesive
pressure
weight
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PCT/JP2019/032973
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English (en)
Japanese (ja)
Inventor
聡司 三田
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日東電工株式会社
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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to JP2020554778A priority Critical patent/JP7126796B2/ja
Priority to CN201980070493.7A priority patent/CN112955791B/zh
Priority to KR1020217012291A priority patent/KR20210084464A/ko
Publication of WO2020090196A1 publication Critical patent/WO2020090196A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • 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 polarizing plate with an adhesive layer.
  • a liquid crystal display device which is a typical image display device, has a polarizer (substantially a polarizing plate including a polarizer) arranged on both sides of a liquid crystal cell due to its image forming method.
  • the polarizer is typically manufactured by dyeing a polyvinyl alcohol (PVA) resin film with a dichroic material such as iodine.
  • PVA polyvinyl alcohol
  • the polarizer is usually attached to another component (for example, a protective film) via an adhesive layer.
  • a protective film for example, a protective film
  • Various materials may be used for the composition forming the pressure-sensitive adhesive layer (pressure-sensitive adhesive composition) in order to impart desired properties.
  • the composition contained in the pressure-sensitive adhesive composition is impaired by the migration of the material to the polarizer, and desired characteristics cannot be maintained.
  • JP 2012-247574 A JP, 2017-102476, A JP, 2005-094906, A JP, 2005-094907, A
  • the present invention has been made to solve the above problems, its main purpose is to have a very excellent heat resistance, and a pressure-sensitive adhesive layer-attached polarizing plate with little change over time in the properties of the pressure-sensitive adhesive layer. To provide.
  • the pressure-sensitive adhesive layer-attached polarizing plate of the present invention comprises a polarizer, a protective film arranged on one side of the polarizer, and a pressure-sensitive adhesive layer containing a lithium salt arranged on the other side of the polarizer.
  • the lithium content (Li POL ) of the polarizer is 0.3% by weight or more
  • the lithium content (Li PSA ) of the pressure-sensitive adhesive layer is 0.0035% by weight or more.
  • the ratio (Li POL / Li PSA ) of the lithium content (Li POL ) of the polarizer and the lithium content (Li PSA ) of the adhesive layer is 100 or less.
  • the iodine content of the polarizer is 10% to 25% by weight.
  • the polarizer contains at least one selected from the group consisting of citric acid and citrate ions.
  • the thickness of the polarizer is 3 ⁇ m or less.
  • the pressure-sensitive adhesive layer-attached polarizing plate of the present invention comprises a polarizer, a protective film arranged on one side of the polarizer, and a pressure-sensitive adhesive layer containing a lithium salt arranged on the other side of the polarizer. Including.
  • the lithium content (Li POL ) of the polarizer of this polarizing plate is 0.3% by weight or more and the lithium content (Li PSA ) of the pressure-sensitive adhesive layer is 0.0035% by weight or more, heat resistance is improved.
  • a polarizing plate with an adhesive layer having excellent properties can be provided.
  • the polarizer and the pressure-sensitive adhesive layer contain lithium in a specific content, it is possible to reduce changes over time in the characteristics (specifically, conductivity) of the pressure-sensitive adhesive layer.
  • FIG. 1 is a schematic cross-sectional view of a polarizing plate with an adhesive layer according to one embodiment of the present invention.
  • the pressure-sensitive adhesive layer-attached polarizing plate 100 of the illustrated example is a pressure-sensitive adhesive layer including a polarizer 10, a protective film 20 arranged on one side of the polarizer 10, and a lithium salt arranged on the other side of the polarizer. 30 and.
  • the adhesive layer 30 is typically the outermost layer on the image display device side. Practically, a separator (not shown) is detachably temporarily attached to the pressure-sensitive adhesive layer 30 to protect the pressure-sensitive adhesive layer until actual use and enable roll formation.
  • the pressure-sensitive adhesive layer-attached polarizing plate of the present invention is used in combination with a pressure-sensitive adhesive layer containing a lithium salt that functions as a conductive agent, and a polarizer having a lithium content (Li POL ) of 0.3% by weight or more. It is considered that lithium ions contained in the pressure-sensitive adhesive layer can stabilize the iodine complex more than other cations (eg potassium ions) contained in the polarizer.
  • Li POL lithium content
  • the lithium ions contained in the pressure-sensitive adhesive layer and the iodine complex in the polarizer are bonded to each other to form a more stable iodine complex, and the lithium ions in the pressure-sensitive adhesive layer and other ions contained in the polarizer ( Exchange reactions with, for example, potassium ions) can occur.
  • a more stable iodine complex it is possible to suppress the reduction of iodine (particularly, polyiodine ions such as I 3 ⁇ and I 5 ⁇ ) in the polarizer under a high temperature environment.
  • lithium contained in the pressure-sensitive adhesive layer excessively shifts to the polarizer, the lithium content (Li POL ) of the pressure-sensitive adhesive layer itself is lowered, and desired characteristics (for example, surface resistance value) are deteriorated with time. obtain. As a result, this may also result in deterioration of the characteristics of the polarizing plate with time.
  • the polarizer used in the present invention is treated with a treatment liquid containing lithium ions as described later. Therefore, first, it is considered that an exchange reaction between lithium ions contained in the treatment liquid and other ions (for example, potassium ions) of the polarizer occurs. Due to this exchange reaction, the polarizer itself contains lithium. Therefore, an excessive exchange reaction with lithium ions contained in the pressure-sensitive adhesive layer is suppressed, and it is possible to reduce the change over time in the characteristics (for example, conductivity) of the pressure-sensitive adhesive layer.
  • the lithium content (Li POL ) of the polarizer is 0.3% by weight or more, preferably 0.35% by weight or more.
  • the lithium content (Li POL ) of the polarizer is, for example, 10% by weight or less.
  • the lithium content (Li POL ) can be measured, for example, by ICP-MS.
  • the lithium content (Li PSA ) of the pressure-sensitive adhesive layer is 0.0035% by weight or more, preferably 0.0040% by weight or more, and more preferably 0.0050% by weight or more.
  • the pressure-sensitive adhesive layer can exhibit desired conductive performance.
  • the lithium content (Li PSA ) of the pressure-sensitive adhesive layer can be measured by ICP-MS.
  • the pressure-sensitive adhesive layer-attached polarizing plate of the present invention has a ratio (Li POL / Li PSA ) between the lithium content (Li POL ) of the polarizer and the lithium content (Li PSA ) of the pressure-sensitive adhesive layer, which is hereinafter referred to as “lithium content ratio”. (Also referred to as)) is preferably 100 or less, and more preferably 85 or less. Since the lithium content ratio (Li POL / Li PSA ) of the polarizing plate is within the above range, excellent heat resistance can be achieved even when the thickness is thin, and the characteristics of the pressure-sensitive adhesive layer can be changed with time. Can be made smaller.
  • the lithium content ratio is, for example, 30 or more, preferably 60 or more.
  • the polarizer, the protective film, and the pressure-sensitive adhesive layer that compose the polarizing plate with the pressure-sensitive adhesive layer will be specifically described.
  • the polarizer is typically composed of a polyvinyl alcohol (PVA) resin film.
  • PVA polyvinyl alcohol
  • Examples of the PVA-based resin forming the PVA-based resin film 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 mol% or more and less than 100 mol%, preferably 95.0 mol% to 99.95 mol%, more preferably 99.0 mol% to 99.93 mol%. is there.
  • the saponification degree 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. If the degree of saponification is too high, gelation may occur.
  • 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 4500, and more preferably 1500 to 4300.
  • the average degree of polymerization can be determined according to JIS K 6726-1994.
  • the PVA-based resin film may be a PVA-based resin layer formed on the base material.
  • the laminate of the base material and the PVA-based resin layer can be obtained by, for example, a method of applying the coating liquid containing the PVA-based resin to the base material, a method of laminating a PVA-based resin film on the base material, or the like.
  • the lithium content (Li POL ) of the polarizer is 0.3% by weight or more, preferably 0.35% by weight or more.
  • the polarizer may include lithium during its manufacturing process.
  • the polarizer obtained by treating the PVA-based resin film with a treatment liquid containing lithium may contain lithium.
  • the polarizer contains lithium, it is possible to suppress changes in characteristics of the pressure-sensitive adhesive layer with time due to excessive migration of lithium contained in the pressure-sensitive adhesive layer to the polarizer.
  • the lithium content (Li POL ) of the polarizer is, for example, 10% by weight or less.
  • the iodine content of the polarizer can be appropriately set so as to achieve both sufficient polarization performance and optimum single transmittance.
  • the iodine content is preferably 10% by weight to 25% by weight, more preferably 15% by weight to 25% by weight. According to the pressure-sensitive adhesive layer-attached polarizing plate of the present invention, even if it is a polarizing plate including a polarizer having such an extremely high iodine content, it is difficult in the past by adopting a specific pressure-sensitive adhesive layer described below. It is possible to realize the very excellent heat resistance that was present.
  • the “iodine content” means the total amount of iodine contained in the polarizer (PVA-based resin film).
  • iodine is present in the polarizer in the form of iodine ion (I ⁇ ), iodine molecule (I 2 ), polyiodine ion (I 3 ⁇ , I 5 ⁇ ), etc.
  • the iodine content means the amount of iodine including all these forms.
  • the iodine content can be calculated, for example, by a calibration curve method of fluorescent X-ray analysis.
  • the polyiodine ion exists in a state of forming a PVA-iodine complex in the polarizer. By forming such a complex, absorption dichroism can be exhibited in the wavelength range of visible light.
  • the complex of PVA and triiodide ion (PVA ⁇ I 3 ⁇ ) has an absorption peak near 470 nm, and the complex of PVA and pentaiodide ion (PVA ⁇ I 5 ⁇ ) is around 600 nm. Has an absorption peak at.
  • polyiodine ions can absorb light in a wide range of visible light, depending on their morphology.
  • iodine ion (I ⁇ ) has an absorption peak near 230 nm and does not substantially participate in absorption of visible light. Therefore, the polyiodine ion existing in the form of a complex with PVA may be mainly involved in the absorption performance of the polarizer.
  • the thickness of the polarizer is preferably 5 ⁇ m or less in one embodiment, preferably 3 ⁇ m or less in another embodiment, and preferably 2 ⁇ m or less in yet another embodiment.
  • the thickness of the polarizer is preferably 0.5 ⁇ m or more in one embodiment, preferably 0.6 ⁇ m or more in another embodiment, and 0.8 ⁇ m in still another embodiment. Above, in another embodiment, it is preferably 1 ⁇ m or more, and in yet another embodiment, preferably 2 ⁇ m or more. According to the embodiments of the present invention, it is possible to achieve desired single transmittance and degree of polarization even with a thin polarizer.
  • the single transmittance (Ts) of the polarizer is preferably 30.0% to 43.0%, more preferably 35.0% to 41.0%.
  • the polarization degree of the polarizer is preferably 99.9% or more, more preferably 99.95% or more, and further preferably 99.98% or more.
  • the single transmittance is a value measured by a spectrophotometer with an integrating sphere.
  • the single transmittance is a Y value measured by a JIS Z 8701 2 degree visual field (C light source) and subjected to luminosity correction.
  • an ultraviolet-visible spectrophotometer with an integrating sphere manufactured by JASCO Corporation, product name : V7100.
  • the iodine content of the polarizer is extremely high as described above, changes in optical properties under a high temperature environment can be significantly suppressed. Further, the hue change under the high temperature environment is also suppressed. As described above, such an excellent effect can be realized by using a pressure-sensitive adhesive layer containing a lithium salt functioning as a conductive agent in combination with the above-mentioned polarizer.
  • the polarizer may preferably contain citric acid and / or citrate ions.
  • the polarizer may more preferably include citrate ions. This is due to the treatment (B-2-2) with the treatment liquid in the production method (B) described later.
  • the polarizer contains such a compound (in other words, by manufacturing the polarizer by the manufacturing method including the treatment described in the paragraph B-2-2), the discoloration of the polarizer in a high temperature environment becomes remarkable. Can be suppressed to. This can suppress the generation of protons in the PVA-based resin by the buffering action of the treatment liquid in a predetermined pH region, and as a result, the generation of a large number of double bonds (polyene) in the PVA-based resin under a high temperature environment.
  • a polarizer can be manufactured by a manufacturing method including at least stretching and dyeing a PVA-based resin film.
  • the manufacturing method includes a step of preparing a PVA-based resin film, a stretching step, a swelling step, a dyeing step, a crosslinking step, a washing step, and a drying step.
  • the steps of providing the PVA-based resin film can be performed in any suitable order and timing. Therefore, the steps may be performed in the above order or may be performed in a different order from the above. You may perform one process several times as needed.
  • steps other than the above may be performed at any appropriate timing, and steps other than the dyeing step may be omitted.
  • the PVA-based resin film is the PVA-based resin layer formed on the base material, the laminate of the base material and the PVA-based resin layer is subjected to the above steps.
  • the polarizer of the polarizing plate of the present invention contains lithium. Therefore, it is preferable that the method for manufacturing the polarizer includes a treatment step with a treatment liquid containing lithium.
  • a treatment liquid containing lithium specifically, a treatment liquid containing lithium iodide and / or lithium hydroxide in water or an appropriate solvent other than water is used.
  • the polarizer may contain lithium by undergoing a treatment process with a treatment liquid containing lithium. The treatment process with the treatment liquid can be performed at any appropriate timing after the above-mentioned staining.
  • the method for producing the polarizer used in the present invention includes treating the PVA-based resin film with a treatment liquid containing lithium after dyeing.
  • the treatment with the treatment liquid may be performed at any appropriate timing after dyeing. Specifically, the treatment with the treatment liquid may be performed before or after the crosslinking step, or may be performed before or after the washing step.
  • the treatment with the treatment liquid may be performed before or after the stretching step.
  • the swelling step is performed after the dyeing step
  • the treatment with the treatment liquid may be performed before or after the swelling step.
  • the insolubilization step is performed after the dyeing step, the treatment with the treatment liquid may be performed before or after the insolubilization step.
  • the treatment with the treatment liquid can be performed after the washing step and before the drying step, or between the first drying step and the second drying step when the drying step is performed in two steps.
  • the pH of the treatment liquid is preferably 2.5 to 6.0, more preferably 3.0 to 5.7, and further preferably 3.5 to 4.8. Furthermore, the treatment liquid preferably has a buffering action in the pH range (that is, in the pH range of 2.5 to 6.0).
  • a treatment liquid may be, for example, an aqueous solution containing sodium hydrogen carbonate, potassium hydrogen carbonate, disodium hydrogen phosphate, potassium carbonate, sodium carbonate, and citric acid.
  • the treatment liquid containing these compounds has a buffering action in a high pH region as compared with the treatment liquid containing an acetic acid compound, and as a result, it may have a better discoloration preventing effect in a high temperature environment.
  • the aqueous solution may contain these compounds individually and may contain 2 or more types.
  • the treatment liquid is preferably an aqueous solution of citric acid. Therefore, the polarizer used in the present invention may include citrate and / or citrate ions.
  • the concentration of the aqueous solution can be set appropriately depending on the desired pH and buffering effect. For example, the concentration of the aqueous citric acid solution may preferably be 0.10% by weight to 3.0% by weight.
  • the aqueous solution preferably contains a pH adjuster. Examples of the pH adjuster include lithium hydroxide. By using the treatment liquid containing lithium hydroxide as the pH adjuster, the obtained polarizer may contain lithium.
  • the treatment with the treatment liquid typically includes contacting the treatment liquid with a PVA-based resin film.
  • the contact method includes any appropriate method. Specific examples include immersion of the PVA-based resin film in the treatment liquid and application or spraying of the treatment liquid on the PVA-based resin film. Application or spraying of the treatment liquid is preferred. This is because it is possible to prevent a defect that the absorption spectrum of the polarizer changes before and after the immersion, and as a result, it is possible to more favorably prevent polyeneization of PVA. Any appropriate method (means) can be adopted as a method (means) for applying or spraying the treatment liquid onto the PVA-based resin film.
  • the coating means examples include a reverse coater, a gravure coater (direct, reverse or offset), a bar reverse coater, a roll coater, a die coater, a bar coater, and a rod coater.
  • a spraying means any suitable spraying device (for example, a pressure nozzle type, a rotating disk type) can be mentioned.
  • the PVA-based resin film is typically uniaxially or biaxially stretched 3 to 7 times.
  • the stretching direction may be the longitudinal direction (MD direction) of the film, the width direction (TD direction) of the film, or both the longitudinal direction and the width direction.
  • the stretching method may be dry stretching, wet stretching, or a combination thereof.
  • the PVA-based resin film may be stretched when performing the crosslinking step, the swelling step, the dyeing step, and the like.
  • the stretching direction may correspond to the absorption axis direction of the obtained polarizer.
  • the swelling step is usually performed before the dyeing step.
  • the swelling step is performed, for example, by immersing the PVA-based resin film in a swelling bath.
  • a swelling bath water such as distilled water or pure water is usually used.
  • the swelling bath may include any suitable other component than water.
  • Other components include solvents such as alcohols, additives such as surfactants, iodides and the like.
  • Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. Etc. Preferably potassium iodide is used.
  • the temperature of the swelling bath is, for example, 20 ° C to 45 ° C.
  • the immersion time is, for example, 10 seconds to 300 seconds.
  • the dyeing step is a step of dyeing the PVA-based resin film with a dichroic material. It is preferably carried out by adsorbing a dichroic substance.
  • the adsorption method include a method of immersing a PVA-based resin film in a dyeing solution containing a dichroic substance, a method of applying the dyeing solution to the PVA-based resin film, and a spraying of the dyeing solution onto the PVA-based resin film. And the like.
  • the preferred method is to immerse the PVA resin film in the dyeing solution. This is because the dichroic substance can be favorably adsorbed.
  • dichroic substances examples include iodine and dichroic dyes.
  • an iodine aqueous solution is preferably used as the dyeing solution.
  • the iodine content of the aqueous iodine solution is preferably 0.04 to 5.0 parts by weight with respect to 100 parts by weight of water.
  • iodide is added to the aqueous iodine solution.
  • Potassium iodide is preferably used as the iodide.
  • the iodide content is preferably 0.3 to 15 parts by weight with respect to 100 parts by weight of water.
  • the temperature of the dyeing solution at the time of dyeing can be set to any appropriate value, for example, 20 ° C to 50 ° C.
  • the immersion time is, for example, 5 seconds to 5 minutes.
  • a boron compound is usually used as a crosslinking agent.
  • the boron compound include boric acid and borax. Boric acid is preferred.
  • the boron compound is usually used in the form of an aqueous solution.
  • the boric acid concentration of the boric acid aqueous solution is, for example, 1% by weight to 15% by weight, preferably 1% by weight to 10% by weight.
  • the boric acid aqueous solution may further contain an iodide such as potassium iodide and a zinc compound such as zinc sulfate and zinc chloride.
  • the cross-linking step can be performed by any appropriate method.
  • a method of immersing a PVA-based resin film in an aqueous solution containing a boron compound a method of applying an aqueous solution containing a boron compound to a PVA-based resin film, or a method of spraying an aqueous solution containing a boron compound onto a PVA-based resin film is mentioned. Be done. Immersion in an aqueous solution containing a boron compound is preferred.
  • the temperature of the solution used for crosslinking is, for example, 25 ° C or higher, preferably 30 ° C to 85 ° C, more preferably 40 ° C to 70 ° C.
  • the immersion time is, for example, 5 seconds to 800 seconds, preferably 8 seconds to 500 seconds.
  • the washing step can be typically performed after the crosslinking step.
  • the cleaning step is typically performed by immersing the PVA-based resin film in a cleaning liquid. Pure water is a typical example of the cleaning liquid. You may add potassium iodide to pure water.
  • the temperature of the cleaning liquid is, for example, 5 ° C to 50 ° C.
  • the immersion time is, for example, 1 second to 300 seconds.
  • the drying step can be performed by any appropriate method. Examples of the drying method include natural drying, blast drying, reduced pressure drying, and heat drying. Heat drying is preferably used. When heat drying is performed, the heating temperature is, for example, 30 ° C. to 100 ° C. The drying time is, for example, 20 seconds to 10 minutes.
  • any suitable resin film is used as the protective film (and another protective film when present).
  • the material for forming the resin film include (meth) acrylic resins, cellulose resins such as diacetyl cellulose and triacetyl cellulose, cycloolefin resins such as norbornene resins, olefin resins such as polypropylene, and polyethylene terephthalate resins. And the like, ester-based resins, polyamide-based resins, polycarbonate-based resins, copolymer resins thereof, and the like.
  • the “(meth) acrylic resin” means an acrylic resin and / or a methacrylic resin.
  • a (meth) acrylic resin having a glutarimide structure is used as the (meth) acrylic resin.
  • the (meth) acrylic resin having a glutarimide structure (hereinafter, also referred to as glutarimide resin) is disclosed in, for example, JP-A-2006-309033, JP-A-2006-317560, JP-A-2006-328329, and JP-A-2006-328329. No. 2006-328334, No. 2006-337491, No. 2006-337492, No. 2006-337493, No. 2006-337569, No. 2007-009182, No. 2009- It is described in Japanese Patent Application No. 161744 and Japanese Patent Application Laid-Open No. 2010-284840. These descriptions are incorporated herein by reference.
  • the base material When a polarizer is manufactured using a laminate of a base material and a PVA-based resin layer, the base material may be directly used as a protective film without being peeled off. Alternatively, the base material may be peeled off and the polarizer may be attached to the protective film.
  • any suitable optical functional film may be used as the protective film (and another protective film if present).
  • the optical functional film include a retardation film and a reflective polarizer (brightness improving film).
  • Adhesive Layer A polarizing plate with an adhesive layer according to an embodiment of the present invention typically has a protective film disposed on one side of the polarizer and an adhesive layer disposed on the other side of the polarizer, as described above. Has been done. That is, in this embodiment, the pressure-sensitive adhesive layer is directly arranged on the polarizer without disposing the protective film on the other side of the polarizer.
  • the lithium content (Li PSA ) of the pressure-sensitive adhesive layer is 0.0035% by weight or more, preferably 0.0040% by weight or more, and more preferably 0.0050% by weight or more.
  • the pressure-sensitive adhesive layer can exhibit desired conductive performance.
  • the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer contains a base polymer and a lithium salt.
  • Base Polymer A typical example of the base polymer is a (meth) acrylic polymer ((meth) acrylic resin).
  • the (meth) acrylic polymer typically contains a monomer unit derived from an alkyl (meth) acrylate as a main component.
  • Alkyl (meth) acrylate is an alkyl ester of (meth) acrylic acid. Examples of the alkyl group forming the alkyl ester include a linear or branched alkyl group having 1 to 18 carbon atoms.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, nonyl group, decyl group.
  • the average carbon number of the alkyl group contained in the (meth) acrylic polymer is preferably 3-9.
  • the base polymer may include monomer units derived from any appropriate copolymerization component depending on the purpose.
  • the copolymerization component include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an acid anhydride group-containing monomer, a sulfonic acid group-containing monomer, a phosphoric acid group-containing monomer, an (N-substituted) amide monomer, and a (meth) acryl.
  • Acid alkylaminoalkyl-based monomer (meth) acrylic acid alkoxyalkyl-based monomer, succinimide-based monomer, maleimide-based monomer, itaconimide-based monomer, vinyl-based monomer, cyano (meth) acrylate-based monomer, epoxy group-containing (meth) acrylic-based monomer , Glycol (meth) acrylic ester monomers, silane monomers, and polyfunctional monomers.
  • the proportion of the copolymerization component in all the monomer components is preferably 0% to 20% by weight, more preferably 0.1% to 15% by weight, further preferably 0.1% by weight, based on 100% by weight of the total monomer components. % To 10% by weight.
  • the weight average molecular weight of the base polymer is typically 500,000 to 3,000,000, preferably 700,000 to 270,000, and more preferably 800,000 to 2,500,000. If the weight average molecular weight is too small, the heat resistance may be insufficient. If the weight average molecular weight is too large, the handleability may deteriorate. In addition, a large amount of diluting solvent is required for viscosity adjustment for coating, which may increase the cost.
  • the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.
  • the pressure-sensitive adhesive layer contains a lithium salt (lithium-anion salt).
  • the lithium salt can function as a conductive agent.
  • anions constituting the anion part include Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , ClO 4 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ .
  • fluorine-containing imide anion examples include imide anions having a perfluoroalkyl group. Specific examples thereof include the above (CF 3 SO 2 ) (CF 3 CO) N ⁇ , and general formulas (1), (2) and (4). (1): (C n F 2n + 1 SO 2 ) 2 N ⁇ (n is an integer of 1 to 10), (2): CF 2 (C m F 2m SO 2 ) 2 N ⁇ (m is an integer of 1 to 10), (4): (C p F 2p + 1 SO 2 ) N ⁇ (C q F 2q + 1 SO 2 ), (p and q are integers from 1 to 10), An anion represented by Preferred are (CF 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ , and other (perfluoroalkylsulfonyl) imides represented by general formula (1), and more preferred are (CF 3 SO 2) 2 N - bis represented by (trifluoromethanesulfony
  • the content of the lithium salt in the pressure-sensitive adhesive composition is preferably 0.01 to 5 parts by weight, more preferably 0.5 parts by weight, based on 100 parts by weight of the base polymer. To 3 parts by weight, more preferably 0.7 to 1.5 parts by weight.
  • the content of the lithium salt is in such a range, the heat resistance of the thin polarizer having a high iodine content (as a result, the polarizing plate including such a polarizer) can be significantly improved.
  • the pressure-sensitive adhesive composition may further contain an organic cationic salt, if necessary.
  • an organic cationic salt By using the lithium salt and the organic cation salt in combination, the surface resistance value can be further reduced without causing the lithium salt to bleed out.
  • the organic cation salt is specifically an organic cation-anion salt.
  • an organic onium having an onium ion formed by substitution with an organic group can be mentioned.
  • onium in the organic onium include nitrogen-containing onium, sulfur-containing onium, and phosphorus-containing onium. Of these, nitrogen-containing onium and sulfur-containing onium are preferred.
  • an ammonium cation, a piperidinium cation and a pyrrolidinium cation are preferable, and a pyrrolidinium cation is more preferable.
  • the sulfur-containing onium include a sulfonium cation.
  • the phosphorus-containing onium include a phosphonium cation.
  • the organic group in the organic onium include an alkyl group, an alkoxyl group, and an alkenyl group.
  • preferable organic onium include a tetraalkylammonium cation, an alkylpiperidinium cation, and an alkylpyrrolidinium cation.
  • the preferred organic cation salt that can be used in the embodiments of the present invention is a pyrrolidinium salt, more preferably ethylmethylpyrrolidinium bis (trifluoromethanesulfonyl) imide.
  • the content of the organic cation salt in the pressure-sensitive adhesive composition is preferably 0.1 part by weight to 10 parts by weight, more preferably 0.3 part by weight, relative to 100 parts by weight of the base polymer. Parts to 3 parts by weight, more preferably 0.5 to 1.5 parts by weight.
  • the content of the organic cation salt is in such a range, the effect of the combination of the above organic cation salt and the lithium salt becomes remarkable.
  • the pressure-sensitive adhesive composition may further contain a silane coupling agent.
  • the durability can be improved by using the silane coupling agent.
  • the silane coupling agent one having any appropriate functional group can be used. Specific examples of the functional group include a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth) acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, and a polysulfide group.
  • vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, and vinyltributoxysilane; ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycine Epoxy group-containing silane coupling agents such as cidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, ⁇ -triethoxysilyl-N- (1,3-dimethylbutylidene) Propylamine
  • the pressure-sensitive adhesive composition may further contain any appropriate additive.
  • additives include cross-linking agents, silane coupling agents, rework improving agents, antioxidants, antistatic agents, cross-linking retarders, emulsifiers, colorants, powders such as pigments, dyes, surfactants, plasticizers.
  • the number, type, amount and combination of additives can be appropriately set according to the purpose.
  • the pressure-sensitive adhesive composition is applied to a release-treated separator or the like, and a method of transferring to a polarizer after forming a pressure-sensitive adhesive layer by drying and removing a polymerization solvent, or a polarizer
  • a method of applying the above-mentioned pressure-sensitive adhesive composition and drying and removing a polymerization solvent and the like to form a pressure-sensitive adhesive layer on the polarizer is mentioned.
  • one or more solvents other than the polymerization solvent may be newly added, if necessary.
  • the thickness of the adhesive layer is preferably 10 ⁇ m to 200 ⁇ m, more preferably 10 ⁇ m to 100 ⁇ m. When the thickness of the pressure-sensitive adhesive layer is in such a range, the effect of improving the heat resistance by the lithium salt can be remarkable.
  • the surface resistance value (initial) of the pressure-sensitive adhesive layer is preferably 1.0 ⁇ 10 11 ⁇ ⁇ ⁇ or less, more preferably 8.0 ⁇ 10 10 ⁇ ⁇ ⁇ or less, and further preferably 5.0 ⁇ . It is 10 10 ⁇ ⁇ ⁇ or less.
  • the surface resistance value of the adhesive layer may be, for example, 5.0 ⁇ 10 9 ⁇ ⁇ ⁇ or more.
  • Nebulizer Teflon (registered trademark) coaxial nebulizer m / z: Li (7)
  • DRC mode OFF
  • a polarizing plate with a pressure-sensitive adhesive layer from which the pressure-sensitive adhesive composition was removed was prepared and measured in the same manner as above to obtain the lithium content in the polarizer.
  • the lithium content of the pressure-sensitive adhesive layer was calculated by subtracting the lithium content of the polarizer from the lithium content of the polarizing plate with the pressure-sensitive adhesive layer (the following formula).
  • the separator was peeled off from the pressure-sensitive adhesive layer-attached polarizing plate obtained in each of the examples and comparative examples, and laminated on a non-alkali glass having a thickness of 1.3 mm. After that, it was placed in an oven at 105 ° C. for 60 hours, and the heating reliability was evaluated.
  • the polarizing plates before and after the addition were visually compared to confirm the presence or absence of red color change of the polarizing plate due to occurrence of polyene.
  • Example 1 (Preparation of Base Polymer for Adhesive Composition) A monomer mixture containing 99 parts of butyl acrylate and 1 part of 4-hydroxybutyl acrylate was charged into a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas introduction tube, and a condenser. Further, to 100 parts of the above monomer mixture (solid content), 0.1 part of 2,2′-azobisisobutyronitrile as a polymerization initiator was charged together with ethyl acetate, and nitrogen gas was introduced while gently stirring. After purging with nitrogen, the liquid temperature in the flask was kept at around 60 ° C. to carry out a polymerization reaction for 7 hours. Then, ethyl acetate was added to the obtained reaction solution to adjust the solid content concentration to 30%. Thus, a solution of the acrylic polymer (A-1) (base polymer) having a weight average molecular weight of 1.4 million was prepared.
  • A-1 base polymer
  • IPA copolymerized PET film (thickness: 100 ⁇ m) having a water absorption of 0.75% and a Tg of 75 ° C. was used as a thermoplastic resin substrate.
  • One side of the base material is subjected to corona treatment, and polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (polymerization degree 1200, acetoacetyl modification degree 4.6) are applied to the corona-treated surface.
  • the laminate was immersed in a cleaning bath (pure water) having a liquid temperature of 25 ° C. for 6 seconds (first cleaning treatment). Then, it was immersed for 16 seconds in a crosslinking bath (aqueous solution having a boron concentration of 1% by weight and a potassium iodide concentration of 1% by weight) at a liquid temperature of 60 ° C. (crosslinking treatment). Next, the laminated body was immersed in a cleaning bath having a liquid temperature of 25 ° C.
  • a laminate having a PVA-based resin layer (polarizer) having a thickness of 1.2 ⁇ m.
  • the iodine content of the polarizer was 20.9% by weight, and the single transmittance was 40.3%.
  • the pressure-sensitive adhesive composition is uniformly applied to the surface of a polyethylene terephthalate film (separator) treated with a silicone-based release agent with a fountain coater, and dried for 2 minutes in a constant temperature air-circulation oven at 155 ° C. to form a separator surface. An adhesive layer having a thickness of 20 ⁇ m was formed. Next, this pressure-sensitive adhesive layer was transferred onto the surface of the polarizer of the above polarizing plate to obtain a polarizing plate with a pressure-sensitive adhesive layer.
  • Example 2 A polarizing plate with a pressure-sensitive adhesive layer was obtained in the same manner as in Example 1 except that the treatment liquid was applied so that the film thickness in the wet state was 5 ⁇ m. The obtained polarizing plate with an adhesive layer was subjected to the same evaluations as in Example 1. The results are shown in Table 1.
  • Example 1 A polarizing plate with a pressure-sensitive adhesive layer was obtained in the same manner as in Example 1 except that the treatment liquid was not applied. The obtained polarizing plate with an adhesive layer was subjected to the same evaluations as in Example 1. The results are shown in Table 1.
  • the polarizing plate with an adhesive layer of the present invention is widely used for liquid crystal panels such as liquid crystal televisions, liquid crystal displays, mobile phones, digital cameras, video cameras, portable game machines, car navigations, copiers, printers, fax machines, watches and microwave ovens. Can be applied.
  • liquid crystal panels such as liquid crystal televisions, liquid crystal displays, mobile phones, digital cameras, video cameras, portable game machines, car navigations, copiers, printers, fax machines, watches and microwave ovens. Can be applied.
  • Polarizer 10 Polarizer 20 Protective Film 30 Adhesive Layer 100 Polarizing Plate with Adhesive Layer

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Inorganic Chemistry (AREA)
  • Polarising Elements (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention fournit une plaque de polarisation avec couche d'adhésif de type mince et possédant une résistance à la chaleur exceptionnelle. La plaque de polarisation avec couche d'adhésif de l'invention possède un polariseur, un film protecteur placé sur un côté de ce polariseur, et une couche d'adhésif contenant un sel de lithium placée de l'autre côté du polariseur. La teneur en lithium (ＬｉＰＯＬ) du polariseur est supérieure ou égale à 0,3% en masse, et la teneur en lithium (ＬｉＰＳＡ) de la couche d'adhésif est supérieure ou égale à ０,００３５% en masse.
PCT/JP2019/032973 2018-11-01 2019-08-23 Plaque de polarisation avec couche d'adhésif WO2020090196A1 (fr)

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JP2020554778A JP7126796B2 (ja) 2018-11-01 2019-08-23 粘着剤層付偏光板
CN201980070493.7A CN112955791B (zh) 2018-11-01 2019-08-23 带粘合剂层的偏光板
KR1020217012291A KR20210084464A (ko) 2018-11-01 2019-08-23 점착제층 부착 편광판

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CN112955791A (zh) 2021-06-11
JPWO2020090196A1 (ja) 2021-09-24
TWI813752B (zh) 2023-09-01
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