WO2016208510A1 - 偏光子の製造方法 - Google Patents

偏光子の製造方法 Download PDF

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Publication number
WO2016208510A1
WO2016208510A1 PCT/JP2016/068133 JP2016068133W WO2016208510A1 WO 2016208510 A1 WO2016208510 A1 WO 2016208510A1 JP 2016068133 W JP2016068133 W JP 2016068133W WO 2016208510 A1 WO2016208510 A1 WO 2016208510A1
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WO
WIPO (PCT)
Prior art keywords
polarizer
polarizing
adhesive layer
protective film
sensitive adhesive
Prior art date
Application number
PCT/JP2016/068133
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English (en)
French (fr)
Japanese (ja)
Inventor
忍 永野
将寛 八重樫
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020177036950A priority Critical patent/KR102003632B1/ko
Priority to CN201680037343.2A priority patent/CN107710038B/zh
Publication of WO2016208510A1 publication Critical patent/WO2016208510A1/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
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133528—Polarisers
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/8793—Arrangements for polarized light emission

Definitions

  • the present invention relates to a method for manufacturing a polarizer.
  • this invention relates to the manufacturing method of the polarizer which has a non-polarizing part.
  • Some image display devices such as mobile phones and notebook personal computers (PCs) are equipped with internal electronic components such as cameras.
  • Various studies have been made for the purpose of improving the camera performance and the like of such an image display device (for example, Patent Documents 1 to 7).
  • Patent Documents 1 to 7 For example, Patent Documents 1 to 7
  • smartphones and touch panel type information processing devices further improvements in camera performance and the like are desired.
  • a polarizing plate partially having polarization performance.
  • the present invention has been made to solve the above-described conventional problems, and a main object thereof is a method for manufacturing a polarizer capable of realizing multi-function and high-performance electronic devices such as image display apparatuses.
  • a main object thereof is a method for manufacturing a polarizer capable of realizing multi-function and high-performance electronic devices such as image display apparatuses.
  • a surface protective film is laminated on one side of the polarizer via an adhesive layer having a thickness of 10 ⁇ m or less, and at least a part of the polarizer is exposed on the one side.
  • a step of producing a polarizing film laminate having a portion a step of bringing a basic solution into contact with an exposed portion of the polarizing film laminate, and a step of removing the surface protective film from the polarizing film laminate.
  • the step of bringing the basic solution into contact with the exposed portion includes immersing the polarizing film laminate in the basic solution.
  • the pressure-sensitive adhesive layer contains an acrylic resin.
  • the said manufacturing method further includes the process of making an acidic solution contact the exposed part of the said polarizing film laminated body.
  • the step of bringing the acidic solution into contact with the exposed portion includes immersing the polarizing film laminate in the acidic solution.
  • the step of bringing the basic solution into contact with the exposed portion includes immersing the polarizing film laminate in the basic solution, and the step of bringing the acidic solution into contact with the exposed portion is the polarized light. Immersing the film laminate in an acidic solution.
  • the polarizing film laminate is elongated.
  • a polarizer is obtained. This polarizer is obtained by the manufacturing method described above.
  • a polarizing plate is obtained. This polarizing plate includes the polarizer.
  • an image display device is provided. The image display device includes the polarizing plate.
  • the polarizing film laminate used in the production method of the present invention has a surface protective film laminated on one side of a polarizer with an adhesive layer having a thickness of 10 ⁇ m or less.
  • a non-polarizing portion having a desired shape can be formed with high accuracy.
  • A. Manufacturing method of polarizer In the manufacturing method of the present invention, a surface protective film is laminated on one surface side of a polarizer via an adhesive layer having a thickness of 10 ⁇ m or less, and at least a part of the polarizer is exposed on the one surface side.
  • a step of producing a polarizing film laminate having the exposed portion a step of bringing a basic solution into contact with the exposed portion of the polarizing film laminate, and a step of removing the surface protective film from the polarizing film laminate.
  • the polarizing film laminate having an exposed portion only a desired portion of the polarizer (that is, a portion exposed from the exposed portion) can be brought into contact with the basic solution.
  • the polarizer By bringing the polarizer into contact with the basic solution, the content of the dichroic substance contained in the contact part can be reduced, and the non-polarizing part having a lower content of the dichroic substance than other parts can be obtained. Can be formed.
  • stacked the polarizer and the surface protection film through the adhesive layer of thickness 10 micrometers or less is used.
  • the thickness of the pressure-sensitive adhesive layer is 10 ⁇ m or less, it is possible to prevent bubbles from adhering to the exposed portion due to the surface tension of the pressure-sensitive adhesive.
  • the basic solution is sufficiently in contact with the entire exposed portion, and a non-polarized portion having a desired shape can be formed with high accuracy.
  • the polarizer before forming a non-polarization part is an intermediate body of the polarizer which has a non-polarization part obtained by the manufacturing method of this invention strictly, it is only called a polarizer in this specification. A person skilled in the art can easily understand from the description of the present specification whether "polarizer” means an intermediate or a polarizer having a non-polarization part obtained by the production method of the present invention. be able to.
  • a polarizing film laminate is produced by laminating a surface protective film on one side of a polarizer with a pressure-sensitive adhesive layer having a thickness of 10 ⁇ m or less.
  • the polarizing film laminate used in the present invention has an exposed portion where at least a part of the polarizer is exposed on the one surface side.
  • FIG. 1 is a schematic cross-sectional view of a polarizing film laminate used in one embodiment of the present invention.
  • a polarizing plate having a polarizer / protective film configuration is used.
  • the surface protective film 50 is laminated on the surface of the polarizer 10 of the polarizer 10 / protective film 20 via an adhesive layer 60 having a thickness of 10 ⁇ m or less.
  • the surface protective film 50 has a through hole 71.
  • the polarizing film laminate 100 has an exposed portion 51 where the polarizer 10 is exposed from the through hole 71.
  • the surface protective film 50 is detachably laminated on the polarizing plate (substantially, the polarizer 10). It goes without saying that the same procedure can be applied to a polarizer having a form other than that of the polarizing plate (for example, a polarizer that is a single resin film, a laminate of a resin base material / polarizer).
  • the polarizing film laminate 100 may have another surface protective film (the surface protective film 30 in FIG. 1) further laminated on the surface where the surface protective film 50 having a through hole is not laminated. Good.
  • the surface protective film 50 having a through hole is used as the first surface protective film, and the surface protective film 30 laminated on the side where the surface protective film having the through hole of the polarizing film laminate 100 is not laminated is the second surface. Also called protective film.
  • the polarizing film laminate is typically long.
  • the long polarizing film laminate is formed by, for example, laminating a long surface protective film having through holes arranged at predetermined intervals in the long direction and / or the width direction and a long polarizer. Can be obtained.
  • a step of contacting with a basic solution and a step of contacting with another treatment solution are continuously performed by immersion. be able to.
  • the productivity of the polarizer can be further improved.
  • the elongate polarizing film laminated body may have a some exposed part. Even in such a case, the basic solution can be sufficiently brought into contact with each exposed portion, and a non-polarizing portion having a desired shape can be formed with high accuracy.
  • a polarizer having a non-polarizing part in a pattern corresponding to the pattern of the exposed part, so that the non-polarizing part is precisely controlled over the entire long polarizer. Can be arranged.
  • a polarizer as a final product of a predetermined size is cut from the long polarizer, the quality variation for each final product can be remarkably suppressed.
  • such a non-polarizing part is selectively and easily formed at the position of the through hole, and thus does not require a complicated device or operation.
  • the position of the non-polarizing portion can be set in accordance with the size of the polarizer as the final product cut and mounted on the image display device and the position of the camera portion of the image display device.
  • the yield in obtaining a sized polarizer is very good.
  • the polarizer is typically composed of a resin film containing a dichroic substance.
  • the resin film is, for example, a polyvinyl alcohol resin (hereinafter referred to as “PVA resin”) film.
  • PVA resin polyvinyl alcohol resin
  • the dichroic substance include iodine and organic dyes. These may be used alone or in combination of two or more.
  • iodine is used.
  • the iodine complex is reduced and the content of iodine is reduced, resulting in the formation of a non-polarizing part with properties suitable for use as a part corresponding to a camera Because it can be done.
  • any appropriate resin can be used as the resin forming the resin film.
  • a PVA resin is used.
  • the PVA resin include polyvinyl alcohol and ethylene-vinyl alcohol copolymer.
  • Polyvinyl alcohol is obtained by saponifying polyvinyl acetate.
  • the ethylene-vinyl alcohol copolymer can be obtained by saponifying an ethylene-vinyl acetate copolymer.
  • the saponification degree of the PVA 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 degree of saponification can be determined according to JIS K 6726-1994. By using a PVA-based resin having such a saponification degree, a polarizer having excellent durability can be obtained. If the degree of saponification is too high, there is a risk of gelation.
  • 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 10,000, 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 thickness of the polarizer can be set to any appropriate value.
  • the thickness is preferably 30 ⁇ m or less, more preferably 25 ⁇ m or less, still more preferably 20 ⁇ m or less, and particularly preferably less than 10 ⁇ m.
  • the thickness is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more. If it is such thickness, a non-polarizing part can be favorably formed by making it contact with a basic solution. Furthermore, the time for contacting the basic solution can be shortened. Moreover, the thickness of the part contacted with the basic solution may be thinner than other parts. By using a thin resin film, it is possible to reduce the difference in thickness between the part that is in contact with the basic solution and the part that is not in contact with it. Can be done.
  • the resin film is preferably subjected to various treatments such as a swelling treatment, a stretching treatment, a dyeing treatment with the dichroic substance, a crosslinking treatment, a washing treatment, and a drying treatment so as to function as a polarizer.
  • the resin film may be a resin layer formed on a substrate.
  • the laminated body of a base material and a resin layer can be obtained by the method of apply
  • the dyeing process is performed, for example, by immersing a resin film in a dyeing solution.
  • a dyeing solution an aqueous iodine solution is preferably used.
  • the amount of iodine is preferably 0.04 to 5.0 parts by weight per 100 parts by weight of water.
  • an iodide is preferably used as the iodide.
  • potassium iodide is preferably used as the iodide.
  • the blending amount of iodide is preferably 0.3 to 15 parts by weight with respect to 100 parts by weight of water.
  • the resin film is typically uniaxially stretched 3 to 7 times.
  • the stretching direction can correspond to the absorption axis direction of the obtained polarizer.
  • the surface protective film 50 is provided with a through hole 71 corresponding to a portion to be brought into contact with the obtained basic solution of the polarizer (that is, a portion corresponding to the exposed portion 51 of the polarizing film laminate).
  • Arbitrary appropriate shape can be employ
  • Specific examples include a circle, an ellipse, a square, a rectangle, and a rhombus.
  • the through hole of the surface protective film can be formed by, for example, mechanical punching (for example, punching, engraving blade punching, plotter, water jet) or removal of a predetermined portion of the surface protective film (for example, laser ablation or chemical dissolution).
  • FIG. 2A is a schematic plan view for explaining an example of the arrangement pattern of the through holes of the surface protective film
  • FIG. 2B is a schematic plan view for explaining another example of the arrangement pattern of the through holes
  • FIG. It is a schematic plan view explaining another example of the arrangement pattern of the through holes.
  • the through holes 71 can be arranged at substantially equal intervals in both the longitudinal direction and the width direction of the surface protection film 50. Note that “substantially equidistant in both the longitudinal direction and the width direction” means that the spacing in the longitudinal direction is equal and the spacing in the width direction is equal.
  • the interval in the scale direction and the interval in the width direction need not be equal.
  • L1 L2 may be satisfied, or L1 ⁇ L2.
  • the through holes may be arranged at substantially equal intervals in the longitudinal direction and at different intervals in the width direction; they are arranged at different intervals in the longitudinal direction and substantially in the width direction. May be arranged at equal intervals (none of which are shown).
  • the through holes are arranged at different intervals in the longitudinal direction or the width direction, the intervals between the adjacent through holes may be all different, or only a part (the interval between specific adjacent through holes) may be different. Good.
  • region may prescribe
  • the through-hole 71 has a straight line that connects adjacent through-holes in the longitudinal direction substantially parallel to the longitudinal direction, and has a width.
  • a straight line connecting adjacent through holes in the direction may be arranged to be substantially parallel to the width direction.
  • the through-hole 71 has a straight line connecting adjacent through-holes in the longitudinal direction substantially parallel to the longitudinal direction, and in the width direction. a straight line connecting the adjacent through-holes are arranged so as to have a predetermined angle theta W in the width direction.
  • FIG. 2A the through-hole 71 has a straight line that connects adjacent through-holes in the longitudinal direction substantially parallel to the longitudinal direction, and has a width.
  • a straight line connecting adjacent through holes in the direction may be arranged to be substantially parallel to the width direction.
  • the through-hole 71 has a straight line connecting adjacent through-holes in the longitudinal direction substantially parallel to the longitudinal direction, and in the width direction. a straight line connecting the adjacent through-holes are arranged so as to have a predetermined
  • a straight line connecting adjacent through holes in the longitudinal direction has a predetermined angle ⁇ L with respect to the longitudinal direction
  • a straight line connecting adjacent through holes in the width direction is arranged to have a predetermined angle ⁇ W with respect to the width direction.
  • ⁇ L and / or ⁇ W is preferably more than 0 ° and not more than ⁇ 10 °.
  • “ ⁇ ” means to include both clockwise and counterclockwise directions with respect to the reference direction (long direction or width direction).
  • a non-polarizing part can be formed by a desired pattern (pattern corresponding to the arrangement pattern of a through-hole), carrying a roll.
  • a desired pattern pattern corresponding to the arrangement pattern of a through-hole
  • the absorption axis of the polarizer is expressed in the longitudinal direction or the width direction, in such a case, by forming the non-polarizing part having a pattern as shown in FIGS. 2B and 2C, the non-polarizing part and the absorption axis Can be controlled uniformly over the entire long polarizer, and a final product with excellent axial accuracy (and therefore excellent optical properties) can be obtained. Therefore, the direction of the absorption axis of the cut polarizer (for example, cutting in the longitudinal direction and / or the width direction, punching) can be precisely controlled to a desired angle, and for each polarizer. Variation in the direction of the absorption axis can be remarkably suppressed.
  • a straight line connecting adjacent through holes in the longitudinal direction has a predetermined angle ⁇ L with respect to the longitudinal direction, and a straight line connecting adjacent through holes in the width direction is It may be arranged to be substantially parallel to the direction. Further, a plurality of regions may be defined in the longitudinal direction of the surface protective film 50, and ⁇ L and / or ⁇ W may be set for each region.
  • the surface protective film is preferably a film having high hardness (for example, elastic modulus). This is because deformation of the through-hole can be prevented, and particularly when used as a long polarizing film laminate, deformation of the through-hole during transportation and / or bonding can be prevented.
  • Surface protective film forming materials include ester resins such as polyethylene terephthalate resins, cycloolefin resins such as norbornene resins, olefin resins such as polypropylene, polyamide resins, polycarbonate resins, and copolymer resins thereof. Etc. Preference is given to ester resins (especially polyethylene terephthalate resins).
  • the elastic modulus is sufficiently high and deformation of the through-hole can be prevented.
  • the elastic modulus is sufficiently high and deformation of the through-hole can be prevented.
  • the thickness of the surface protective film can be set to any appropriate value.
  • the thickness of the surface protective film is, for example, 30 ⁇ m because it has the advantage that deformation of the through-hole hardly occurs even when tension is applied during transportation and / or bonding. ⁇ 150 ⁇ m.
  • the elastic modulus of the surface protective film is preferably 2.2 kN / mm 2 to 4.8 kN / mm 2 . If the elastic modulus of the surface protective film is in such a range, deformation of the through-hole can be prevented, and particularly when used as a long polarizing film laminate, tension is applied during transportation and / or bonding. Also has the advantage that deformation of the through-hole is unlikely to occur.
  • the elastic modulus is measured according to JIS K 6781.
  • the tensile elongation of the surface protective film is preferably 90% to 170%.
  • the tensile elongation is measured according to JIS K 6781.
  • the thickness of the adhesive layer 60 is 10 ⁇ m or less, preferably 5 ⁇ m or less.
  • a basic solution may not fully contact an exposed part by a bubble adhering to the surface protection film and adhesive layer of an exposed part.
  • the size of the exposed portion is small or the shape of the exposed portion is complicated, this influence becomes remarkable, and there is a possibility that a non-polarized portion having a desired shape cannot be formed.
  • the thickness of the pressure-sensitive adhesive layer is in such a range, it is possible to prevent bubbles from attaching to the exposed portion due to the surface tension of the pressure-sensitive adhesive. As a result, the basic solution can be sufficiently brought into contact with the exposed portion, and a polarizer having a non-polarized portion having a desired shape can be obtained.
  • the pressure-sensitive adhesive layer is formed using any appropriate composition.
  • the composition for forming an adhesive layer includes, for example, a resin component and any appropriate additive. Any appropriate resin can be used as the base resin of the pressure-sensitive adhesive, and a resin having a glass transition temperature Tg of 0 ° C. or lower is preferable. Specific examples include acrylic resins, silicone resins, rubber resins, and urethane resins. An acrylic resin is preferred because the laminated state of the surface protective film and the polarizer can be maintained well even with a thickness of 10 ⁇ m or less.
  • the acrylic resin is preferably an acrylic polymer containing at least one acrylate and / or methacrylate (hereinafter also referred to as (meth) acrylate) having an alkyl group having 1 to 14 carbon atoms.
  • the acrylic polymer preferably contains 50 to 100% by weight of (meth) acrylate having an alkyl group having 1 to 14 carbon atoms as a monomer component.
  • Examples of the (meth) acrylate having an alkyl group having 1 to 14 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, and isobutyl (meth) ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) ) Acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl
  • (meth) acrylate having an alkyl group having 4 to 14 carbon atoms it becomes easy to control the adhesive force, and it has excellent removability.
  • the acrylic polymer may contain any appropriate other monomer component in addition to the (meth) acrylate having an alkyl group having 1 to 14 carbon atoms.
  • Other monomer components include sulfonic acid group-containing monomers, phosphate group-containing monomers, cyano group-containing monomers, vinyl esters, aromatic vinyl compounds and other monomer components that can contribute to improving cohesion and heat resistance, and carboxyl groups Functional group that acts as an adhesive strength-improving and cross-linking base point for monomers containing acid anhydride groups, monomers containing hydroxyl groups, monomers containing amide groups, monomers containing amide groups, monomers containing amino groups, monomers containing epoxy groups, N-acryloylmorpholine, vinyl ethers, etc.
  • Other monomer components may be used alone or in combination of two or more.
  • Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, and (meth).
  • Examples include acryloyloxynaphthalene sulfonic acid.
  • Examples of the phosphate group-containing monomer include 2-hydroxyethyl acryloyl phosphate.
  • Examples of the cyano group-containing monomer include acrylonitrile.
  • Examples of vinyl esters include vinyl acetate.
  • Examples of the aromatic vinyl compound include styrene.
  • carboxyl group-containing monomer examples include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid.
  • acid anhydride group-containing monomer examples include maleic anhydride and itaconic anhydride.
  • hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl Examples include vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether.
  • Examples of the amide group-containing monomer include acrylamide and diethyl acrylamide.
  • Examples of the amino group-containing monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like.
  • Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate and allyl glycidyl ether.
  • Examples of vinyl ethers include vinyl ethyl ether.
  • Tg of the resulting polymer is 0 ° C. or less, for example, because it is easy to adjust the adhesive strength.
  • the Tg of the polymer is preferably, for example, ⁇ 100 ° C. or higher.
  • the weight average molecular weight of the acrylic polymer is, for example, 100,000 or more.
  • the acrylic polymer can be obtained by any appropriate polymerization method.
  • polymerization methods generally used as synthetic methods for acrylic polymers such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and the like can be mentioned.
  • the pressure-sensitive adhesive layer forming composition may contain a resin other than the base resin as a resin component.
  • resins include polyether resins, modified polyether resins, and epoxy resins.
  • the content of other resins is preferably 20% by weight or less.
  • the composition for forming the pressure-sensitive adhesive layer may contain any appropriate additive in addition to the resin component.
  • crosslinking agent for example, crosslinking agent, coupling agent, tackifier, surface lubricant, leveling agent, surfactant, antistatic agent, slipperiness improver, wettability improver, antioxidant, corrosion inhibitor, light
  • examples thereof include stabilizers, ultraviolet absorbers, polymerization inhibitors, crosslinking accelerators, crosslinking catalysts, inorganic or organic fillers, powders such as metal powders and pigments, particles, and foils.
  • crosslinking agent Any appropriate crosslinking agent can be used as the crosslinking agent.
  • an isocyanate compound, an epoxy compound, an aziridine compound, and a melamine compound are mentioned.
  • a crosslinking agent may be used independently and may be used in combination of 2 or more type.
  • the content of the crosslinking agent is preferably 0.1 to 15 parts by weight, more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the resin component.
  • the pressure-sensitive adhesive layer can be formed by any appropriate method. Specific examples include a method of applying and drying a pressure-sensitive adhesive forming composition on the surface protective film, a method of forming a pressure-sensitive adhesive layer on a separator, and transferring the pressure-sensitive adhesive layer to the surface protective film.
  • the coating method include roll coating methods such as reverse coating and gravure coating, spin coating methods, screen coating methods, fountain coating methods, dipping methods, and spray methods.
  • the first surface protective film is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer having a thickness of 10 ⁇ m or less.
  • the first surface protective film in this embodiment is a laminate having a resin film used as the surface protective film and an adhesive layer provided on one surface of the resin film, the resin film and the It has a through hole that penetrates the adhesive layer.
  • the first surface protective film is an adhesive sheet, the long polarizer and the long first surface protective film can be bonded to each other by roll-to-roll, and the production efficiency is further improved. obtain.
  • a separator can be temporarily attached to the pressure-sensitive adhesive layer in a peelable manner.
  • the separator has a function as a protective material that protects the adhesive layer until it is put to practical use.
  • a plastic for example, polyethylene terephthalate (PET), polyethylene, polypropylene
  • a release agent such as a silicone release agent, a fluorine release agent, or a long-chain alkyl acrylate release agent
  • paper for example, paper.
  • Arbitrary appropriate thickness can be employ
  • the thickness of the separator is, for example, 10 ⁇ m to 100 ⁇ m.
  • the separator may be laminated on a laminate of the resin film used as the surface protective film and the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive layer is formed on the separator, and the laminate of the separator and the pressure-sensitive adhesive layer is formed on the surface protective film. You may laminate
  • the second surface protective film 30 may be further laminated on the side where the first surface protective film 50 is not disposed.
  • a film similar to the first surface protective film 50 can be used except that no through hole is provided.
  • a soft (eg, low elastic modulus) film such as a polyolefin (eg, polyethylene) film can be used.
  • A-2. Step of contacting with basic solution the basic solution is brought into contact with the exposed portion of the polarizing film laminate.
  • the content of the dichroic material in the exposed portion is reduced, and the non-polarizing portion can be formed by reducing the content of the dichroic material.
  • the polarizer containing an iodine is preferable.
  • the polarizer contains iodine as a dichroic substance, the exposed portion of the polarizer and the basic solution are brought into contact with each other to reduce the iodine content of the exposed portion.
  • a polarizing part can be formed.
  • the non-polarizing portion in a predetermined portion of the polarizer with very high manufacturing efficiency without complicated operation.
  • iodine remains in the polarizer, even if the iodine complex is destroyed to form a non-polarizing part, the iodine complex is formed again with the use of the polarizer, and the non-polarizing part has the desired characteristics. There is a risk that it will disappear.
  • iodine itself is removed from the polarizer (substantially, the non-polarizing part). As a result, it is possible to prevent a change in the characteristics of the non-polarizing part associated with the use of the polarizer.
  • the step of bringing the basic solution into contact with the polarizing film laminate can be performed by any appropriate means. For example, immersion, dripping, coating, spraying and the like can be mentioned.
  • immersion, dripping, coating, spraying and the like can be mentioned.
  • the iodine content contained in the polarizer is reduced in portions other than the exposed portion of the polarizing film laminate. Therefore, it becomes possible to form a non-polarizing part only in a desired part by immersion. Specifically, by immersing the polarizing film laminate in the basic solution, only the exposed portion of the polarizing film laminate contacts the basic solution.
  • the formation of the non-polarizing part by the basic solution will be described in detail.
  • the basic solution penetrates into the exposed part (specifically, the polarizer).
  • the iodine complex contained in the polarizer is reduced by the base contained in the basic solution to become iodine ions.
  • the polarizing performance of the polarizer exposed from the exposed portion substantially disappears, and a non-polarized portion is formed in the exposed portion.
  • permeability of an exposed part improves by reduction
  • Iodine that has become iodine ions moves from the exposed portion into the solvent of the basic solution.
  • iodine ions are removed from the polarizer together with the basic solution.
  • a non-polarizing portion is selectively formed in a predetermined portion of the polarizer, and the non-polarizing portion is stable without change over time.
  • any appropriate basic compound can be used as the basic compound contained in the basic solution.
  • Examples of basic compounds include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide, inorganic alkali metal salts such as sodium carbonate, acetic acid Organic alkali metal salts such as sodium, aqueous ammonia and the like can be mentioned.
  • the basic compound contained in the basic solution is preferably an alkali metal hydroxide, more preferably sodium hydroxide, potassium hydroxide, or lithium hydroxide.
  • any appropriate solvent can be used as the solvent of the basic solution.
  • Specific examples include water, alcohols such as ethanol and methanol, ethers, benzene, chloroform, and mixed solvents thereof. Since iodine ions migrate to the solvent satisfactorily and iodine ions can be easily removed, the solvent is preferably water or alcohol.
  • the concentration of the basic solution is, for example, 0.01N to 5N, preferably 0.05N to 3N, and more preferably 0.1N to 2.5N.
  • concentration of the basic solution is in such a range, the iodine content inside the polarizer can be efficiently reduced, and ionization of the iodine complex in a portion other than the exposed portion can be prevented.
  • the liquid temperature of the basic solution is, for example, 20 ° C. to 50 ° C.
  • the contact time between the polarizing film laminate (substantially, the exposed portion of the polarizer) and the basic solution depends on the thickness of the polarizer, the type of basic compound contained in the basic solution used, and the basic compound It can be set according to the concentration, and is, for example, 5 seconds to 30 minutes.
  • the basic solution can be removed by any appropriate means as necessary after contact with the exposed portion of the polarizer (after formation of the non-polarizing portion).
  • Specific examples of the method for removing the basic solution include wiping removal with a waste cloth, suction removal, natural drying, heat drying, air drying, vacuum drying, washing, and the like.
  • the drying temperature when the basic solution is removed by drying is, for example, 20 ° C. to 100 ° C.
  • the surface protection film is removed from the polarizing film laminate.
  • the surface protective film is detachably attached to the surface of the polarizer via the pressure-sensitive adhesive layer. Therefore, it can be easily removed from the surface of the polarizer after performing the steps necessary for producing a polarizer having a non-polarizing part.
  • the method for producing a polarizer having a non-polarizing part of the present invention includes a step of producing a polarizing film laminate, a step of contacting an exposed part of the polarizing film laminate and a basic solution, and a surface protective film. Any appropriate process other than the removing process may be further included. Examples of other steps include a step of contacting with an acidic solution and a washing step.
  • Step of contacting with acidic solution may further include a step of contacting the polarizing film laminate and the acidic solution.
  • the non-polarized portion having a desired size and shape can be maintained more stably (particularly in a humidified environment).
  • the step of contacting with the acidic solution can be performed, for example, after the step of contacting with the basic solution.
  • any appropriate acidic compound can be used as the acidic compound contained in the acidic solution.
  • the acidic compound include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrogen fluoride, and organic acids such as formic acid, oxalic acid, citric acid, acetic acid, and benzoic acid.
  • the concentration of the acidic solution is, for example, 0.01N to 5N, preferably 0.05N to 3N, and more preferably 0.1N to 2.5N.
  • the solvent used for the acidic solution, the liquid temperature of the acidic solution, the contact time with the acidic solution, and the contact method are the same as the conditions that can be employed in the contact step with the basic solution described in the above section A-2. Conditions can be employed.
  • the contact step with the acid solution is preferably performed before the surface protective film peeling step (specifically, in the state of a polarizing film laminate).
  • a contact process with an acidic solution can be performed continuously with a contact process with a basic solution.
  • the production method of the present invention may further include a cleaning step.
  • the cleaning process may be performed only once or a plurality of times.
  • the cleaning process can be performed at any suitable stage in the process of manufacturing a polarizer having a non-polarizing part. For example, after washing the polarizer brought into contact with the basic solution with any appropriate liquid, the contact step with the acidic solution may be performed, or the contact step with the basic solution and the contact step with the acidic solution are performed. Thereafter, a cleaning step with any appropriate liquid may be performed.
  • any appropriate liquid can be used as the liquid used for cleaning.
  • examples thereof include pure water, alcohols such as methanol and ethanol, acidic aqueous solutions, and mixed solvents thereof.
  • the temperature of the liquid to be used can be set to any appropriate temperature.
  • the polarizer obtained by the method of the present invention may have a non-polarizing portion having a desired shape and size formed with high accuracy. Therefore, the polarizer of the present invention can have excellent functionality and design.
  • a polarizer having a non-polarizing portion can be applied to, for example, an image display device including a camera. This is because even when a smaller non-polarizing portion is formed, the camera can sufficiently exhibit the photographing function and the appearance of the obtained image display device can be excellent.
  • the transmittance of the non-polarizing part is preferably 50% or more, more preferably 60% or more, and further preferably 75% or more. Yes, particularly preferably 90% or more. With such transmittance, desired transparency as a non-polarizing portion can be ensured. As a result, when the polarizer is arranged so that the non-polarizing part corresponds to the camera part of the image display device, it is possible to prevent an adverse effect on the photographing performance of the camera.
  • the non-polarizing part is a part having a small dichroic substance content as compared with other parts of the polarizer (parts having polarization performance).
  • the content of the dichroic substance contained in the non-polarizing part is preferably 1.0% by weight or less, more preferably 0.5% by weight or less, and further preferably 0.2% by weight or less.
  • the lower limit value of the dichroic substance content of the non-polarizing part is usually not more than the detection limit value.
  • the iodine content of the non-polarizing part is a value obtained from a calibration curve prepared in advance using a standard sample from the X-ray intensity measured by fluorescent X-ray analysis.
  • the difference between the content of the dichroic substance contained in the part other than the non-polarizing part of the polarizer (part having the polarization performance) and the content of the dichroic substance contained in the non-polarizing part is preferably 0. It is 5% by weight or more, more preferably 1% by weight or more.
  • the difference between the content of the dichroic substance contained in the part other than the non-polarizing part and the content of the dichroic substance contained in the non-polarizing part is within this range, so that the non-polarizing part is sufficiently transparent.
  • a non-polarizing portion can be suitably used as a portion corresponding to an image display camera.
  • Polarizing plate A polarizer can be provided practically as a polarizing plate.
  • the polarizing plate has a polarizer and a protective film disposed on at least one side of the polarizer.
  • the polarizing plate has an adhesive layer as the outermost layer.
  • the pressure-sensitive adhesive layer is typically the outermost layer on the image display device side.
  • a separator can be temporarily attached to the pressure-sensitive adhesive layer in a peelable manner.
  • the material for forming the protective film examples include cellulose resins such as diacetyl cellulose and triacetyl cellulose, (meth) acrylic resins, cycloolefin resins, olefin resins such as polypropylene, and ester resins such as polyethylene terephthalate resins. , Polyamide resins, polycarbonate resins, copolymer resins thereof, and the like.
  • the thickness of the protective film is preferably 10 ⁇ m to 100 ⁇ m.
  • the protective film is typically laminated on the polarizer via an adhesive layer (specifically, an adhesive layer or an adhesive layer).
  • the adhesive layer is typically formed of a PVA adhesive or an active energy ray curable adhesive.
  • the pressure-sensitive adhesive layer is typically formed of an acrylic pressure-sensitive adhesive.
  • the polarizing plate may further have any appropriate optical functional layer depending on the purpose.
  • the optical functional layer include a retardation film (optical compensation film) and a surface treatment layer.
  • the protective film may have an optical compensation function (specifically, it may have an appropriate refractive index ellipsoid, an in-plane retardation, and a thickness direction retardation depending on the purpose). ).
  • the surface treatment layer can be disposed on the viewing side of the polarizing plate.
  • Typical examples of the surface treatment layer include a hard coat layer, an antireflection layer, and an antiglare layer.
  • An image display device of the present invention includes the polarizer.
  • the image display device include a liquid crystal display device and an organic EL device.
  • the liquid crystal display device includes a liquid crystal panel including a liquid crystal cell and the polarizer disposed on one side or both sides of the liquid crystal cell.
  • the organic EL device includes an organic EL panel in which the polarizer is disposed on the viewing side.
  • the polarizer may be disposed so as to correspond to the camera unit of the image display device on which the non-polarizing unit is mounted.
  • a separator was bonded to the formed pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet.
  • 1000 circular holes having a diameter of 2 mm were formed on the obtained adhesive sheet using a pinnacle blade. Each small hole was formed at intervals of 250 mm in length and 400 mm in width to obtain a surface protective film 1 with an adhesive layer.
  • a separator was bonded to the formed pressure-sensitive adhesive layer to obtain a pressure-sensitive adhesive sheet.
  • 1000 circular holes having a diameter of 2 mm were formed on the obtained adhesive sheet using a pinnacle blade. Each small hole was formed at intervals of 250 mm in length and 400 mm in width to obtain a protective film 3 with an adhesive layer.
  • Example 1 As the base material, an amorphous isophthalic acid copolymerized polyethylene terephthalate (IPA copolymerized PET) film (thickness: 100 ⁇ m) having a long water absorption rate of 0.75% and Tg of 75 ° C. was used.
  • IPA copolymerized PET amorphous isophthalic acid copolymerized polyethylene terephthalate
  • One side of the substrate was subjected to corona treatment, and polyvinyl alcohol (degree of polymerization 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (degree of polymerization 1200, degree of acetoacetyl modification 4.6) were applied to this corona-treated surface.
  • the laminate was immersed in an insolubilization bath (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds (insolubilization treatment). Subsequently, it was immersed in a dyeing bath having a liquid temperature of 30 ° C. while adjusting the iodine concentration and the immersion time so that the polarizing plate had a predetermined transmittance.
  • 0.2 parts by weight of iodine was blended with 100 parts by weight of water and immersed in an aqueous iodine solution obtained by blending 1.5 parts by weight of potassium iodide (dyeing treatment). .
  • a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water was immersed for 30 seconds in a crosslinking bath having a liquid temperature of 30 ° C.
  • a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water (Crosslinking treatment).
  • the laminate was immersed in a boric acid aqueous solution (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 70 ° C.
  • a protective film (thickness 25 ⁇ m) was bonded, and this was heated in an oven maintained at 60 ° C. for 5 minutes. Then, the base material was peeled from the PVA resin layer to obtain a polarizing plate (width: 1200 mm, length: 43 m) having a transmittance of 42.3% and a thickness of 5 ⁇ m.
  • the surface protective film 1 with the pressure-sensitive adhesive layer from which the separator was peeled off was bonded to the surface of the polarizing plate of the obtained polarizing plate via the pressure-sensitive adhesive layer to obtain a laminate.
  • the obtained laminate was immersed in a basic solution at room temperature (aqueous sodium hydroxide solution, 1 mol / L (1N)) for 8 seconds and in 0.1 mol / L (0.1N) hydrochloric acid for 30 seconds. Then, it dried at 60 degreeC, the PET film was peeled, and the polarizing plate provided with the polarizer which has a transparent part was obtained.
  • Example 2 to 8 A polarizing plate provided with a polarizer having a transparent part was obtained in the same manner as in Example 1 except that each of the surface protective films with the pressure-sensitive adhesive layer described in Table 1 was used.
  • permeability and iodine content were measured with the following method.
  • Transmittance (Ts) The measurement was performed using a spectrophotometer (product name “DOT-3” manufactured by Murakami Color Research Laboratory Co., Ltd.).
  • the transmittance (T) is a Y value obtained by correcting the visibility with a 2-degree field of view (C light source) of JlS Z 8701-1982.
  • Iodine content The iodine content in the transparent part of the polarizer was determined by fluorescent X-ray analysis.
  • the iodine content of the polarizer was determined from an X-ray intensity measured under the following conditions, using a calibration curve prepared in advance using a standard sample.
  • ⁇ Analyzer X-ray fluorescence analyzer (XRF) manufactured by Rigaku Denki Kogyo Co., Ltd.
  • Product name “ZSX100e” ⁇
  • Anti-cathode Rhodium ⁇
  • Spectral crystal Lithium fluoride
  • Excitation light energy 40 kV-90 mA
  • the transparent portions of the polarizers obtained in the respective examples and comparative examples all had a transmittance of 90% or more and an iodine content of less than 1% by weight. These transparent portions could function as non-polarizing portions.
  • the shape matching degree of each transparent part formed on the polarizing plate was measured by the following method. Among the 1000 transparent portions on the polarizer, those having a shape matching degree exceeding 0.05 are 40% or less, ⁇ , those having 50% or less are ⁇ , and those having more than 60% are ⁇ . . The results are shown in Table 1.
  • the distance between the non-polarizing part 2 and the non-polarizing part approximate circle a is measured, and when the boundary between the polarizer 1 and the non-polarization part 2 is inside the non-polarization part approximate circle (that is, in the case of FIG. 3B), the non-polarization part 2 and the non-polarization part approximate circle
  • the distance b was measured.
  • the total value of the maximum value of the distance a and the maximum value of the distance b was calculated as hole roughness.
  • the calculated hole roughness value is the diameter of the small hole formed in the PET film (Examples 1 to 4 and Comparative Examples 1 to 3 and 7 to 9: 2 mm, Examples 5 to 8 and Comparative Examples 4 to 6 and 10 to 12: 4 mm) to obtain the value of the shape matching degree.
  • a polarizer having such a non-polarizing part for example, when the non-polarizing part is used so as to correspond to the camera part of the image display device, the alignment processability is improved and the camera can be aligned well. it can.
  • Examples 1 to 4 where the small hole provided in the surface protective film was as small as 2 mm a polarizer having a non-polarizing portion close to the shape of the small hole formed in the PET film was obtained.
  • the polarizer obtained by the method of the present invention is suitably used for a mobile phone such as a smartphone, an image display device with a camera (liquid crystal display device, organic EL device) such as a notebook PC or tablet PC.
  • a mobile phone such as a smartphone
  • an image display device with a camera liquid crystal display device, organic EL device
  • a notebook PC or tablet PC such as a notebook PC or tablet PC.

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PCT/JP2016/068133 2015-06-25 2016-06-17 偏光子の製造方法 WO2016208510A1 (ja)

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JP7412972B2 (ja) * 2019-11-19 2024-01-15 日東電工株式会社 偏光板および偏光板ロール
CN111239883B (zh) * 2020-02-19 2022-08-23 京东方科技集团股份有限公司 偏光片、lcd屏幕和oled屏幕

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