WO2017204162A1 - 偏光フィルム、粘着剤層付き偏光フィルム、及び画像表示装置 - Google Patents

偏光フィルム、粘着剤層付き偏光フィルム、及び画像表示装置 Download PDF

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Publication number
WO2017204162A1
WO2017204162A1 PCT/JP2017/019030 JP2017019030W WO2017204162A1 WO 2017204162 A1 WO2017204162 A1 WO 2017204162A1 JP 2017019030 W JP2017019030 W JP 2017019030W WO 2017204162 A1 WO2017204162 A1 WO 2017204162A1
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Prior art keywords
film
polarizer
polarizing film
resin film
adhesive layer
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PCT/JP2017/019030
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English (en)
French (fr)
Japanese (ja)
Inventor
和也 吉村
哲郎 竹田
岬 鯖江
吉紹 北村
史枝 新保
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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 KR1020187031475A priority Critical patent/KR102095144B1/ko
Priority to CN201780030036.6A priority patent/CN109154689B/zh
Publication of WO2017204162A1 publication Critical patent/WO2017204162A1/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
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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

Definitions

  • the present invention relates to a polarizing film and a polarizing film with an adhesive layer having the polarizing film and an adhesive layer. Moreover, this invention relates to the image display apparatus containing the said polarizing film with an adhesive layer.
  • a polarizing film is used for image display.
  • a liquid crystal display device LCD
  • a circularly polarizing film in which a polarizing film and a quarter wavelength plate are laminated is disposed on the viewing side of the organic light emitting layer in order to shield the specular reflection of external light on the metal electrode.
  • polarizing film generally, a polyvinyl alcohol film and a polarizer made of a dichroic material such as iodine are bonded to one or both surfaces with a protective film bonded with a polyvinyl alcohol adhesive or the like. ing.
  • a polarizing film In a severe environment of thermal shock (for example, a heat shock test in which a temperature condition of ⁇ 40 ° C. and 85 ° C. is repeated), the polarizing film spreads along the absorption axis direction of the polarizer due to a change in the contraction stress of the polarizer. There is a problem that cracks (through cracks) are likely to occur. Therefore, in order to suppress the shrinkage of the polarizer and reduce the influence of thermal shock, a polarizing film usually has a 40 to 80 ⁇ m triacetyl cellulose (TAC) film as a protective film on both sides of the polarizer. A combined laminate is used. However, even in the polarizing film protected on both sides, the change in the shrinkage stress of the polarizer is not negligible, and it is difficult to completely suppress the influence of the shrinkage. It was inevitable that the shrinkage occurred.
  • TAC triacetyl cellulose
  • polarizers are also required to be thinner. If it is a thin polarizer with a thickness of 10 ⁇ m or less, the change in shrinkage stress is small, so that a through-crack is hardly generated.
  • a polarizing film is disclosed in which a protective film is bonded to one or both sides of a thin polarizer having a thickness of 10 ⁇ m or less and generation of through cracks is suppressed (see, for example, Patent Document 1).
  • the protective film is a double-sided protective polarizing film with both sides of a thin polarizer bonded
  • the protective film provided on both sides can suppress the amount of shrinkage of the polarizer during the heat shock test. Can be effectively suppressed.
  • a thin polarizer having a thickness of 10 ⁇ m or less has a problem that the optical characteristics in a humidified environment are likely to deteriorate. Therefore, even if it is a double-sided protective polarizing film using the said thin polarizer described in patent document 1, etc., depending on the kind of protective film, a polarizer deteriorates with a water
  • the moisture permeability is extremely low (specifically, 30 g / (m 2 ⁇ day) or less as a protective film bonded to both surfaces of the thin polarizer).
  • the use of a resin film is being studied.
  • the polarizer can be prevented from degrading in a humidified environment, but a thin polarizer having a thickness of 10 ⁇ m or less is used.
  • produces in a polarizing film was discovered, although the protective film was bonded together on both surfaces of the said thin polarizer.
  • a polarizing film in which a resin film having extremely low moisture permeability is laminated on both surfaces of a polarizer having a thickness of 10 ⁇ m or less, the deterioration of the polarizer due to humidification is suppressed (humidification reliability), and thermal shock is prevented. It aims at providing the polarizing film which can suppress generation
  • the present invention is a polarizing film having a first resin film on one surface of a polarizer having a thickness of 10 ⁇ m or less and a second resin film on the other surface,
  • the moisture permeability of the first resin film and the second resin film are both 30 g / (m 2 ⁇ day) or less
  • the present invention relates to a polarizing film comprising a protective plate on a surface of the first resin film opposite to the side having the polarizer.
  • the linear expansion coefficient of the protective plate is preferably 1.0 ⁇ 10 ⁇ 5 / K or less in a direction orthogonal to the absorption axis of the polarizer.
  • the linear expansion coefficients of the first resin film and the second resin film are 5.0 ⁇ 10 ⁇ 5 to 8.0 ⁇ 10 ⁇ 5 / K in the direction orthogonal to the absorption axis of the polarizer. preferable.
  • the dimensional change rate when the first resin film and the second resin film are heated at 85 ° C. for 120 hours is ⁇ 0.40 to 0% in the direction perpendicular to the absorption axis of the polarizer. Is preferred.
  • the breaking strength of the first resin film and the second resin film is preferably 5 to 30 N in the direction perpendicular to the absorption axis of the polarizer.
  • the first resin film and the second resin film are preferably the same or different cycloolefin resin films.
  • the absolute value of the degree of polarization change after being left in the environment for 500 hours is less than 0.1%.
  • the present invention also relates to a polarizing film with a pressure-sensitive adhesive layer, characterized by having a pressure-sensitive adhesive layer on the second resin film side of the polarizing film.
  • this invention relates to the image display apparatus characterized by having the said polarizing film with an adhesive layer.
  • a resin film having a very low moisture permeability specifically, 30 g / (m 2 ⁇ day) or less
  • the polarizer is deteriorated by humidification. It was newly found this time that through cracks are generated, although it is possible to suppress the humidity (improve humidification reliability).
  • a resin film (protective film) with extremely low moisture permeability generally has a large linear expansion coefficient, a small dimensional change rate in the direction perpendicular to the absorption axis of the polarizer, and / or Or it is possible that the breaking strength is low.
  • the breaking strength of the protective film is low in the direction perpendicular to the absorption axis of the polarizer, it is considered that the brittleness of the protective film is a trigger and penetration cracks are likely to occur in the polarizing film.
  • the heat shock for example, a heat shock test in which a temperature condition of ⁇ 40 ° C. and 85 ° C. is repeated
  • the amount of shrinkage of the entire polarizing film can be reduced, so that a protective film with extremely low moisture permeability on both sides of the polarizer (in other words, a linear expansion coefficient is large).
  • the polarizing film of the present invention can achieve both suppression of polarizer deterioration by humidification (improvement of humidification reliability) and suppression of occurrence of through cracks.
  • the present invention can provide a polarizing film with an adhesive layer that achieves both improved humidification reliability and suppression of the occurrence of through cracks, and an image display device using the polarizing film with the adhesive layer.
  • the polarizing film of the present invention has a first resin film on one surface of a polarizer having a thickness of 10 ⁇ m or less, and a second resin film on the other surface, The moisture permeability of the first resin film and the second resin film are both 30 g / (m 2 ⁇ day) or less, The first resin film has a protective plate on the surface opposite to the side having the polarizer.
  • the polarizing film 1 of the present invention has a first resin film 3 on one surface of a polarizer 2 and a second resin film 4 on the other surface. Further, a protective plate 5 is provided on the side of the first resin film 3 that does not have the polarizer 2.
  • the first resin film 3 and the second resin film 4 can be bonded to the polarizer 2 through an adhesive layer (not shown).
  • the protective plate 5 can be bonded to the first resin film 3 via an adhesive layer or an adhesive layer (not shown).
  • the polarizing film 1 of this invention can contain layers (For example, an easily adhesive layer, various functional layers, etc.) other than the said layer.
  • the first resin film 3 is preferably disposed on the viewing side of the polarizer 2, and the second resin film 4 is preferably disposed on the image display cell side of the polarizer 2.
  • a thin polarizer having a thickness of 10 ⁇ m or less is used.
  • the thickness of the polarizer is preferably 8 ⁇ m or less, more preferably 7 ⁇ m or less, and further preferably 6 ⁇ m or less from the viewpoint of reducing the thickness and preventing the occurrence of through cracks.
  • the thickness of the polarizer is preferably 2 ⁇ m or more, and more preferably 3 ⁇ m or more.
  • Such a thin polarizer has less thickness unevenness, excellent visibility, and less dimensional change, and therefore excellent durability against thermal shock.
  • a polarizer using a polyvinyl alcohol resin is used.
  • polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films.
  • examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products.
  • a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable.
  • a polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous iodine solution and stretching it 3 to 7 times the original length. If necessary, it may contain boric acid, zinc sulfate, zinc chloride or the like, or may be immersed in an aqueous solution of potassium iodide or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing.
  • the polyvinyl alcohol film In addition to washing the polyvinyl alcohol film surface with stains and antiblocking agents by washing the polyvinyl alcohol film with water, the polyvinyl alcohol film is also swollen to prevent unevenness such as uneven coloring. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution of boric acid or potassium iodide or in a water bath.
  • the polarizer preferably contains boric acid from the viewpoint of stretching stability and humidification reliability.
  • the boric acid content contained in the polarizer is preferably 22% by weight or less, more preferably 20% by weight or less, based on the total amount of the polarizer, from the viewpoint of suppressing the occurrence of through cracks.
  • the boric acid content with respect to the total amount of the polarizer is preferably 10% by weight or more, and more preferably 12% by weight or more.
  • the thin polarizer described in the publication 2014/077636 pamphlet etc. or the thin polarizer obtained from the manufacturing method as described in these can be mentioned.
  • Patent No. 4751486, Patent in that it can be stretched at a high magnification and the polarization performance can be improved.
  • stretching in a boric-acid aqueous solution as described in the 4751481 specification and the patent 4815544 specification is preferable, and it describes especially in the patent 4751481 specification and the patent 4815544 specification.
  • stretching in the boric-acid aqueous solution which has this is preferable.
  • These thin polarizers can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin base material in a laminated state.
  • PVA-based resin polyvinyl alcohol-based resin
  • a stretching resin base material in a laminated state.
  • 1st resin film As a material which forms the 1st resin film provided in one surface of the said polarizer, it has transparency and a water vapor transmission rate is 30 g / (m ⁇ 2 > * day) or less. Any material that can form a certain film may be used. Specific examples include a cycloolefin resin film.
  • cycloolefin resin film a known film can be used without particular limitation as long as the moisture permeability is 30 g / (m 2 ⁇ day) or less.
  • the cycloolefin-based resin is a general term for resins that are polymerized using a cycloolefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Resin.
  • cycloolefin ring-opening (co) polymers examples include cycloolefin ring-opening (co) polymers, cycloolefin addition polymers, copolymers of cycloolefins with ⁇ -olefins such as ethylene and propylene (typically random copolymers), Examples thereof include graft polymers obtained by modifying these with unsaturated carboxylic acids or derivatives thereof, and hydrides thereof.
  • Specific examples of the cycloolefin include norbornene monomers.
  • cycloolefin resins Various products are commercially available as cycloolefin resins. Specific examples include trade names “ZEONEX” and “ZEONOR” manufactured by ZEON CORPORATION, trade names “ARTON” manufactured by JSR Corporation, “TOPASS” manufactured by TICONA, and products manufactured by Mitsui Chemicals, Inc. Product name “APEL” and the like.
  • the moisture permeability of the first resin film is 30 g / (m 2 ⁇ day) or less, preferably 25 g / (m 2 ⁇ day) or less, and preferably 20 g / (m 2 ⁇ day) or less. More preferred. Further, the lower limit value of moisture permeability is not particularly limited, but ideally, it is preferable that water vapor is not permeated at all (that is, 0 g / (m 2 ⁇ day)). When the moisture permeability of the first resin film is in the above range, deterioration of the polarizer due to moisture can be suppressed.
  • the thickness of the first resin film is not particularly limited, but is 10 ⁇ m or more from the viewpoint of lowering moisture permeability to increase humidification reliability and further increasing fracture strength to further suppress penetration cracks. It is preferable that it is 12 ⁇ m or more. On the other hand, from the viewpoint of thinning, it is preferably 40 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • the linear expansion coefficient of the first resin film is not particularly limited.
  • 5.0 ⁇ 10 ⁇ 5 to 8.0 ⁇ 10 ⁇ 5 / K may be mentioned, and it may be about 5.5 ⁇ 10 ⁇ 5 to 7.5 ⁇ 10 ⁇ 5 / K.
  • the polarizing film of the present invention can suppress the occurrence of through cracks even when the first resin film having extremely low moisture permeability and a linear expansion coefficient in the above range is used.
  • a linear expansion coefficient it can measure with the measuring method as described in an Example.
  • the breaking strength of the first resin film is not particularly limited.
  • it in the direction perpendicular to the absorption axis of the polarizer, it can be about 5 to 30 N, and about 8 to 25 N. It may be about 8 to 23N.
  • the polarizing film of this invention is a case where the 1st resin film which has very low moisture permeability and has the breaking strength of the said range is used, generation
  • breaking strength it can measure by the measuring method as described in an Example.
  • the dimensional change rate when the first resin film is heat-treated at 85 ° C. for 120 hours is not particularly limited.
  • ⁇ 0 in the direction perpendicular to the absorption axis of the polarizer, ⁇ 0. It can be about 40 to 0%, can be about -0.34 to 0%, or can be about -0.33 to -0.01%.
  • the polarizing film of the present invention can suppress the occurrence of through cracks even when the first resin film having extremely low moisture permeability and a dimensional change rate in the above range is used.
  • About a dimensional change rate it can measure by the measuring method as described in an Example.
  • the polarizer and the first resin film are usually in close contact with each other through an adhesive such as an active energy ray-curable adhesive from the viewpoint of humidification reliability.
  • the active energy ray curable adhesive is an adhesive that cures by an active energy ray such as an electron beam or ultraviolet rays (radical curable type, cationic curable type), for example, in an electron beam curable type or an ultraviolet curable type. Can be used.
  • an active energy ray curable adhesive for example, a photo radical curable adhesive can be used.
  • the photo radical curable active energy ray curable adhesive is used as an ultraviolet curable adhesive, the adhesive contains a radical polymerizable compound and a photo polymerization initiator.
  • the adhesive coating method is appropriately selected depending on the viscosity of the adhesive and the target thickness.
  • coating methods include reverse coaters, gravure coaters (direct, reverse and offset), bar reverse coaters, roll coaters, die coaters, bar coaters, rod coaters and the like.
  • a method such as a dapping method can be appropriately used.
  • the surface of the first resin film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
  • the material for forming the second resin film may be any material that can form a film having transparency and moisture permeability of 30 g / (m 2 ⁇ day) or less. Specific examples include a cycloolefin resin film.
  • Examples of the cycloolefin-based resin film include those listed for the first resin film.
  • the moisture permeability of the second resin film is 30 g / (m 2 ⁇ day) or less, preferably 25 g / (m 2 ⁇ day) or less, and preferably 20 g / (m 2 ⁇ day) or less. More preferred. Further, the lower limit value of moisture permeability is not particularly limited, but ideally, it is preferable that water vapor is not permeated at all (that is, 0 g / (m 2 ⁇ day)). When the moisture permeability of the second resin film is within the above range, deterioration of the polarizer due to moisture can be suppressed.
  • the thickness of the second resin film is not particularly limited, but is 10 ⁇ m or more from the viewpoint of lowering moisture permeability to increase humidification reliability and further increasing fracture strength to further suppress penetration cracks. It is preferable that it is 12 ⁇ m or more. On the other hand, from the viewpoint of thinning, it is preferably 40 ⁇ m or less, and more preferably 30 ⁇ m or less.
  • the linear expansion coefficient of the second resin film is not particularly limited.
  • 5.0 ⁇ 10 ⁇ 5 to 8.0 ⁇ 10 ⁇ 5 / K may be mentioned, and it may be about 5.5 ⁇ 10 ⁇ 5 to 7.5 ⁇ 10 ⁇ 5 / K.
  • the polarizing film of the present invention can suppress the occurrence of through cracks even when the second resin film having extremely low moisture permeability and a linear expansion coefficient in the above range is used.
  • a linear expansion coefficient it can measure with the measuring method as described in an Example.
  • the breaking strength of the second resin film is not particularly limited.
  • it in the direction perpendicular to the absorption axis of the polarizer, it can be about 5 to 30 N, and about 8 to 25 N. It may be about 8 to 23N.
  • the polarizing film of the present invention can suppress the occurrence of through cracks even when a second resin film having extremely low moisture permeability and a breaking strength in the above range is used.
  • breaking strength it can measure by the measuring method as described in an Example.
  • the dimensional change rate when the second resin film is heat-treated at 85 ° C. for 120 hours is not particularly limited.
  • ⁇ 0 in the direction perpendicular to the absorption axis of the polarizer, ⁇ 0. It can be about 40 to 0%, can be about -0.34 to 0%, or can be about -0.33 to -0.01%.
  • the polarizing film of the present invention can suppress the occurrence of through cracks even when the second resin film having extremely low moisture permeability and a dimensional change rate in the above range is used.
  • about a dimensional change rate it can measure by the measuring method as described in an Example.
  • the polarizer and the second resin film are usually in close contact via an adhesive.
  • the adhesive include those listed for the first resin film.
  • the surface of the second resin film to which the polarizer is not adhered may be subjected to a treatment for the purpose of hard coat layer, antireflection treatment, sticking prevention, diffusion or antiglare.
  • the polarizing film of the present invention has a protection plate on the side of the first resin film that does not have the polarizer.
  • the protective plate is not particularly limited as long as it can suppress the shrinkage of the polarizing film even when the polarizing film of the present invention is exposed to a thermal shock environment.
  • the linear expansion coefficient of the protective plate is preferably 1.0 ⁇ 10 ⁇ 5 / K or less in the direction perpendicular to the absorption axis of the polarizer, and is 9.0 ⁇ 10 ⁇ 6 / K or less. Is more preferably 8.0 ⁇ 10 ⁇ 6 / K or less.
  • the protective plate can suppress the amount of contraction of the polarizer. Generation
  • the lower limit value of the linear expansion coefficient is not particularly limited, but is preferably 1.0 ⁇ 10 ⁇ 6 / K or more, for example.
  • the thickness of the protective plate is not particularly limited, but is preferably 0.5 to 1.0 mm, and more preferably 0.5 to 0.8 mm. It is preferable that the thickness of the protective plate is in the above range because the size does not easily shrink.
  • the pencil hardness of the protective plate is preferably 8H or more, and more preferably 10H or more. Since the pencil hardness of the protective plate is in the above range, it is preferable because the size does not easily shrink.
  • the pencil hardness is a pencil hardness according to JIS K 5600-5-4.
  • the specific gravity of the protective plate is preferably 2.0 or more, and more preferably 2.3 or more. It is preferable that the specific gravity of the protective plate is in the above-mentioned range because it is difficult to shrink the dimensions.
  • the thermal conductivity of the protective plate is preferably 2.0 W / (m ⁇ K) or less, and more preferably 1.5 W / (m ⁇ K) or less. Since the thermal conductivity of the protective plate is within the above range, heat is not easily transmitted to the polarizer even in a heat shock test, and the amount of contraction of the polarizer can be suppressed in a direction perpendicular to the absorption axis of the polarizer. Therefore, it is preferable.
  • the material for forming the protective plate is not particularly limited, and examples thereof include glass and an acrylic plate. Among these, glass is preferable.
  • the protective plate and the first resin film can be laminated via an adhesive layer or an adhesive layer.
  • the adhesive layer the adhesive layer described in this specification can be used as appropriate.
  • the pressure-sensitive adhesive layer is not particularly limited, and a known layer can be used.
  • an adhesive layer specifically, for example, a (meth) acrylic polymer, a silicone polymer, a polyester, a polyurethane, a polyamide, a polyether, a fluorine-based or a rubber-based polymer is used as a base polymer.
  • acrylic pressure-sensitive adhesives based on (meth) acrylic polymers are excellent in optical transparency, exhibiting moderate wettability, cohesiveness, and adhesive pressure-sensitive adhesive properties, weather resistance and heat resistance. Etc. are preferable.
  • the (meth) acrylic polymer is not particularly limited, and can be obtained by polymerizing a monomer component containing an alkyl (meth) acrylate having an alkyl group having 4 to 24 carbon atoms at the terminal of the ester group. Can be mentioned.
  • Alkyl (meth) acrylate refers to alkyl acrylate and / or alkyl methacrylate, and (meth) in the present invention has the same meaning.
  • alkyl (meth) acrylate examples include those having a linear or branched alkyl group having 4 to 24 carbon atoms, and having a linear or branched alkyl group having 4 to 9 carbon atoms.
  • Alkyl (meth) acrylates are preferred because they are easy to balance the adhesive properties. These alkyl (meth) acrylates can be used alone or in combination of two or more.
  • the monomer component forming the (meth) acrylic polymer can contain a copolymerizable monomer other than the alkyl (meth) acrylate as a monofunctional monomer component.
  • copolymerizable monomers include cyclic nitrogen-containing monomers, hydroxyl group-containing monomers, carboxyl group-containing monomers, and monomers having a cyclic ether group.
  • the monomer component forming the (meth) acrylic polymer can contain a polyfunctional monomer as necessary in order to adjust the cohesive force of the pressure-sensitive adhesive.
  • the polyfunctional monomer is a monomer having at least two polymerizable functional groups having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, such as dipentaerythritol hexa (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate.
  • a polyfunctional monomer can be used individually by 1 type or in combination of 2 or more types.
  • the production of such a (meth) acrylic polymer can be appropriately selected from known production methods such as radiation polymerization such as solution polymerization and ultraviolet polymerization, various radical polymerizations such as bulk polymerization and emulsion polymerization. Further, the (meth) acrylic polymer obtained may be a random copolymer, a block copolymer, a graft copolymer or the like.
  • the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited, and known ones commonly used in this field can be appropriately selected and used.
  • the weight average molecular weight of the (meth) acrylic polymer can be controlled by the amount of polymerization initiator, the amount of chain transfer agent used, and the reaction conditions, and the amount used is appropriately adjusted according to these types.
  • the weight average molecular weight of the (meth) acrylic polymer used in the present invention is preferably 400,000 to 4,000,000. By making the weight average molecular weight larger than 400,000, it is possible to satisfy the durability of the pressure-sensitive adhesive layer, or to suppress the occurrence of adhesive residue due to the reduced cohesive force of the pressure-sensitive adhesive layer. On the other hand, when the weight average molecular weight is larger than 4 million, the bonding property tends to be lowered. Furthermore, in the solution system, the viscosity becomes too high, and coating may be difficult.
  • the weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene. In addition, it is difficult to measure the molecular weight of the (meth) acrylic polymer obtained by radiation polymerization.
  • the pressure-sensitive adhesive composition used in the present invention can contain a crosslinking agent.
  • crosslinking agents include isocyanate crosslinking agents, epoxy crosslinking agents, silicone crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, silane crosslinking agents, alkyletherified melamine crosslinking agents, metal chelate crosslinking agents,
  • the crosslinking agent include oxides, and these can be used alone or in combination of two or more.
  • an isocyanate type crosslinking agent and an epoxy-type crosslinking agent are used preferably.
  • the crosslinking agent may be used alone or in combination of two or more, but the total content is based on 100 parts by weight of the (meth) acrylic polymer.
  • the crosslinking agent is preferably contained in the range of 0.01 to 10 parts by weight.
  • a (meth) acrylic oligomer can be contained in order to improve the adhesive force.
  • the pressure-sensitive adhesive composition used in the present invention may contain a silane coupling agent in order to increase the water resistance at the interface when applied to a hydrophilic adherend such as glass of the pressure-sensitive adhesive layer.
  • the pressure-sensitive adhesive composition used in the present invention may contain other known additives, such as polyether compounds of polyalkylene glycols such as polypropylene glycol, powders of colorants and pigments, dyes, and the like. , Surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, UV absorbers, polymerization inhibitors, inorganic or organic fillers, It can be added as appropriate depending on the application in which metal powder, particles, foil, etc. are used. Moreover, you may employ
  • the formation method of the pressure-sensitive adhesive layer can be performed by a known method.
  • an adhesive layer for laminating the protective plate and the first resin film “LUCIACS” manufactured by Nitto Denko Corporation, “Clear Fit” manufactured by Mitsubishi Plastics Co., Ltd., manufactured by Dexerials Corporation
  • a pressure-sensitive adhesive layer pressure-sensitive adhesive sheet
  • SVR optical elastic resin
  • the absolute value of the degree of polarization change after standing in the environment for 500 hours is preferably less than 0.1%, more preferably 0.05% or less, and further preferably 0.03% or less. preferable. Since the polarizing film of the present invention has a protective plate laminated on the first resin film, it can be used in a severe environment of thermal shock (for example, a heat shock test in which temperature conditions of ⁇ 40 ° C. and 85 ° C. are repeated).
  • the shrinkage force of the polarizing film as a whole becomes extremely small, and furthermore, since the low moisture permeation protective film is used, the deterioration of the polarizer due to water is suppressed, and as a result, even when exposed to harsh environments, the degree of polarization The change is small and the optical characteristics are excellent.
  • the polarizing film with an adhesive layer of this invention has an adhesive layer in the said 2nd resin film side of the said polarizing film, It is characterized by the above-mentioned.
  • the pressure-sensitive adhesive layer can be laminated on the side having no polarizer of the second resin film.
  • the polarizing film 10 with the pressure-sensitive adhesive layer of the present invention comprises a protective plate 5, a first resin film 3, a polarizer 2, a second resin film 4, and a pressure-sensitive adhesive layer 6. In order.
  • the polarizing film with the pressure-sensitive adhesive layer of the present invention is obtained by directly applying the pressure-sensitive adhesive composition on the second resin film of the polarizing film having the protective plate, and removing the solvent and the like by heating and drying. Can be formed. Moreover, the adhesive layer formed in the support body etc. can be transcribe
  • the pressure-sensitive adhesive composition those described in the present specification can be appropriately used, and among them, an acrylic pressure-sensitive adhesive having the above-mentioned (meth) acrylic polymer as a base polymer is preferable.
  • Various methods are used as a method for applying the pressure-sensitive adhesive composition. Specifically, for example, by roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, die coater, etc. Examples thereof include an extrusion coating method.
  • the heating and drying temperature is preferably about 30 to 200 ° C, more preferably about 40 to 180 ° C, and further preferably about 80 to 150 ° C. By setting the heating temperature in the above range, an adhesive layer having excellent adhesive properties can be obtained.
  • As the drying time an appropriate time can be adopted as appropriate.
  • the drying time is preferably about 5 seconds to 20 minutes, more preferably about 30 seconds to 10 minutes, and further preferably 1 minute to 8 minutes.
  • a peeled sheet for example, a peeled sheet (separator) can be used.
  • a silicone release liner is preferably used as the release-treated sheet.
  • constituent material of the separator examples include, for example, plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
  • plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films
  • porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof.
  • a plastic film is used suitably from the point which is excellent in surface smoothness.
  • plastic film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
  • plastic film examples include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, and ethylene.
  • -Vinyl acetate copolymer film and the like.
  • the thickness of the separator is usually about 5 to 200 ⁇ m, preferably about 5 to 100 ⁇ m.
  • An antistatic treatment such as a mold can also be performed.
  • the release property from the pressure-sensitive adhesive layer can be further improved by appropriately performing a release treatment such as silicone treatment, long-chain alkyl treatment, or fluorine treatment on the surface of the separator.
  • seat which carried out the peeling process used in preparation of said polarizing film with an adhesive layer can be used as a separator of the polarizing film with an adhesive layer as it is, and can simplify in a process surface.
  • the pressure-sensitive adhesive layer is formed after an anchor layer is formed on the surface of the second resin film, or after various easy adhesion treatments such as corona treatment and plasma treatment.
  • An agent layer can be formed. Moreover, you may perform an easily bonding process on the surface of an adhesive layer.
  • the thickness of the pressure-sensitive adhesive layer is not particularly limited, and is preferably 5 to 100 ⁇ m, for example, and preferably 10 to 50 ⁇ m.
  • the polarizing film with the pressure-sensitive adhesive layer of the present invention uses a double-sided protective polarizing film with a polarizer thickness of 10 ⁇ m or less, the polarizing film with the pressure-sensitive adhesive layer as a whole can be thinned.
  • the thickness of the polarizing film with the pressure-sensitive adhesive layer can be 70 ⁇ m or less.
  • the polarizing film with an adhesive layer of the present invention can be attached to an image display cell such as a liquid crystal cell through the adhesive layer.
  • the polarizing film with an adhesive layer of this invention can be used suitably as a visual recognition side polarizing film of a liquid crystal display device.
  • Image display device The image display device of the present invention has the above-mentioned polarizing film with an adhesive layer.
  • the image display device of the present invention only needs to include the polarizing film with the pressure-sensitive adhesive layer of the present invention, and other configurations can be the same as those of the conventional image display device.
  • the image display device of the present invention includes the polarizing film with the pressure-sensitive adhesive layer, it has high reliability.
  • 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 1.0 part 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 laminated body was added to a boric acid aqueous solution having a liquid temperature of 70 ° C. (an aqueous solution obtained by adding 4.5 parts by weight of boric acid and 5 parts by weight of potassium iodide to 100 parts by weight of water).
  • An ultraviolet curable adhesive was prepared by mixing 40 parts by weight of N-hydroxyethylacrylamide (HEAA), 60 parts by weight of acryloylmorpholine (ACMO), and 3 parts by weight of a photoinitiator “IRGACURE 819” (manufactured by BASF).
  • HEAA N-hydroxyethylacrylamide
  • ACMO acryloylmorpholine
  • UVGACURE 819 a photoinitiator
  • the viewing-side transparent protective film First resin film (Cycloolefin film having a thickness of 27 ⁇ m (trade name: ZF12-025-1300UHC, manufactured by Nippon Zeon Co., Ltd.), moisture permeability at 40 ° C., 92% RH: 17 g / (m 2 ⁇ day), linear expansion coefficient: 6 ⁇ 10 ⁇ 5 / K, dimensional change rate: ⁇ 0.33%, breaking strength: 13 N), and then irradiated with ultraviolet rays as active energy rays, adhesive was cured.
  • First resin film Cycloolefin film having a thickness of 27 ⁇ m (trade name: ZF12-025-1300UHC, manufactured by Nippon Zeon Co., Ltd.)
  • linear expansion coefficient 6 ⁇ 10 ⁇ 5 / K
  • dimensional change rate ⁇ 0.33%
  • breaking strength 13 N
  • Ultraviolet irradiation is performed using a gallium-encapsulated metal halide lamp, an irradiation device: Fusion UV Systems, Inc.
  • the illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.
  • the amorphous PET base material is peeled off, and the UV curable adhesive is applied to the peeled surface so that the thickness of the adhesive layer after curing is 0.1 ⁇ m, and corona treatment in advance.
  • Image display cell side transparent protective film (second resin film) (cycloolefin film having a thickness of 13 ⁇ m (trade name: ZF-014-1330, manufactured by Nippon Zeon Co., Ltd.), 40 ° C., 92% RH
  • the moisture permeability is 12 g / (m 2 ⁇ day)
  • the coefficient of linear expansion is 7.1 ⁇ 10 ⁇ 5 / K
  • the dimensional change rate is ⁇ 0.01%
  • the breaking strength is 9 N.
  • ultraviolet rays were irradiated to cure the adhesive, and a double-sided protective polarizing film (1) using a thin polarizer was produced.
  • UV irradiation is performed using a gallium-filled metal halide lamp, irradiation device: Fusion UVSystems, Inc.
  • the illuminance of ultraviolet rays was measured using a Sola-Check system manufactured by Solatell.
  • the amorphous PET base material is peeled off, and the UV curable adhesive produced in Example 1 is applied to the peeled surface so that the thickness of the cured adhesive layer is 0.1 ⁇ m.
  • Image display cell side transparent protective film (cycloolefin film having a thickness of 13 ⁇ m (trade name: ZF-014-1330, manufactured by Nippon Zeon Co., Ltd.), moisture permeability at 40 ° C., 92% RH: 12 g / (M 2 ⁇ day), linear expansion coefficient: 7.1 ⁇ 10 ⁇ 5 / K, dimensional change rate: ⁇ 0.01%, breaking strength: 9 N), and then irradiated with ultraviolet rays in the same manner as above.
  • the adhesive was cured to prepare a double-sided protective polarizing film (2) using a thin polarizer.
  • Production Example 3 (Production of Polarizing Film (3)) While applying a polyvinyl alcohol-based adhesive on the surface of the polarizer (thickness: 5 ⁇ m) of the optical film laminate obtained in Production Example 1 so that the thickness of the adhesive layer is 0.1 ⁇ m, the viewing side is transparent.
  • Protective film (Acrylic film having a thickness of 40 ⁇ m (trade name: HX-40UC-1330, manufactured by Kaneka Corporation), moisture permeability at 40 ° C., 92% RH: 70 g / (m 2 ⁇ day), wire (Expansion coefficient: 4.3 ⁇ 10 ⁇ 5 / K, dimensional change rate: ⁇ 0.5%, breaking strength: 39 N), and then drying at 50 ° C. for 5 minutes.
  • the amorphous PET base material was peeled off, and the image display cell side transparent protective film (with the polyvinyl alcohol adhesive applied to the peeled surface so that the thickness of the adhesive layer was 0.1 ⁇ m
  • Acrylic film having a thickness of 20 ⁇ m (trade name: RV-20UB-1330, manufactured by Toyo Kohan Co., Ltd.), moisture permeability at 40 ° C. and 92% RH: 170 g / (m 2 ⁇ day), linear expansion
  • the coefficient 5.6 ⁇ 10 ⁇ 5 / K, dimensional change rate: ⁇ 0.35%, breaking strength: 19 N
  • a protective polarizing film (3) was produced.
  • Example 1 On the viewing-side protective film of the double-sided protective polarizing film (1) obtained in Production Example 1, an adhesive sheet (thickness: 150 ⁇ m, “LUCIACS” (trade name), which is an adhesive sheet manufactured by Nitto Denko Corporation) To form a pressure-sensitive adhesive layer, and a protective plate (500 ⁇ m thick cover glass, linear expansion coefficient: 8 ⁇ 10 ⁇ 6 / K, pencil hardness: 10H, specific gravity: 2.5, Thermal conductivity: 1 W / (m ⁇ K)) was laminated to form a polarizing film with a protective plate.
  • an adhesive sheet thickness: 150 ⁇ m, “LUCIACS” (trade name), which is an adhesive sheet manufactured by Nitto Denko Corporation
  • a protective plate 500 ⁇ m thick cover glass, linear expansion coefficient: 8 ⁇ 10 ⁇ 6 / K, pencil hardness: 10H, specific gravity: 2.5, Thermal conductivity: 1 W / (m ⁇ K)
  • Example 2 A polarizing film with a protective plate was formed in the same manner as in Example 1 except that the double-sided protective polarizing film (2) obtained in Production Example 2 was used.
  • Comparative Examples 1 to 3 In Comparative Examples 1 to 3, the double-sided protective polarizing films (1) to (3) obtained in Production Examples 1 to 3 were used as they were (no protective plate was laminated).
  • Example moisture permeability of protective film used in comparative example, linear expansion coefficient of protective film and protective plate, polarizing film with protective film obtained in example, dimensional change rate of polarizing film used in comparative example, and penetration
  • the occurrence of cracks was measured by the following method.
  • the moisture permeability was measured according to a moisture permeability test (cup method) of JIS Z0208. A sample cut to a diameter of 6 cm was set in a moisture permeable cup (opening diameter: diameter 6 cm) containing about 15 g of calcium chloride, and the temperature was 40 ° C. and the humidity was 92% R.D. H. The moisture permeability (g / (m 2 ⁇ day)) was determined by measuring the weight increase of calcium chloride before and after being left for 24 hours.
  • a sample was prepared by cutting the double-sided protective polarizing film used in Examples and Comparative Examples into a size of 100 mm ⁇ 100 mm (absorption axis direction of polarizer is 100 mm). The sample was autoclaved at 50 ° C. and 0.5 MPa for 15 minutes, removed from the autoclave, and allowed to stand for 24 hours in an environment at room temperature (23 ° C.). Thereafter, it was put into an oven at 85 ° C. for 120 hours.
  • the protective film After taking out from the oven, the protective film is peeled off from the sample, and for each protective film, the length of each protective film is measured using a non-contact type two-dimensional image analyzer (trade name: QVA606L1L-C, manufactured by Mitutoyo Corporation). Was measured. From the measured values before and after the treatment, the dimensional change rate was calculated based on the following formula.
  • the linear expansion coefficient was measured using a thermomechanical analyzer (product name: TMA7100, manufactured by Hitachi High-Tech Science Co., Ltd.). Specifically, a sample (length 20 mm ⁇ width 5 mm) was cut out from the protective film used in Examples and Comparative Examples, the sample was set in a tensile measurement jig, a tensile load 20 mN, a temperature increase rate, 10 ° C./min. The linear expansion coefficient was obtained by measuring -40 ° C to 85 ° C under the conditions of 4 cycles (heat shock conditions). The linear expansion coefficient was measured in a direction perpendicular to the absorption axis of the polarizer.
  • ⁇ Measurement of change in polarization degree ( ⁇ P) of polarizing film The polarizing films obtained in Examples and Comparative Examples were subjected to 85 ° C./85% R.D. H. For 500 hours.
  • the polarization degree of the polarizing film before and after the addition was measured using a spectrophotometer with an integrating sphere (V7100 manufactured by JASCO Corporation), and the amount of change ⁇ P in the polarization degree was determined by the following equation.
  • Polarization degree P (%) ⁇ (Tp ⁇ Tc) / (Tp + Tc) ⁇ 1/2 ⁇ 100
  • Each transmittance is represented by a Y value obtained by correcting visibility with a two-degree field of view (C light source) of JIS Z8701, with 100% of the completely polarized light obtained through the Granteller prism polarizer.
  • heat shock test> A pressure-sensitive adhesive layer was provided on the image display cell side transparent protective film side of the double-sided protective polarizing film obtained in Examples and Comparative Examples to prepare a polarizing film with a pressure-sensitive adhesive layer.
  • the polarizing film with a pressure-sensitive adhesive layer was cut into 50 mm ⁇ 150 mm (absorption axis direction was 50 mm), and bonded to 0.5 mm-thick alkali-free glass to prepare a sample.
  • the sample was subjected to a heat shock of ⁇ 40 to 85 ° C. for 30 minutes ⁇ 100 times in each environment, and then taken out, and it was visually confirmed whether or not there were through cracks (number) in the polarizing film. . This test was performed 10 times.

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JP7288306B2 (ja) 2018-02-26 2023-06-07 日東電工株式会社 偏光フィルムおよびその製造方法、光学フィルム、ならびに画像表示装置
JP2019219525A (ja) * 2018-06-20 2019-12-26 日東電工株式会社 偏光フィルム、粘着剤層付き偏光フィルム、及び画像表示装置
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