WO2014084154A1 - Film stratifié - Google Patents

Film stratifié Download PDF

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Publication number
WO2014084154A1
WO2014084154A1 PCT/JP2013/081582 JP2013081582W WO2014084154A1 WO 2014084154 A1 WO2014084154 A1 WO 2014084154A1 JP 2013081582 W JP2013081582 W JP 2013081582W WO 2014084154 A1 WO2014084154 A1 WO 2014084154A1
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WO
WIPO (PCT)
Prior art keywords
film
pva
thermoplastic resin
stretching
polarizing
Prior art date
Application number
PCT/JP2013/081582
Other languages
English (en)
Japanese (ja)
Inventor
絵美 藤井
修 風藤
Original Assignee
株式会社クラレ
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 株式会社クラレ filed Critical 株式会社クラレ
Priority to JP2014505453A priority Critical patent/JP6444732B2/ja
Priority to CN201380062611.2A priority patent/CN104903761B/zh
Priority to KR1020157017287A priority patent/KR102072261B1/ko
Publication of WO2014084154A1 publication Critical patent/WO2014084154A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2551/00—Optical elements

Definitions

  • the present invention relates to a laminated film useful as a raw film for producing a polarizing film, a film roll formed by winding the laminated film, and a method for producing a polarizing film using the laminated film.
  • a polarizing plate having a light transmission and shielding function is a basic component of a liquid crystal display (LCD) together with a liquid crystal that changes a polarization state of light.
  • LCD liquid crystal display
  • Many polarizing plates have a structure in which a protective film such as a cellulose triacetate (TAC) film is bonded to the surface of a polarizing film.
  • TAC cellulose triacetate
  • iodine dye stretched film was oriented uniaxially stretched (I 3 - and I 5 -, etc.), such as a dichroic organic dye dichroic dye is adsorbed What you are doing is the mainstream.
  • a polarizing film can be obtained by uniaxially stretching a PVA film preliminarily containing a dichroic dye, adsorbing a dichroic dye simultaneously with uniaxial stretching of the PVA film, or dichroic after uniaxially stretching the PVA film. Manufactured by adsorbing dyes.
  • LCDs are used in a wide range of devices such as small devices such as calculators and wrist watches, notebook computers, liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, mobile phones, and measuring devices used indoors and outdoors.
  • small devices such as calculators and wrist watches
  • notebook computers liquid crystal monitors, liquid crystal color projectors, liquid crystal televisions, in-vehicle navigation systems, mobile phones, and measuring devices used indoors and outdoors.
  • LCDs liquid crystal monitors
  • liquid crystal color projectors liquid crystal televisions
  • in-vehicle navigation systems mobile phones
  • mobile phones and measuring devices used indoors and outdoors.
  • thinner polarizing plates such as small notebook personal computers and mobile phones.
  • One way to reduce the thickness of the polarizing plate is to reduce the thickness of the polarizing film.
  • a thin PVA film is likely to be stretched at the time of stretching, and the productivity and yield of the polarizing film are lowered, which leads to high costs.
  • the method using a laminate formed by forming a PVA layer on a thermoplastic resin film by a coating method has the following problems.
  • a laminate in which a PVA layer is formed on a thermoplastic resin film by a coating method has a relatively high adhesive strength between the thermoplastic resin film and the PVA layer, and such a laminate having a high adhesive strength. When the film is stretched, an appropriate neck-in of the PVA layer is hindered, and it is difficult to obtain a polarizing film having excellent polarization performance.
  • the present invention provides a laminated film for producing a polarizing film, a thin PVA, which is capable of easily producing a polarizing film which is less likely to be stretched during stretching even when a thin PVA film is used and which has excellent polarizing performance. Even when a film is used, it is difficult to cause stretching breakage at the time of stretching, and a laminated film capable of extremely easily producing a polarizing film excellent in polarizing performance, a film roll in which they are wound, and It aims at providing the manufacturing method of the polarizing film using the said laminated
  • the inventors of the present invention when producing a polarizing film using a thin single-layer PVA film, have a water process such as a swelling process and a dyeing process performed before stretching. After passing through the step of bringing into contact with the film, curling is likely to occur at both ends in the width direction of the film.
  • the thermoplastic resin film is laminated on the PVA film with an adhesive strength of a specific value or less, curling is suppressed, the occurrence of stretch breakage can be reduced, and the adhesive strength is below the specific value.
  • the thermoplastic resin film is finally removed, it is found that the removal becomes extremely easy, and further studies are made based on these findings. The present invention has been completed.
  • the present invention [1] A laminated film for producing a polarizing film in which a PVA film and a thermoplastic resin film are adjacent to each other, and an adhesive strength between the two films is 200 mN / 15 mm or less; [2] A laminated film in which a PVA film and a thermoplastic resin film are adjacent to each other, and an adhesive strength between the films is less than 1.5 mN / 15 mm; [3] The laminated film of [1] or [2] above, wherein the PVA film has a thickness of 45 ⁇ m or less; [4] The laminated film according to any one of [1] to [3], which is a long laminated film; [5] The laminated film of [4] above, wherein the width of the thermoplastic resin film is 1.1 times or more of the width of the PVA film; [6] A film roll formed by winding the laminated film of [4] or [5] above; [7] A method for producing a polarizing film, comprising a water contact step
  • a laminated film for producing a polarizing film that is less likely to be stretched at the time of stretching and can easily produce a polarizing film having excellent polarizing performance Even when thin PVA film is used, it is difficult to cause stretching breakage during stretching, and a laminated film that can extremely easily produce a polarizing film having excellent polarization performance, and a film roll formed by winding them up And the manufacturing method of the polarizing film using the said laminated
  • the present invention will be described in detail.
  • the PVA film and the thermoplastic resin film are adjacent to each other.
  • PVA film As PVA constituting the PVA film, vinyl esters such as vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, isopropenyl acetate, etc. Those obtained by saponifying a polyvinyl ester obtained by polymerizing one or more of the above can be used. Among the above-mentioned vinyl esters, a compound having a vinyloxycarbonyl group (H 2 C ⁇ CH—O—CO—) in the molecule is preferable from the viewpoint of ease of production, availability, and cost of PVA, More preferred is vinyl acetate.
  • the polyvinyl ester is preferably obtained using only one or two or more vinyl esters as monomers, and more preferably obtained using only one vinyl ester as a monomer.
  • a copolymer of one or more vinyl esters and other monomers copolymerizable therewith may be used.
  • Examples of the other monomer copolymerizable with the vinyl ester include ⁇ -olefins having 2 to 30 carbon atoms such as ethylene, propylene, 1-butene, and isobutene; (meth) acrylic acid or a salt thereof; (Meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate i-propyl, (meth) acrylate n-butyl, (meth) acrylate i-butyl, ( (Meth) acrylic acid esters such as t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate and octadecyl (meth) acrylate; (meth) acrylamide; N-methyl ( (Meth) acrylamide, N-ethyl (meth) acrylamide, N,
  • Vinyl ether vinyl cyanide such as (meth) acrylonitrile
  • vinyl halide such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride
  • Allyl compounds such as allyl acetate and allyl chloride; maleic acid or salts thereof, esters or acid anhydrides; itaconic acid or salts thereof, esters or acid anhydrides
  • vinylsilyl compounds such as vinyltrimethoxysilane; unsaturated sulfonic acids or salts thereof And so on.
  • Said polyvinyl ester can have a structural unit derived from 1 type, or 2 or more types of an above described other monomer.
  • the proportion of structural units derived from the other monomers in the polyvinyl ester is preferably 15 mol% or less based on the number of moles of all structural units constituting the polyvinyl ester, and is preferably 10 mol% or less. More preferably, it is more preferably 5 mol% or less.
  • those not graft-copolymerized can be preferably used, but PVA can be used for one or more kinds of graft copolymer as long as the effects of the present invention are not significantly impaired. It may be modified with a monomer.
  • the said graft copolymerization can be performed with respect to at least one of polyvinyl ester and PVA obtained by saponifying it.
  • the graft copolymerizable monomer include unsaturated carboxylic acids or derivatives thereof; unsaturated sulfonic acids or derivatives thereof; ⁇ -olefins having 2 to 30 carbon atoms, and the like.
  • the proportion of structural units derived from the graft copolymerizable monomer in the polyvinyl ester or PVA is preferably 5 mol% or less based on the number of moles of all structural units constituting the polyvinyl ester or PVA.
  • the hydroxyl group may be cross-linked or may not be cross-linked.
  • the PVA may have a hydroxyl group partially reacted with an aldehyde compound such as acetaldehyde or butyraldehyde to form an acetal structure, or may not react with these compounds to form an acetal structure. Also good.
  • the polymerization degree of the above PVA is not particularly limited, but is preferably 1000 or more.
  • the polymerization degree of PVA is 1000 or more, there is an advantage that the polarizing performance of the obtained polarizing film can be further improved. If the polymerization degree of PVA is too high, it tends to lead to an increase in the production cost of PVA and poor processability during film formation. Therefore, the polymerization degree of PVA is more preferably in the range of 1000 to 10,000. A range of 1500 to 8000 is more preferable, and a range of 2000 to 5000 is particularly preferable.
  • the degree of polymerization of PVA as used herein means the average degree of polymerization measured according to the description of JIS K6726-1994.
  • the saponification degree of PVA is preferably 99.0 mol% or more, more preferably 99.8 mol% or more, and 99.9 mol% from the viewpoint of good wet heat resistance of the obtained polarizing film or the like. It is still more preferable that it is above.
  • the saponification degree of PVA refers to the vinyl alcohol unit relative to the total number of moles of structural units (typically vinyl ester units) and vinyl alcohol units that can be converted into vinyl alcohol units by saponification of PVA. The ratio (mol%) which the number of moles occupies.
  • the degree of saponification can be measured according to the description of JIS K6726-1994.
  • the PVA film may contain a plasticizer together with the above PVA.
  • a plasticizer polyhydric alcohol is preferably used, and specific examples include ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, tetraethylene glycol, trimethylolpropane, and the like.
  • PVA film Can contain one or more of these plasticizers. Among these, glycerin is preferable because the stretchability of the PVA film becomes better.
  • the content of the plasticizer in the PVA film is preferably 3 to 20 parts by mass, more preferably 5 to 17 parts by mass, and still more preferably 7 to 14 parts by mass with respect to 100 parts by mass of PVA. .
  • the content of the plasticizer in the PVA film is 3 parts by mass or more with respect to 100 parts by mass of PVA, the stretchability of the PVA film is improved.
  • the content of the plasticizer in the PVA film is 20 parts by mass or less with respect to 100 parts by mass of PVA, the plasticizer bleeds out on the surface of the PVA film and the handling property of the PVA film is reduced. be able to.
  • a PVA film is produced using a film-forming stock solution for producing a PVA film, which will be described later, the film-forming property is improved and the occurrence of film thickness unevenness is suppressed, and a metal roll is used for film formation. Since a PVA film can be easily peeled off from these metal rolls and belts when a belt or a belt is used, it is preferable to add a surfactant to the film-forming stock solution.
  • the PVA film may contain a surfactant.
  • surfactant that is blended in the film-forming stock solution for producing the PVA film, and thus the surfactant contained in the PVA film, but from the viewpoint of releasability from a metal roll or belt, an anion is used.
  • Surfactants or nonionic surfactants are preferred, and nonionic surfactants are particularly preferred.
  • anionic surfactant for example, a carboxylic acid type such as potassium laurate; a sulfate ester type such as octyl sulfate; a sulfonic acid type such as dodecylbenzene sulfonate is suitable.
  • Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether; alkylphenyl ether types such as polyoxyethylene octylphenyl ether; alkyl ester types such as polyoxyethylene laurate; polyoxyethylene laurylamino Alkylamine type such as ether; alkylamide type such as polyoxyethylene lauric acid amide; polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether; alkanolamide type such as lauric acid diethanolamide and oleic acid diethanolamide; polyoxy An allyl phenyl ether type such as alkylene allyl phenyl ether is preferred. These surfactants can be used alone or in combination of two or more.
  • the content of the surfactant in the film-forming stock solution, and thus the content of the surfactant in the PVA film is determined as the film-forming stock solution or the PVA film.
  • the amount is preferably in the range of 0.01 to 0.5 parts by mass, more preferably in the range of 0.02 to 0.3 parts by mass with respect to 100 parts by mass of PVA contained in.
  • the content of the surfactant is 0.01 parts by mass or more with respect to 100 parts by mass of PVA, the film forming property and the peelability can be improved.
  • the content of the surfactant is 0.5 parts by mass or less with respect to 100 parts by mass of PVA, the surfactant bleeds out on the surface of the PVA film, resulting in blocking, and handling properties are reduced. Can be suppressed.
  • the PVA film may be composed only of PVA, or may be composed only of PVA and the above-described plasticizer and / or surfactant. If necessary, an antioxidant, an antifreeze agent, a pH adjuster, You may contain other components other than above-mentioned PVA, a plasticizer, and surfactant, such as a masking agent, a coloring inhibitor, and an oil agent.
  • the PVA content in the PVA film is preferably in the range of 50 to 100% by mass, more preferably in the range of 80 to 100% by mass, and in the range of 85 to 100% by mass. Further preferred.
  • the said thickness may be 45 micrometers or less. Preferably, it is 35 ⁇ m or less, more preferably 25 ⁇ m or less.
  • the said thickness is 3 micrometers or more.
  • the length of the long film is not particularly limited, and can be set as appropriate according to the application of the polarizing film to be produced.
  • the length can be in the range of 5 to 20000 m.
  • variety of the said elongate film For example, although it can be set to 50 cm or more, it is preferable that it is 1 m or more because a wide polarizing film is calculated
  • the width of the long film is preferably 7 m or less.
  • the manufacturing method of a PVA film is not specifically limited, The manufacturing method from which the thickness and width
  • above-mentioned PVA which comprises a PVA film, and as needed
  • the film-forming stock solution contains at least one of a plasticizer, a surfactant, and other components, it is preferable that these components are uniformly mixed.
  • liquid medium used for the preparation of the membrane forming stock solution examples include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol. , Trimethylolpropane, ethylenediamine, diethylenetriamine and the like, and one or more of them can be used. Among these, water is preferable from the viewpoint of a small environmental load and recoverability.
  • the volatile fraction of the film-forming stock solution (the content ratio of volatile components such as a liquid medium removed by volatilization or evaporation during film-forming in the film-forming stock solution) varies depending on the film-forming method, film-forming conditions, etc., but 50 to 95 It is preferably within the range of mass%, more preferably within the range of 55 to 90 mass%, and even more preferably within the range of 60 to 85 mass%.
  • the volatile fraction of the film-forming stock solution is 50% by mass or more, the viscosity of the film-forming stock solution does not become too high, and filtration and defoaming are smoothly performed during preparation of the film-forming stock solution, and there are few foreign matters and defects. Film production is facilitated.
  • the volatile fraction of the film-forming stock solution is 95% by mass or less, the concentration of the film-forming stock solution does not become too low, and the production of an industrial PVA film becomes easy.
  • Examples of the film forming method for forming a PVA film using the above-described film forming stock solution include a cast film forming method, an extrusion film forming method, a wet film forming method, a gel film forming method, and the like.
  • a membrane method and an extrusion film forming method are preferred. These film forming methods may be used alone or in combination of two or more.
  • the extrusion film forming method is more preferable because a PVA film having a uniform thickness and width and good physical properties can be obtained.
  • the PVA film can be dried or heat-treated as necessary.
  • thermoplastic resin film examples include various thermoplastic resins such as polyolefin (polyethylene, polypropylene, polymethylpentene, etc.), polystyrene, polycarbonate, polyvinyl chloride, methacrylic resin, nylon, polyethylene terephthalate, and the like. Examples thereof include a copolymer having a plurality of types of monomer units constituting these thermoplastic resins.
  • polyolefin polyethylene, polypropylene, polymethylpentene, etc.
  • polystyrene polycarbonate
  • polyvinyl chloride methacrylic resin
  • nylon polyethylene terephthalate
  • thermoplastic resin film examples include a copolymer having a plurality of types of monomer units constituting these thermoplastic resins.
  • polyolefin is preferable because it has high stretchability.
  • limiting in particular in the method of manufacturing a thermoplastic resin film It can manufacture by well-known methods, such as melt molding and calendar molding.
  • the said thickness is preferably 10 micrometers or more, 15 micrometers or more It is more preferable that it is 20 ⁇ m or more.
  • the said thickness is 100 micrometers or less.
  • thermoplastic resin film is also preferably a long film, and the length can be set within a range of, for example, 5 to 20000 m.
  • the width of the thermoplastic resin film is preferably 1.1 times or more the width of the PVA film. This is because, in the water contact step, the width of the PVA film tends to expand due to swelling, while the width of the thermoplastic resin film hardly changes. Therefore, when the width of the thermoplastic resin film satisfies the above relationship, This is because curling occurring at both end portions in the width direction can be more effectively suppressed even when swollen.
  • the width of the thermoplastic resin film is more preferably 1.15 times or more, and further preferably 1.2 times or more the width of the PVA film.
  • the upper limit of the width of the thermoplastic resin film is not particularly limited. However, even if it is made wider than necessary, no further curling suppression effect can be expected. Therefore, the width of the thermoplastic resin film is 1. of the width of the PVA film. It is preferably 8 times or less, and more preferably 1.6 times or less.
  • the adhesive strength between the PVA film and the thermoplastic resin film needs to be 200 mN / 15 mm or less. If the adhesive strength exceeds 200 mN / 15 mm, the removal of the thermoplastic resin film becomes considerably difficult, and the stretching process is performed in a state where the thermoplastic resin film and the PVA film are adjacent to each other as will be described later. In some cases, an appropriate neck-in of the PVA film is hindered, and it becomes difficult to obtain a polarizing film having excellent polarization performance.
  • the adhesive strength is preferably 100 mN / 15 mm or less, more preferably 10 mN / 15 mm or less, and further preferably 5 mN / 15 mm or less.
  • the adhesive strength is more preferably less than 1.3 mN / 15 mm, and the two films are merely adjacent to each other and are not substantially bonded (adhesive strength is less than 1.0 mN / 15 mm). More preferably, The adhesive strength can be measured by a T-shaped peeling test as described in JIS K6854-3: 1999, and specifically by the method described later in the examples.
  • the long laminated film formed by using a long film for both the PVA film and the thermoplastic resin film is wound into a roll to form a film roll from the viewpoint of handleability.
  • the laminated film of the present invention having an adhesive strength of 200 mN / 15 mm or less is used as a raw film for producing a polarizing film.
  • the laminated film of the present invention having an adhesive strength of less than 1.5 mN / 15 mm suppresses the occurrence of curling even after passing through the step of contacting with water. Since it can be reduced and the removal of the thermoplastic resin film is extremely easy, it is conventionally known as a general PVA film application such as a raw film for producing a retardation film. Although it can use suitably for various uses, also in the said laminated
  • a swelling process process As a water contact process, a swelling process process, a dyeing process process, a bridge
  • the contact between the laminated film and water in the water contact step may be either a method of spraying water on the laminated film or a method of immersing the laminated film in water. From the viewpoint, a method of immersing the laminated film in water is preferable.
  • the water used is not limited to pure water, According to the objective of each process, the aqueous solution which is mentioned later, Furthermore, an aqueous dispersion liquid etc. can also be used.
  • the swelling treatment in the swelling treatment step can be performed by immersing the laminated film in water.
  • the temperature of the water when immersed in water is preferably in the range of 20 to 40 ° C, more preferably in the range of 22 to 38 ° C, and preferably in the range of 25 to 35 ° C. Further preferred.
  • the time for immersion in water is, for example, preferably in the range of 0.5 to 5 minutes, and more preferably in the range of 1 to 3 minutes.
  • the water at the time of immersing in water is not limited to a pure water, The aqueous solution in which various components melt
  • the dyeing process in the dyeing process can be performed by immersing the laminated film in an aqueous solution containing a dichroic dye.
  • concentration of the dichroic dye in the aqueous solution containing the dichroic dye can be appropriately set according to the type of the dichroic dye to be used, for example, within the range of 0.001 to 1% by mass.
  • iodine-potassium iodide aqueous solution when used as an aqueous solution containing a dichroic dye, iodine-based dye can be efficiently adsorbed on the PVA film, so that the concentration of iodine (I 2 ) used is Is preferably in the range of 0.01 to 1.0 mass%, and the concentration of potassium iodide (KI) used is preferably in the range of 0.01 to 10 mass%.
  • the temperature of the aqueous solution containing the dichroic dye is preferably within a range of 20 to 50 ° C., and preferably within a range of 25 to 40 ° C., because the dichroic dye can be efficiently adsorbed to the PVA film. It is more preferable.
  • dichroic dye examples include iodine based dye (I 3 - and I 5 -, etc.), and the like dichroic organic dyes.
  • the iodine dye can be obtained, for example, by bringing iodine (I 2 ) into contact with potassium iodide.
  • dichroic organic dye examples include direct black 17, 19, 154; direct brown 44, 106, 195, 210, 223; direct red 2, 23, 28, 31, 37, 39, 79, 81, 240, 242, 247; Direct Blue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; Direct Violet 9, 12, 51, 98; Direct Green 1, 85; Direct Yellow 8, 12, 44, 86, 87; Direct Orange 26, 39, 106, 107 and the like.
  • dichroic dyes iodine-based dyes are preferable from the viewpoints of handleability, availability, and polarization performance.
  • the dichroic dye may either be two or more even alone, for example, I 3 - may be a balanced mixture as - and I 5.
  • the cross-linking treatment step is preferably performed after the dyeing treatment step and before the stretching step.
  • the crosslinking treatment can be performed by immersing the laminated film in an aqueous solution containing a crosslinking agent.
  • a crosslinking agent one or more of boron compounds such as boric acid and borate such as borax can be used.
  • the concentration of the crosslinking agent in the aqueous solution containing the crosslinking agent is preferably in the range of 1 to 15% by mass, and more preferably in the range of 2 to 7% by mass.
  • the aqueous solution containing a crosslinking agent may contain an auxiliary agent such as potassium iodide.
  • the temperature of the aqueous solution containing the crosslinking agent is preferably in the range of 20 to 50 ° C., and more preferably in the range of 25 to 40 ° C.
  • the film can be stretched.
  • the draw ratio of the pre-stretching is preferably 4 times or less based on the original length of the laminated film before stretching from the viewpoint of the polarizing performance of the polarizing film to be obtained, and is in the range of 1.5 to 3.5 times More preferably, it is within.
  • the stretching ratio in the swelling treatment step is preferably in the range of 1.1 to 3 times, preferably in the range of 1.2 to 2.5 times. More preferably, it is more preferably within the range of 1.4 to 2.3 times; the draw ratio in the dyeing treatment step is preferably 2 times or less, and preferably 1.8 times or less. More preferably, it is more preferably in the range of 1.1 to 1.5 times; the draw ratio in the crosslinking treatment step is preferably 2 times or less, more preferably 1.5 times or less. More preferably, it is in the range of 1.05 to 1.3 times.
  • the laminated film subjected to the water contact step may be one unrolled from a film roll formed by winding a long laminated film as described above into a roll shape.
  • a film roll and a film roll of a single layer thermoplastic resin film are prepared in advance, and each film is continuously unwound from these film rolls so that they are adjacent to each other. Also good.
  • a polarizing film can be manufactured by performing the extending
  • the PVA film may be stretched in a state where the thermoplastic resin film and the PVA film are adjacent to each other, or after removing the thermoplastic resin film before the stretching step, the PVA The film may be stretched.
  • the thermoplastic resin film may be removed after the stretching step or the subsequent fixing treatment step and before the drying treatment step, or when the heat resistance of the thermoplastic resin film is high.
  • the thermoplastic resin film may be removed after the drying process.
  • the wet stretching method is preferable from the viewpoint of the uniformity of the thickness in the width direction of the obtained polarizing film, and it is more preferable to stretch in a boric acid aqueous solution.
  • concentration of boric acid in the boric acid aqueous solution is preferably within the range of 0.5 to 6.0% by mass, more preferably within the range of 1.0 to 5.0% by mass, More preferably, it is in the range of -4.0 mass%.
  • the aqueous solution containing the boron compound may contain potassium iodide, and its concentration is preferably in the range of 0.01 to 10% by mass.
  • the temperature at which the PVA film is stretched in the stretching step is preferably within a range of 30 to 90 ° C, more preferably within a range of 40 to 80 ° C, and within a range of 50 to 70 ° C. Is more preferable.
  • the stretching ratio in the stretching step is preferably 1.2 times or more, more preferably 1.5 times or more, and more preferably 2 times or more, because a polarizing film superior in polarization performance can be obtained. Is more preferable.
  • the total draw ratio including the above-described draw ratio of the pre-stretch (the ratio obtained by multiplying the draw ratios of the respective stretches) is 5.5 times or more based on the original length of the laminated film used. Is preferably 5.7 times or more, more preferably 5.8 times or more, and particularly preferably 5.9 times or more.
  • the upper limit of the total draw ratio is not particularly limited, but is preferably 8 times or less.
  • the stretching of the PVA film in the stretching step is preferably uniaxial stretching from the viewpoint of the performance of the obtained polarizing film.
  • the direction of uniaxial stretching and uniaxial stretching or lateral uniaxial stretching in the length direction of a long film can be adopted, but since it is easy to obtain a polarizing film superior in polarization performance, in the length direction Uniaxial stretching is preferred.
  • Uniaxial stretching in the length direction can be performed by changing the peripheral speed between the rolls using a stretching apparatus including a plurality of rolls parallel to each other.
  • lateral uniaxial stretching can be performed using a tenter type stretching machine.
  • the fixing process in a fixing process is mainly performed in order to strengthen adsorption
  • the fixing treatment can be performed by immersing the stretched PVA film in a fixing treatment bath.
  • an aqueous solution containing one or more of boron compounds such as boric acid such as boric acid and borax can be used.
  • the concentration of the boron compound in the aqueous solution containing the boron compound used as the fixing treatment bath is generally preferably in the range of 2 to 15% by mass, and more preferably in the range of 3 to 10% by mass.
  • the temperature of the fixing treatment bath is preferably in the range of 15 to 60 ° C, more preferably in the range of 25 to 40 ° C.
  • the conditions of the drying treatment in the drying treatment step are not particularly limited, but the drying temperature is preferably in the range of 30 to 150 ° C, and more preferably in the range of 50 to 130 ° C. A polarizing film excellent in dimensional stability is easily obtained by drying at a temperature within the above range.
  • the polarizing film obtained as described above is usually used as a polarizing plate by attaching a protective film having optical transparency and mechanical strength on both sides or one side.
  • a protective film a cellulose triacetate (TAC) film, an acetic acid / cellulose butyrate (CAB) film, an acrylic film, a polyester film, or the like can be used.
  • TAC cellulose triacetate
  • CAB acetic acid / cellulose butyrate
  • acrylic film a polyester film, or the like
  • polyester film or the like
  • the adhesive for bonding include PVA adhesives and urethane adhesives, among which PVA adhesives are suitable.
  • Adhesive strength between films A strip-shaped film piece of 200 mm in the length direction and 15 mm in the width direction is cut out from the laminated film produced in the following examples or comparative examples, and this film piece is used as described in JIS K6854-3: 1999. Then, the T-shaped peeling test was carried out 5 times, and the average value was defined as the adhesive strength. In this test, the measurement conditions were as follows: temperature: 28 ° C., humidity: 50% RH, tensile tester chuck interval: 50 mm, tensile speed: 250 mm / min (moving speed of the peeling point in the film piece was 125 mm / min). In addition, when both films are peeled off when the film is cut out because the adhesive strength is too low, such as when the two films are not substantially bonded, the adhesive strength between the films is evaluated as less than 1.0 mN / 15 mm. did.
  • a long PVA film having a thickness of 30 ⁇ m and a width of 1 m (including PVA, glycerin and a surfactant, the glycerin content being 12 parts by mass with respect to 100 parts by mass of PVA, and the surfactant content being 100 parts by mass of PVA)
  • PVA film is a saponified product of 0.03 parts by mass of PVA, which is a homopolymer of vinyl acetate, the degree of polymerization of PVA is 2400, and the degree of saponification of PVA is 99.9 mol%. Unwinding continuously from the film roll.
  • LLDPE film Long linear low-density polyethylene film (LLDPE film, manufactured by Tamapoly Co., Ltd., SE620N) having a thickness of 50 ⁇ m and a width of 1.2 m was continuously unwound from the film roll. Then, the unwound films are overlapped so that the center lines in the width direction substantially coincide (the adhesive strength between the films is less than 1.0 mN / 15 mm), and the swelling process, the dyeing process, and the crosslinking process are continuously performed in this order. The long laminated film was brought into contact with water.
  • LLDPE film linear low-density polyethylene film
  • the laminated film was immersed in distilled water (temperature: 30 ° C.) for 1 minute, and uniaxially stretched at a stretch ratio of 2 in the length direction during that time.
  • the laminated film is in an aqueous solution containing iodine-based pigment (concentration of iodine used: 0.05 mass%, concentration of potassium iodide used: 1.2 mass%, temperature: 30 ° C.). And uniaxially stretched in the length direction at a stretch ratio of 1.2.
  • the laminated film was immersed in an aqueous boric acid solution (boric acid concentration: 2.6 mass%, temperature: 30 ° C.) for 2 minutes, and uniaxially stretched at a draw ratio of 1.1 times in the length direction during that time. .
  • the stretching step was continuously performed.
  • the stretching step the stretching process was performed in a state where the thermoplastic resin film and the PVA film are adjacent to each other. Thereafter, the thermoplastic resin film was removed, and the stretched PVA film was dried to continuously produce a polarizing film.
  • the PVA film adjacent to the thermoplastic resin film is lengthened in an aqueous boric acid solution (boric acid concentration: 2.8% by mass, potassium iodide concentration: 5% by mass, temperature: 57 ° C.).
  • the film was uniaxially stretched in the direction at a stretching ratio of 2.4 times (the total stretching ratio including the stretching ratio of the pre-stretching in the water contact step was 6.3 times).
  • the stretched PVA film was dried at 60 ° C. for 1 minute.
  • Example 2 A polarizing film was continuously produced in the same manner as in Example 1 except that the thickness of the PVA film was changed to 15 ⁇ m. In the laminated film, the adhesive strength between the two films was less than 1.0 mN / 15 mm.
  • Example 3 Continuously in the same manner as in Example 1 except that a long low-density polyethylene film (LDPE film, manufactured by Tamapoly Co., Ltd., A-1) having a thickness of 50 ⁇ m and a width of 1.2 m was used as the thermoplastic resin film. A polarizing film was manufactured. In the laminated film, the adhesive strength between the two films was less than 1.0 mN / 15 mm.
  • LDPE film low-density polyethylene film
  • Example 4 A high-density polyethylene film (HDPE film, manufactured by Sanei Kaken Co., Ltd., PAC-4K-80) having a thickness of 50 ⁇ m and a width of 1.2 m is used as the thermoplastic resin film, and the PVA adhesive surface is PVA.
  • a polarizing film was continuously produced in the same manner as in Example 1 except that they were superposed so as to be on the film side. In the laminated film, the adhesive strength between the two films was 150 mN / 15 mm.
  • Example 5 Prior to the stretching step, a polarizing film was continuously produced in the same manner as in Example 1 except that the thermoplastic resin film was removed and the PVA film was stretched alone.
  • Example 1 A polarizing film was continuously produced in the same manner as in Example 1 except that the PVA film was used as a single layer without using the thermoplastic resin film, and the water contact step and the subsequent stretching step were performed.
  • a long amorphous polyethylene terephthalate film (A-PET film, “Novaclear” manufactured by Mitsubishi Plastics, Inc.) having a thickness of 200 ⁇ m and a width of 1 m is added to an aqueous solution (PVA, glycerin and a surfactant) having a PVA concentration of 10% by mass.
  • a PVA aqueous solution having a glycerin content of 12 parts by mass with respect to 100 parts by mass of PVA and a surfactant content of 0.03 parts by mass with respect to 100 parts by mass of PVA.
  • a PVA film having a thickness of 30 ⁇ m is formed on the thermoplastic resin film by applying a saponified product, having a polymerization degree of PVA of 2400 and a PVA saponification degree of 99.9 mol%) and drying at 60 ° C.
  • the formed laminated film was produced (adhesive strength between the thermoplastic resin film and the PVA film was 250 mN / 15 mm).
  • the laminated film thus obtained was subjected to a swelling treatment, a dyeing treatment and a crosslinking treatment in this order in the same manner as in Example 1, and then a water contact step was carried out. The drying process was performed in this order and the polarizing film was continuously manufactured.
  • thermoplastic resin film is removed after the drying treatment. Although the polarizing film was obtained, it was still difficult to remove the thermoplastic resin film.
  • a polarizing plate made of a polarizing film produced using a film can be suitably used for mobile applications such as small notebook computers and mobile phones.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polarising Elements (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Laminated Bodies (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)

Abstract

L'invention fournit un film stratifié destiné à la fabrication d'un film polarisant dans lequel une rupture d'étirement est peu susceptible de se produire lors de son étirement, y compris dans le cas de la mise en œuvre d'un film PVA mince, et qui permet de fabriquer aisément un film polarisant aux performances de polarisation excellentes. Plus précisément, l'invention fournit en outre un film stratifié qui permet de fabriquer très aisément un film polarisant, ou similaire, dans lequel une rupture d'étirement est peu susceptible de se produire lors de son étirement, et qui présente des performances de polarisation excellentes. Ainsi, l'invention concerne un film stratifié destiné à la fabrication d'un film polarisant dans lequel un film PVA et un film de résine thermoplastique sont adjacents, et la résistance d'adhésion entre ces deux films est inférieure ou égale à 200mN/15mm ; et l'invention concerne aussi un film stratifié dans lequel un film PVA et un film de résine thermoplastique sont adjacents, et la résistance d'adhésion entre ces deux films est inférieure à 1,5mN/15mm.
PCT/JP2013/081582 2012-11-30 2013-11-25 Film stratifié WO2014084154A1 (fr)

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CN201380062611.2A CN104903761B (zh) 2012-11-30 2013-11-25 层叠膜
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WO2016021432A1 (fr) * 2014-08-04 2016-02-11 住友化学株式会社 Procédé de fabrication de film polarisant
JP2017107157A (ja) * 2015-12-03 2017-06-15 日本合成化学工業株式会社 積層体、偏光膜製造用ポリビニルアルコール系フィルム、偏光膜、ならびに偏光膜製造用ポリビニルアルコール系フィルムの保管または輸送方法
WO2019054295A1 (fr) * 2017-09-12 2019-03-21 株式会社ウィンテック Conditionnement d'une feuille polarisante pliée thermiquement et lentille polarisante moulée par injection

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JPWO2019054295A1 (ja) * 2017-09-12 2020-12-10 株式会社ウインテック 熱曲げ偏光シートの包装体および射出偏光レンズ
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JP6444732B2 (ja) 2018-12-26
TW201424995A (zh) 2014-07-01
TWI615265B (zh) 2018-02-21
CN104903761B (zh) 2018-11-16
CN104903761A (zh) 2015-09-09
KR102072261B1 (ko) 2020-01-31
KR20150091493A (ko) 2015-08-11

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