WO2012032984A1 - 薄型偏光膜の製造方法 - Google Patents
薄型偏光膜の製造方法 Download PDFInfo
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- WO2012032984A1 WO2012032984A1 PCT/JP2011/069751 JP2011069751W WO2012032984A1 WO 2012032984 A1 WO2012032984 A1 WO 2012032984A1 JP 2011069751 W JP2011069751 W JP 2011069751W WO 2012032984 A1 WO2012032984 A1 WO 2012032984A1
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- WIPO (PCT)
- Prior art keywords
- polarizing film
- thin polarizing
- laminate
- stretching
- thermoplastic resin
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
- B29C55/026—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets of preformed plates or sheets coated with a solution, a dispersion or a melt of thermoplastic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/0074—Production of other optical elements not provided for in B29D11/00009- B29D11/0073
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- 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
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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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
- B29K2029/04—PVOH, i.e. polyvinyl alcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/0034—Polarising
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- 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 method for producing a thin polarizing film.
- Patent Document 1 a method for obtaining a polarizing film by stretching a laminate of a thermoplastic resin substrate and a polyvinyl alcohol resin layer (hereinafter referred to as a PVA resin layer) is proposed.
- a PVA resin layer a polyvinyl alcohol resin layer
- the PVA-based resin layer can be made thin, but there is a problem that its optical characteristics are low.
- the present invention has been made to solve the above-described conventional problems, and its main purpose is to provide a method for producing a thin polarizing film having excellent optical characteristics and excellent in-plane uniformity. It is in.
- the method for producing a thin polarizing film of the present invention comprises a step of drawing a thermoplastic resin substrate in a first direction and then forming a PVA-based resin layer on the thermoplastic resin substrate to produce a laminate,shrinking the laminate in a first direction and stretching in a second direction.
- a coating solution containing a PVA-based resin is applied and dried to form the PVA-based resin layer, and the drying temperature is equal to or lower than the glass transition temperature (Tg) of the thermoplastic resin substrate. is there.
- Tg glass transition temperature
- the first direction and the second direction are orthogonal to each other.
- the laminate is contracted and stretched while being conveyed, the first direction is MD, and the second direction is TD.
- the laminate is contracted / stretched while being conveyed, the first direction is TD, and the second direction is MD.
- the shrinkage in the first direction of the laminate is greater than 25%.
- the draw ratio of the 2nd direction of a laminated body is 4.0 times or more.
- an optical laminate is provided.
- This optical laminated body has a thin polarizing film manufactured by the method for manufacturing a thin polarizing film, and a substrate provided on at least one side of the thin polarizing film.
- the substrate is an optical functional film different from the thermoplastic resin substrate, and the optical functional film is provided on one side of the thin polarizing film via an adhesive layer.
- a laminate having a thermoplastic resin base material and a PVA resin layer that has been previously stretched in the first direction is contracted in the first direction and stretched in the second direction.
- a thin polarizing film having excellent optical characteristics and excellent in-plane uniformity can be manufactured.
- the uniaxiality of the second direction can be improved and excellent optical characteristics can be obtained by shrinking the laminate in the first direction and stretching in the second direction.
- the thermoplastic resin base material that has been stretched in the first direction can return to the state before stretching by stretching in the second direction, heat, etc., and shrinks uniformly in the first direction. Can be made.
- excellent in-plane uniformity can be obtained.
- thermoplastic resin substrate is stretched in a first direction, and then a PVA resin layer is formed on the thermoplastic resin substrate to form a laminate.
- a laminated body is produced by forming a PVA-type resin layer on a thermoplastic resin substrate, after extending a thermoplastic resin substrate in the 1st direction.
- the thermoplastic resin base material has any appropriate configuration as long as it can support the PVA-based resin layer and the resulting thin polarizing film from one side.
- the laminate is typically formed in a long shape.
- the thickness of the thermoplastic resin substrate (before stretching) is preferably 50 ⁇ m to 250 ⁇ m. If it is less than 50 ⁇ m, there is a risk of breaking during stretching. In addition, the thickness may become too thin after stretching, which may make conveyance difficult. If it exceeds 250 ⁇ m, an excessive load may be applied to the stretching machine. Moreover, there exists a possibility that conveyance may become difficult.
- thermoplastic resin substrate examples include ester resins such as polyethylene terephthalate resin, cycloolefin resins, olefin resins such as polypropylene, polyamide resins, polycarbonate resins, and copolymer resins thereof. Can be mentioned. Among these, cycloolefin resins (for example, norbornene resins) and amorphous polyethylene terephthalate resins are preferable. Specific examples of the amorphous polyethylene terephthalate resin include a copolymer further containing isophthalic acid as a dicarboxylic acid, and a copolymer further containing cyclohexanedimethanol as a glycol.
- ester resins such as polyethylene terephthalate resin, cycloolefin resins, olefin resins such as polypropylene, polyamide resins, polycarbonate resins, and copolymer resins thereof. Can be mentioned. Among these, cycloolefin
- the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 170 ° C. or lower. By using such a thermoplastic resin base material, it is possible to stretch the laminate at a temperature at which crystallization of the PVA resin does not proceed rapidly, and defects due to the crystallization (for example, the PVA resin layer due to stretching). Which prevents orientation).
- the glass transition temperature (Tg) is a value determined according to JIS K 7121.
- a 1st direction is a conveyance direction (MD) of a thermoplastic resin base material.
- the conveying direction is preferably the long direction of the long thermoplastic resin base material, and includes the direction of ⁇ 5 ° to + 5 ° counterclockwise with respect to the long direction of the thermoplastic resin base material. obtain.
- the first direction is a direction (TD) orthogonal to the transport direction.
- the direction orthogonal to the conveying direction is preferably the width direction of the long thermoplastic resin base material, and the direction of 85 ° to 95 ° counterclockwise with respect to the long direction of the thermoplastic resin base material.
- the term “orthogonal” includes the case of being substantially orthogonal.
- substantially orthogonal includes the case of 90 ° ⁇ 5.0 °, preferably 90 ° ⁇ 3.0 °, more preferably 90 ° ⁇ 1.0 °.
- Arbitrary appropriate methods can be employ
- the stretching of the thermoplastic resin substrate may be performed in one step or in multiple steps. When performed in multiple stages, the stretch ratio of the thermoplastic resin substrate described later is the product of the stretch ratios of the respective stages.
- stretching system in this process is not specifically limited, An air extending
- the stretching temperature of the thermoplastic resin substrate can be set to any appropriate value depending on the forming material of the thermoplastic resin substrate, the stretching method, and the like.
- the stretching temperature is typically not less than the glass transition temperature (Tg) of the thermoplastic resin substrate, preferably not less than Tg + 10 ° C., more preferably not less than Tg + 15 ° C. to Tg + 30 ° C.
- Tg glass transition temperature
- the stretching temperature is set to the glass transition temperature of the thermoplastic resin base material (for example, 60 ° C. to 100 ° C. ° C).
- the draw ratio (first direction) of the thermoplastic resin substrate is preferably 1.5 times or more, more preferably 1.75 times or more with respect to the original length of the thermoplastic resin substrate. By setting the draw ratio to 1.5 times or more, a laminated body described later can be contracted more uniformly. On the other hand, the draw ratio is preferably 2.5 times or less.
- the surface of the thermoplastic resin substrate may be subjected to surface modification treatment (for example, corona treatment), or an easy adhesion layer may be formed on the thermoplastic resin substrate.
- surface modification treatment for example, corona treatment
- an easy adhesion layer may be formed on the thermoplastic resin substrate.
- a PVA-based resin layer is formed by applying a coating solution containing a PVA-based resin on a thermoplastic resin substrate that has been subjected to a stretching treatment, and drying.
- any appropriate resin can be used as the PVA resin.
- Examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol copolymer.
- Polyvinyl alcohol is obtained by saponifying polyvinyl acetate.
- the ethylene-vinyl alcohol copolymer can be obtained by saponifying an ethylene-vinyl acetate copolymer.
- the degree of saponification of the PVA-based resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, more preferably 99.0 mol% to 99.93 mol%. .
- the degree of saponification can be determined according to JIS K 6726-1994. By using a PVA-based resin having such a saponification degree, a thin polarizing film having excellent durability can be obtained. If the saponification degree is too high, the coating solution is likely to gel, and it may be difficult to form a uniform coating film.
- the average degree of polymerization of the PVA resin can be appropriately selected according to the purpose.
- the average degree of polymerization is usually 1000 to 10,000, preferably 1200 to 4500, and more preferably 1500 to 4300.
- the average degree of polymerization can be determined according to JIS K 6726-1994.
- the coating solution is typically a solution obtained by dissolving the PVA resin in a solvent.
- the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine. These may be used alone or in combination of two or more. Among these, water is preferable.
- the concentration of the PVA resin in the solution is preferably 3 to 20 parts by weight with respect to 100 parts by weight of the solvent. With such a resin concentration, a uniform coating film in close contact with the thermoplastic resin substrate can be formed.
- Additives may be added to the coating solution.
- the additive include a plasticizer and a surfactant.
- the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin.
- the surfactant include nonionic surfactants. These can be used for the purpose of further improving the uniformity, dyeability and stretchability of the resulting PVA resin layer.
- any appropriate method can be adopted as a coating method of the coating solution. Examples thereof include a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, a knife coating method (comma coating method, etc.).
- the drying temperature is preferably not higher than the glass transition temperature (Tg) of the thermoplastic resin substrate, more preferably not higher than Tg-20 ° C.
- Tg glass transition temperature
- the thermoplastic resin base material is prevented from being deformed before the PVA resin layer is formed, and the orientation of the resulting PVA resin layer is prevented from deteriorating. Can do.
- the thermoplastic resin substrate can be deformed well together with the PVA-based resin layer, and the later-described laminate can be satisfactorily contracted and stretched. As a result, good orientation can be imparted to the PVA resin layer, and a thin polarizing film having excellent optical properties can be obtained.
- “orientation” means the orientation of molecular chains of the PVA resin layer.
- the thickness of the PVA resin layer is preferably 3 ⁇ m to 20 ⁇ m. Even such a thin thickness can be satisfactorily stretched by using the thermoplastic resin substrate.
- the moisture content of the PVA-based resin layer is preferably 20% or less, more preferably 15% or less.
- the laminate is contracted in the first direction and stretched in the second direction.
- the thermoplastic resin base material is brought into a state before stretching by stretching in the second direction, heat, or the like. An attempt can be made to return and the laminate can be uniformly shrunk in the first direction. Thus, even in a high shrinkage rate, excellent in-plane uniformity can be obtained. Further, by contracting the laminate and stretching in the second direction, the uniaxiality in the second direction can be improved, and excellent optical characteristics can be obtained.
- the second direction is substantially the absorption axis direction of the obtained thin polarizing film.
- the shrinkage of the laminate may be performed simultaneously with the stretching or may be performed at another timing. Further, the order is not limited, and the laminate may be contracted in one stage or may be contracted in multiple stages. In one embodiment, preferably, the laminate is contracted in the first direction and then stretched in the second direction. In another embodiment, the laminate is preferably contracted in the first direction while being stretched in the second direction.
- a method of shrinking the laminate separately from stretching a method of heating (thermally shrinking) the laminate is preferable. The heating temperature is preferably equal to or higher than the glass transition temperature (Tg) of the thermoplastic resin substrate.
- the shrinkage rate in the first direction of the laminate can be set to any appropriate value. Preferably it exceeds 25%, more preferably more than 30% and less than 50%. By setting such a shrinkage rate, more excellent optical characteristics can be obtained. Even with such a high shrinkage rate, excellent in-plane uniformity can be obtained. Note that the first direction is as described above.
- the second direction can be set to any appropriate direction depending on the desired thin polarizing film.
- the second direction and the first direction are orthogonal to each other.
- the first direction is the conveyance direction (MD) of the thermoplastic resin substrate
- the second direction is preferably a direction (TD) orthogonal to the conveyance direction.
- the first direction is a direction (TD) orthogonal to the transport direction
- the second direction is preferably the transport direction (MD).
- Arbitrary appropriate methods can be employ
- the stretching of the laminate may be performed in one stage or in multiple stages. When performed in multiple stages, the stretch ratio of the laminate described later is the product of the stretch ratios of the respective stages.
- stretching system in this process is not specifically limited, An air extending
- the stretching temperature of the laminate can be set to any appropriate value depending on the material for forming the thermoplastic resin substrate.
- the stretching temperature is typically at least the glass transition temperature (Tg) of the thermoplastic resin substrate, preferably the glass transition temperature (Tg) of the thermoplastic resin substrate + 10 ° C. or more, more preferably Tg + 15 ° C. or more.
- the stretching temperature of the laminate is preferably 170 ° C. or lower.
- the stretching temperature is preferably 85 ° C. or lower, more preferably 30 ° C. to 65 ° C. If it exceeds 85 ° C., there is a risk that iodine adsorbed on the PVA resin will be eluted, and that the PVA resin will be eluted, and the optical properties of the resulting thin polarizing film may be deteriorated.
- a thermoplastic resin substrate that can be stretched even at the above temperature is selected.
- amorphous polyethylene terephthalate resin, olefin resin (for example, polymethylpentene) or the like is used as the forming material.
- the PVA resin layer can be provided with rigidity that can withstand the tension applied during stretching and water resistance that does not dissolve in water.
- boric acid can generate a tetrahydroxyborate anion in an aqueous solution and can be cross-linked with a PVA resin by hydrogen bonding, and can impart rigidity and water resistance.
- the aqueous boric acid solution is obtained by dissolving boric acid and / or borate in water as a solvent.
- the boric acid concentration is usually 1 to 10 parts by weight per 100 parts by weight of water.
- the immersion time of the laminate in the stretching bath is preferably about 15 seconds to 5 minutes.
- the draw ratio (second direction) of the laminate is preferably 4.0 times or more with respect to the original length of the laminate.
- the upper limit of the draw ratio in the single-stage drawing is about 5.0 times. This is because the laminate may be broken.
- the laminate 10 is contracted in the transport direction (MD) using a simultaneous biaxial stretching machine while transporting the laminate 10 in the longitudinal direction, and in the direction (TD) orthogonal to the transport direction. Stretch. Specifically, the laminated body 10 held by the left and right clips 21 and 21 at the tenter entrance is TD-stretched while being conveyed at a predetermined speed. In the illustrated example, the contraction of the laminated body is controlled by, for example, gradually decreasing the moving speed of the clip in the transport direction and reducing the distance between the clips.
- the shrinkage rate can be controlled by adjusting the distance L1 between the clips in the transport direction of the tenter inlet and the distance L2 between the clips in the transport direction of the tenter outlet (the moving speed of the clips in the transport direction).
- the desired shrinkage rate can be achieved by setting the speed of the tenter outlet of the clip to the speed of the tenter inlet ⁇ the shrinkage rate.
- the broken line indicates the rail of the clip 21.
- the laminate when the laminate is contracted / stretched using a simultaneous biaxial stretching machine, the laminate is preferably stretched after being contracted. Specifically, TD stretching is performed after the distance between clips in the transport direction is shortened. According to such an embodiment, it is possible to prevent the clip gripping portion from being selectively stretched by applying a uniform force to the laminate during stretching. Specifically, it is possible to prevent the portion that is not gripped by the clip from bending inward on the edge of the laminate. As a result, uniformity can be improved.
- FIG. 1 Another specific example of the shrinking / stretching process is shown in FIG.
- the laminated body 10 while the laminated body 10 is conveyed in the longitudinal direction, the laminated body 10 is passed between rolls 31, 31, 32, and 32 having different peripheral speeds and stretched in the conveying direction (MD). At that time, the laminate can contract in the first direction (TD).
- This shrinkage is considered to be due to neck-in due to MD stretching and neck-in (thermal shrinkage) due to heat during MD stretching.
- the shrinkage rate can be controlled by controlling the stretching conditions in this step, the stretching conditions of the thermoplastic resin base material, and the like.
- the method for producing a thin polarizing film of the present invention may include other steps in addition to the above.
- Examples of other processes include an insolubilization process, a dyeing process, a crosslinking process, a stretching process different from the above stretching process, a washing process, and a drying process (adjustment of moisture content).
- the other steps can be performed at any appropriate timing.
- the dyeing step is typically a step of dyeing the PVA resin layer with a dichroic substance.
- it is performed by adsorbing a dichroic substance to the PVA resin layer.
- adsorption method for example, a method of immersing a PVA resin layer (laminate) in a dye solution containing a dichroic substance, a method of applying a dye solution to the PVA resin layer, and a dye solution on a PVA resin layer The method of spraying etc. are mentioned.
- the laminate is immersed in a staining solution containing a dichroic substance. It is because a dichroic substance can adsorb
- both surfaces of the laminate may be immersed in the dyeing solution, or only one surface may be immersed.
- the dichroic substance examples include iodine and organic dyes. These may be used alone or in combination of two or more.
- the dichroic material is preferably iodine.
- the staining solution is preferably an iodine aqueous solution.
- the blending amount of iodine is preferably 0.1 to 1.0 part by weight with respect to 100 parts by weight of water. In order to increase the solubility of iodine in water, it is preferable to add an iodide salt to the aqueous iodine solution.
- Examples of the iodide salt include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and iodide.
- Examples include titanium. Among these, potassium iodide and sodium iodide are preferable.
- the blending amount of the iodide salt is preferably 0.3 to 15 parts by weight with respect to 100 parts by weight of water.
- the liquid temperature during staining of the staining liquid is preferably 20 ° C. to 40 ° C.
- the immersion time is preferably 5 seconds to 300 seconds. Under such conditions, the dichroic substance can be sufficiently adsorbed to the PVA resin layer.
- the insolubilization step and the crosslinking step are typically performed by immersing the PVA resin layer in an aqueous boric acid solution.
- the cleaning step is typically performed by immersing the PVA resin layer in an aqueous potassium iodide solution.
- the drying temperature in the drying step is preferably 30 ° C. to 100 ° C.
- the thin polarizing film of the present invention is produced by the above production method.
- the thin polarizing film of the present invention is substantially a PVA resin film in which a dichroic substance is adsorbed and oriented.
- the thin polarizing film preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm.
- the thickness of the thin polarizing film is preferably less than 10 ⁇ m, more preferably 0.5 ⁇ m to 5 ⁇ m.
- any appropriate method can be adopted as a method of using the thin polarizing film. Specifically, it may be used in a state of being integrated with the thermoplastic resin base material, or it is used by transferring from the thermoplastic resin base material to another member (peeling the thermoplastic resin base material). May be.
- the optical laminate of the present invention includes the thin polarizing film and a base material that is provided on at least one side of the thin polarizing film and can support the thin polarizing film.
- the base material the thermoplastic resin base material may be used as it is, or an optical functional film different from the thermoplastic resin base material may be used.
- the same material as the thermoplastic resin is used.
- (meth) acrylic resins, cellulose resins such as diacetylcellulose, triacetylcellulose, and the like are used.
- the optical functional film is preferably provided on one side of the thin polarizing film via an adhesive layer.
- the thickness of the optical functional film is preferably 20 ⁇ m to 100 ⁇ m.
- the thermoplastic resin base material previously provided on one side of the thin polarizing film is preferably peeled off in advance. This is because curling can be more reliably suppressed.
- the adhesive layer is formed of any appropriate adhesive. Examples of the adhesive include a polyvinyl alcohol-based adhesive.
- the optical laminate (thin polarizing film) of the present invention has a small shrinkage stress and can be excellent in dimensional stability even in a high temperature environment.
- the degree of polarization at a single transmittance of 41% is preferably 99.9% or more. Thus, it can be excellent in optical characteristics.
- thermoplastic resin base material As a thermoplastic resin substrate, a long cycloolefin resin film (trade name “ARTON” manufactured by JSR Corporation) having a thickness of 150 ⁇ m and a Tg of 123 ° C. was used.
- the thermoplastic resin substrate was stretched in the air in the first direction (MD) by passing between rolls having different peripheral speeds. At this time, the stretching temperature was 140 ° C., and the stretching ratio was 2.0 times.
- PVA resin having a polymerization degree of 1800 and a saponification degree of 98 to 99% (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name “GOHSENOL (registered trademark) NH-18”) is dissolved in water to a concentration of 7% by weight. An aqueous polyvinyl alcohol solution was prepared.
- the coating solution was applied to one side of the stretched thermoplastic resin substrate by a die coater (die coating method), and then dried at 100 ° C. for 180 seconds to form a 7 ⁇ m thick PVA resin layer. In this way, a laminate was produced.
- the obtained laminate is shrunk by 50% in the first direction (MD) at 140 ° C. using a simultaneous biaxial stretching machine, and at the same time in the second direction (TD).
- the film was stretched in the air by 4.5 times. Specifically, the distance L1 between clips in the conveyance direction of the tenter inlet was 144 mm, and the distance L2 between clips in the conveyance direction of the tenter outlet was 72 mm.
- ⁇ Crosslinking treatment> The layered product after dyeing was immersed in an aqueous boric acid solution at 60 ° C. (boric acid concentration: 5% by weight, potassium iodide concentration: 5% by weight) for 60 seconds.
- Example 2 A laminate was produced in the same manner as in Example 1 except that the thermoplastic resin substrate was stretched at the fixed end in the first direction (TD) with a tenter stretching machine. The obtained laminate was passed between rolls having different peripheral speeds and shrunk by 50% in the first direction (TD) and simultaneously stretched in the air in the second direction (MD) by 4.5 times. The stretching temperature at this time was 140 ° C. Thereafter, in the same manner as in Example 1, dyeing treatment, cross-linking treatment and washing treatment were carried out to produce a thin polarizing film having a thickness of 3.0 ⁇ m on the thermoplastic resin substrate.
- Example 3 A thin polarizing film was produced in the same manner as in Example 1 except that the shrinkage rate in the first direction was 35% (L1: 111 mm, L2: 72 mm) in the shrinkage / stretching treatment. The thickness of the obtained thin polarizing film was 2.4 ⁇ m.
- Example 4 A thin polarizing film was produced in the same manner as in Example 1 except that the shrinkage ratio in the first direction was 28% (L1: 100 mm, L2: 72 mm) in the shrinkage / stretching treatment. The thickness of the obtained thin polarizing film was 2.2 ⁇ m.
- thermoplastic resin substrate was not subjected to stretching treatment.
- the thickness of the obtained thin polarizing film was 3.1 ⁇ m.
- thermoplastic resin substrate was not subjected to stretching treatment.
- the thickness of the obtained thin polarizing film was 3.0 ⁇ m.
- Example 3 A thin polarizing film was produced in the same manner as in Example 3 except that the thermoplastic resin substrate was not subjected to stretching treatment. The thickness of the obtained thin polarizing film was 2.4 ⁇ m.
- Example 4 A thin polarizing film was produced in the same manner as in Example 4 except that the thermoplastic resin substrate was not stretched. The thickness of the obtained thin polarizing film was 2.2 ⁇ m.
- thermoplastic resin substrate was not subjected to stretching treatment and was not shrunk in the first direction in the shrinking / stretching treatment (the shrinkage rate was set to 0%), the same as in Example 1.
- a thin polarizing film was produced.
- the thickness of the obtained thin polarizing film was 1.6 ⁇ m.
- the thin polarizing film (laminated body) obtained in each example and comparative example was evaluated. Evaluation methods and evaluation criteria are as follows. The measurement results are shown in Table 1. 1. In-plane uniformity 1-1. Wrinkles The presence or absence of wrinkles was evaluated visually. (Evaluation criteria) ⁇ : No wrinkle ⁇ : Wrinkle at the end ⁇ : Wrinkle on the entire surface 1-2. Orientation unevenness It evaluated by the laminated body before dyeing
- the two polarizing plates were arranged so that their absorption axes were parallel to each other. Moreover, it arrange
- Comparative Example 5 shows that a thin polarizing film having excellent optical properties can be obtained by contracting in the first direction and stretching in the second direction. This is considered to be because the uniaxiality in the second direction is increased by contraction in the first direction. In Comparative Example 6, the film could not be stretched up to 4.5 times in the second direction.
- Example 5 After bonding a substrate having a thickness of 80 ⁇ m (trade name “TD80UL”, manufactured by Fuji Film Co., Ltd.) to the surface of the thin polarizing film obtained in Example 3 with a vinyl alcohol adhesive, the above thermoplastic resin substrate was peeled off to obtain an optical laminate.
- TD80UL thickness of 80 ⁇ m
- the degree of curling of the optical laminates of Examples 1 to 5 and Comparative Examples 1 to 5 was measured. Specifically, a test piece (length 10 cm ⁇ width 10 cm) was cut out from the obtained optical laminate. The obtained test piece was placed on a glass plate so that the convex surface was on the lower side, and the heights of four corners of the test piece were measured from the glass plate. The largest value among the four corners was evaluated. In Examples 1 to 4 and Comparative Examples 1 to 5, the height was 20 mm or more, whereas in Example 5, the height was less than 10 mm, and curling was well suppressed.
- the thin polarizing film of the present invention is suitably used for liquid crystal panels such as liquid crystal televisions, liquid crystal displays, mobile phones, digital cameras, video cameras, portable game machines, car navigation systems, copy machines, printers, fax machines, watches, and microwave ovens. .
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Abstract
Description
好ましい実施形態においては、PVA系樹脂を含む塗布液を塗布し、乾燥することにより、上記PVA系樹脂層を形成し、該乾燥温度が上記熱可塑性樹脂基材のガラス転移温度(Tg)以下である。
好ましい実施形態においては、上記第1の方向と上記第2の方向とが直交する。
好ましい実施形態においては、上記積層体を搬送しながら収縮・延伸し、上記第1の方向がMDであり、上記第2の方向がTDである。
好ましい実施形態においては、上記積層体を搬送しながら収縮・延伸し、上記第1の方向がTDであり、上記第2の方向がMDである。
好ましい実施形態においては、積層体の第1の方向の収縮率が25%を超える。
好ましい実施形態においては、積層体の第2の方向の延伸倍率が4.0倍以上である。
本発明の別の局面によれば、光学積層体が提供される。この光学積層体は、上記薄型偏光膜の製造方法により製造された薄型偏光膜と、該薄型偏光膜の少なくとも片側に設けられた基材とを有する。
好ましい実施形態においては、上記基材が上記熱可塑性樹脂基材とは別の光学機能フィルムであり、該光学機能フィルムが接着剤層を介して上記薄型偏光膜の片側に設けられている。
A.薄型偏光膜の製造方法
本発明の薄型偏光膜の製造方法は、熱可塑性樹脂基材を第1の方向に延伸した後、熱可塑性樹脂基材上にPVA系樹脂層を形成して積層体を作製する工程(積層体作製工程)と、積層体を第1の方向に収縮させて、第2の方向に延伸する工程(収縮・延伸工程)とを含む。以下、各々の工程について説明する。
積層体は、熱可塑性樹脂基材を第1の方向に延伸した後、熱可塑性樹脂基材上にPVA系樹脂層を形成することにより作製される。熱可塑性樹脂基材は、PVA系樹脂層、得られる薄型偏光膜を片側から支持し得る限り、任意の適切な構成とされる。積層体は、代表的には、長尺状に形成される。
次に、上記積層体を第1の方向に収縮させて、第2の方向に延伸する。予め、第1の方向に延伸処理を施した熱可塑性樹脂基材で積層体を構成することにより、熱可塑性樹脂基材は、第2の方向への延伸、熱等により、延伸前の状態に戻ろうとし得、積層体を第1の方向に均一に収縮させることができる。こうして、高い収縮率であっても、優れた面内均一性を得ることができる。また、積層体を収縮させて、第2の方向に延伸することで、第2の方向の一軸性を高め得、優れた光学特性を得ることができる。なお、第2の方向が、実質的に、得られる薄型偏光膜の吸収軸方向となる。
本発明の薄型偏光膜の製造方法は、上記以外に、その他の工程を含み得る。その他の工程としては、例えば、不溶化工程、染色工程、架橋工程、上記延伸とは別の延伸工程、洗浄工程、乾燥(水分率の調節)工程等が挙げられる。その他の工程は、任意の適切なタイミングで行い得る。
本発明の薄型偏光膜は、上記製造方法により作製される。本発明の薄型偏光膜は、実質的には、二色性物質を吸着配向させたPVA系樹脂膜である。薄型偏光膜は、好ましくは、波長380nm~780nmのいずれかの波長で吸収二色性を示す。薄型偏光膜の厚みは、好ましくは10μm未満であり、さらに好ましくは0.5μm~5μmである。
本発明の光学積層体は、上記薄型偏光膜と、薄型偏光膜の少なくとも片側に設けられ、薄型偏光膜を支持し得る基材とを有する。この基材としては、上記熱可塑性樹脂基材をそのまま用いてもよいし、上記熱可塑性樹脂基材とは別の光学機能フィルムを用いてもよい。光学機能フィルムの形成材料としては、例えば、上記熱可塑性樹脂と同様の材料が用いられる。これら以外にも、例えば、(メタ)アクリル系樹脂、ジアセチルセルロース、トリアセチルセルロース等のセルロース系樹脂等が用いられる。
<積層体の作製>
(熱可塑性樹脂基材)
熱可塑性樹脂基材として、長尺状で厚み150μm、Tg123℃のシクロオレフィン系樹脂フィルム(JSR社製、商品名「ARTON」)を用いた。
上記熱可塑性樹脂基材を、周速の異なるロール間に通して第1の方向(MD)に空中延伸した。このときの、延伸温度は140℃であり、延伸倍率は2.0倍であった。
(塗布液の調製)
重合度1800、ケン化度98~99%のポリビニルアルコール(PVA)樹脂(日本合成化学工業社製、商品名「ゴーセノール(登録商標)NH-18」)を水に溶解させて、濃度7重量%のポリビニルアルコール水溶液を調製した。
(PVA系樹脂層の形成)
延伸処理を施した熱可塑性樹脂基材の片面に、上記塗布液をダイコーター(ダイコート法)により塗布した後、100℃で180秒間乾燥して、厚み7μmのPVA系樹脂層を形成した。このようにして、積層体を作製した。
得られた積層体を、図1に示すように、同時二軸延伸機を用いて、140℃で、第1の方向(MD)に50%収縮させると同時に、第2の方向(TD)に4.5倍に空中延伸した。具体的には、テンター入口の搬送方向のクリップ間距離L1:144mm、テンター出口の搬送方向のクリップ間距離L2:72mmとした。
次いで、積層体を、25℃のヨウ素水溶液(ヨウ素濃度:0.5重量%、ヨウ化カリウム濃度:10重量%)に30秒間浸漬させた。
染色後の積層体を、60℃のホウ酸水溶液(ホウ酸濃度:5重量%、ヨウ化カリウム濃度:5重量%)に60秒間浸漬させた。
架橋処理後、積層体を、25℃のヨウ化カリウム水溶液(ヨウ化カリウム濃度:5重量%)に5秒間浸漬させた。
このようにして、熱可塑性樹脂基材上に、厚み3.1μmの薄型偏光膜を作製した。
上記熱可塑性樹脂基材をテンター延伸機にて第1の方向(TD)に固定端延伸したこと以外は実施例1と同様にして積層体を作製した。
得られた積層体を、周速の異なるロール間に通して、第1の方向(TD)に50%収縮させると同時に、第2の方向(MD)に4.5倍に空中延伸した。このときの、延伸温度は140℃であった。
その後、実施例1と同様にして、染色処理、架橋処理および洗浄処理を行い、熱可塑性樹脂基材上に厚み3.0μmの薄型偏光膜を作製した。
収縮・延伸処理において第1の方向の収縮率を35%(L1:111mm、L2:72mm)としたこと以外は、実施例1と同様にして薄型偏光膜を作製した。
得られた薄型偏光膜の厚みは、2.4μmであった。
収縮・延伸処理において第1の方向の収縮率を28%(L1:100mm、L2:72mm)としたこと以外は、実施例1と同様にして薄型偏光膜を作製した。
得られた薄型偏光膜の厚みは、2.2μmであった。
熱可塑性樹脂基材に延伸処理を施さなかったこと以外は、実施例1と同様にして薄型偏光膜を作製した。
得られた薄型偏光膜の厚みは、3.1μmであった。
熱可塑性樹脂基材に延伸処理を施さなかったこと以外は、実施例2と同様にして薄型偏光膜を作製した。
得られた薄型偏光膜の厚みは、3.0μmであった。
熱可塑性樹脂基材に延伸処理を施さなかったこと以外は、実施例3と同様にして薄型偏光膜を作製した。
得られた薄型偏光膜の厚みは、2.4μmであった。
熱可塑性樹脂基材に延伸処理を施さなかったこと以外は、実施例4と同様にして薄型偏光膜を作製した。
得られた薄型偏光膜の厚みは、2.2μmであった。
熱可塑性樹脂基材に延伸処理を施さなかったこと、および、収縮・延伸処理において第1の方向に収縮させなかった(収縮率を0%とした)こと以外は、実施例1と同様にして薄型偏光膜を作製した。
得られた薄型偏光膜の厚みは、1.6μmであった。
収縮・延伸処理において第1の方向に収縮させなかった(収縮率を0%とした)こと以外は、実施例1と同様にして薄型偏光膜の作製を試みた。
1.面内均一性
1-1.シワ
目視にてシワの有無を評価した。
(評価基準)
◎:シワ無し
○:端部にシワ有り
×:全面にシワ有り
1-2.配向ムラ
染色前の積層体にて評価した。図3に示すように、積層体(サンプル)の上下それぞれに市販の偏光板を重ね合わせた状態で下方から光を照射し、上方から目視にて配向ムラを評価した。その際、2枚の偏光板を、互いの吸収軸が平行となるように配置させた。また、積層体の第2の方向(延伸方向)が、偏光板の吸収軸に対して45°の角度をなすように配置させた。
(評価基準)
◎:配向ムラ無し
○:端部に配向ムラ有り
×:全面に配向ムラ有り
1-3.厚み分布
ダイヤルケージ(PEACOCK社製、製品名「DG-205 type pds-2」)を用いて、1450mm幅の幅方向(TD方向)の厚み分布を評価した。
(評価基準)
◎:±1μm以内
○:±2μm未満
×:±2μm以上
2.偏光度
分光光度計(村上色彩社製、製品名「Dot-41」)を用いて、薄型偏光膜(光学積層体)の単体透過率(Ts)、平行透過率(Tp)および直交透過率(Tc)を測定し、単体透過率41%における偏光度(P)を次式にて求めた。なお、これらの透過率は、JIS Z 8701の2度視野(C光源)により測定し、視感度補正を行ったY値である。
偏光度(P)={(Tp-Tc)/(Tp+Tc)}1/2×100
(評価基準)
◎:99.95%以上
○:99.93%以上
×:99.8%以下
実施例3で得られた薄型偏光膜表面に、ビニルアルコール系接着剤を介して厚み80μmの基材(富士フイルム社製、商品名「TD80UL」)を貼り合わせた後、上記熱可塑性樹脂基材を剥離して光学積層体を得た。
実施例1~4および比較例1~5では高さが20mm以上であったのに対し、実施例5では高さが10mm未満と、カールが良好に抑制されていた。
Claims (9)
- 熱可塑性樹脂基材を第1の方向に延伸した後、該熱可塑性樹脂基材上にポリビニルアルコール系樹脂層を形成して積層体を作製する工程と、
該積層体を第1の方向に収縮させて、第2の方向に延伸する工程と
を含む、薄型偏光膜の製造方法。 - ポリビニルアルコール系樹脂を含む塗布液を塗布し、乾燥することにより、前記ポリビニルアルコール系樹脂層を形成し、該乾燥温度が前記熱可塑性樹脂基材のガラス転移温度(Tg)以下である、請求項1に記載の薄型偏光膜の製造方法。
- 前記第1の方向と前記第2の方向とが直交する、請求項1または2に記載の薄型偏光膜の製造方法。
- 前記積層体を搬送しながら収縮・延伸し、前記第1の方向がMDであり、前記第2の方向がTDである、請求項1から3のいずれかに記載の薄型偏光膜の製造方法。
- 前記積層体を搬送しながら収縮・延伸し、前記第1の方向がTDであり、前記第2の方向がMDである、請求項1から3のいずれかに記載の薄型偏光膜の製造方法。
- 積層体の第1の方向の収縮率が25%を超える、請求項1から5のいずれかに記載の薄型偏光膜の製造方法。
- 積層体の第2の方向の延伸倍率が4.0倍以上である、請求項1から6のいずれかに記載の薄型偏光膜の製造方法。
- 請求項1から7のいずれかに記載の薄型偏光膜の製造方法により製造された薄型偏光膜と、
該薄型偏光膜の少なくとも片側に設けられた基材とを有する、光学積層体。 - 前記基材が前記熱可塑性樹脂基材とは別の光学機能フィルムであり、該光学機能フィルムが接着剤層を介して前記薄型偏光膜の片側に設けられている、請求項8に記載の光学積層体。
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- 2011-08-31 CN CN201180042898.3A patent/CN103097929B/zh active Active
- 2011-08-31 US US13/821,361 patent/US10532526B2/en not_active Expired - Fee Related
- 2011-08-31 WO PCT/JP2011/069751 patent/WO2012032984A1/ja active Application Filing
- 2011-09-08 TW TW100132429A patent/TWI579134B/zh active
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JP2012068677A (ja) * | 2010-03-31 | 2012-04-05 | Sumitomo Chemical Co Ltd | 偏光性積層フィルム、偏光板、およびそれらの製造方法 |
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CN105051579A (zh) * | 2013-03-29 | 2015-11-11 | 日东电工株式会社 | 相位差膜的制造方法及圆偏振板的制造方法 |
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US9796146B2 (en) | 2013-03-29 | 2017-10-24 | Nitto Denko Corporation | Methods for producing phase-difference film and circularly polarizing plate involving simultaneous reduction of clip pitch on one side and increase of clip pitch on another side |
US9804313B2 (en) | 2013-03-29 | 2017-10-31 | Nitto Denko Corporation | Methods for producing phase-difference film and circularly polarizing plate involving simultaneous reduction of clip pitch on one side and increase of clip pitch on another side |
US9950461B2 (en) | 2013-06-10 | 2018-04-24 | Nitto Denko Corporation | Production method for phase shift film and circular polarizing plate involving bilaterally symmetric loops with non-simultaneous reduction of clip pitch |
WO2020166505A1 (ja) * | 2019-02-12 | 2020-08-20 | 日東電工株式会社 | 偏光板およびその製造方法、ならびに該偏光板を用いた画像表示装置 |
JPWO2020166505A1 (ja) * | 2019-02-12 | 2021-10-21 | 日東電工株式会社 | 偏光板およびその製造方法、ならびに該偏光板を用いた画像表示装置 |
JP7288465B2 (ja) | 2019-02-12 | 2023-06-07 | 日東電工株式会社 | 偏光板およびその製造方法、ならびに該偏光板を用いた画像表示装置 |
Also Published As
Publication number | Publication date |
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CN103097929B (zh) | 2016-02-03 |
TWI579134B (zh) | 2017-04-21 |
CN103097929A (zh) | 2013-05-08 |
KR20130115248A (ko) | 2013-10-21 |
TW201217150A (en) | 2012-05-01 |
US20130163080A1 (en) | 2013-06-27 |
US10532526B2 (en) | 2020-01-14 |
JP2012078796A (ja) | 2012-04-19 |
KR101902024B1 (ko) | 2018-09-27 |
JP5162695B2 (ja) | 2013-03-13 |
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