CN116888511A - Polarizing plate - Google Patents
Polarizing plate Download PDFInfo
- Publication number
- CN116888511A CN116888511A CN202280016561.3A CN202280016561A CN116888511A CN 116888511 A CN116888511 A CN 116888511A CN 202280016561 A CN202280016561 A CN 202280016561A CN 116888511 A CN116888511 A CN 116888511A
- Authority
- CN
- China
- Prior art keywords
- film
- polarizing plate
- polarizing
- retardation
- protective
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
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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
- G02B5/3041—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 comprising multiple thin layers, e.g. multilayer stacks
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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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
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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
- G02B5/3083—Birefringent or phase retarding elements
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- 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
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/875—Arrangements for extracting light from the devices
- H10K59/879—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/8793—Arrangements for polarized light emission
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a polarizing plate which has excellent scratch resistance and can inhibit the generation of cracks of a phase difference film even after long-time storage under normal temperature and normal humidity after a heating endurance test. The polarizing plate comprises a polarizing film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol resin film, a protective film in which a hard coat layer is provided on a base film, and a retardation film having a tensile elastic modulus of 3000MPa or less at a temperature of 23 ℃. More than 2 protective films are laminated on the 1 st surface side of the polarizing film. A retardation film is laminated on the 2 nd surface side of the polarizing film opposite to the 1 st surface side.
Description
Technical Field
The present invention relates to a polarizing plate and a display device including the polarizing plate.
Background
Liquid crystal display devices (LCDs) are widely used not only for liquid crystal televisions but also for mobile applications such as personal computers and cellular phones, and for vehicle applications such as navigation devices. In general, a liquid crystal display device includes a liquid crystal panel member to which a polarizing plate is attached with an adhesive on both sides of a liquid crystal cell, and displays are performed by controlling light from a backlight member using the liquid crystal panel member. In recent years, organic EL display devices have come into wide use in mobile applications such as televisions and cellular phones, and in vehicle applications such as navigation systems, as in liquid crystal display devices. In liquid crystal display devices and organic EL display devices, a retardation film may be used to provide a function of expanding a viewing angle, preventing reflection of external light, and the like.
The opportunity for a polarizing plate to be mounted in a vehicle as an optical element constituting a liquid crystal display device and an organic EL display device is increasing. A polarizing plate used in a display device for a vehicle is more exposed to a high-temperature environment than a polarizing plate used in a mobile application such as a television and a mobile phone, and thus a smaller change in characteristics at a high temperature (high-temperature durability) is more required.
When the display device for a vehicle is used in a navigator or the like, a touch panel function is required. In recent years, as a display device having a touch panel function, there has been an increase In the use of On-Cell type and In-Cell type display devices. In these types of display devices, since the polarizing plate is disposed on the outermost surface on the observation side, a scratch prevention function (scratch resistance) is required in addition to high temperature durability.
Patent document 1 describes a polarizing plate including a retardation film made of a cyclic olefin resin film for enlarging a viewing angle. Patent document 2 describes that a film using a cyclic olefin resin can be used as a retardation film functioning as a λ/4 plate constituting a polarizing plate.
Prior art literature
Patent literature
Patent document 1: japanese patent No. 5383594
Patent document 2: japanese patent laid-open publication No. 2014-194483
Disclosure of Invention
Problems to be solved by the invention
Even if no crack (fracture) is recognized after the heat durability test, if the retardation film comprising the polarizing plate is stored for a long period of time in a normal temperature and normal humidity environment, the crack may be recognized.
The purpose of the present invention is to provide a polarizing plate which has excellent scratch resistance and can suppress the occurrence of cracks in a retardation film even when stored for a long period of time in a normal temperature and normal humidity environment after a heat durability test.
Means for solving the problems
The present invention provides the following polarizing plate.
A polarizing plate comprising:
polarizing film comprising a polyvinyl alcohol resin film and a dichroic dye adsorbed and oriented thereon,
A protective film having a hard coat layer on a base film, and
a retardation film having a tensile elastic modulus of 3000MPa or less at a temperature of 23 ℃,
2 or more of the protective films are laminated on the 1 st surface side of the polarizing film,
the retardation film is laminated on the 2 nd surface side of the polarizing film opposite to the 1 st surface side.
The polarizing plate according to item [ 2 ], wherein, among the 2 or more protective films laminated on the 1 st surface side, at least one protective film has a moisture permeability of 200g/m at a temperature of 40℃and a relative humidity of 90% 2 Day or more.
The polarizing plate according to [ 1 ] or [ 2 ], wherein the protective film laminated on the side closest to the polarizing film has a temperature of 40℃and a relative humidity of 90% among 2 or more of the protective films laminated on the side of the 1 st surface of 200g/m 2 Day or more.
The polarizing plate according to any one of [ 1 ] to [ 3 ], wherein the base film of at least one protective film is a cellulose resin film, which is laminated on 2 or more of the protective films on the 1 st surface side.
The polarizing plate according to any one of [ 1 ] to [ 4 ], wherein the retardation film is a cycloolefin resin film.
The polarizing plate according to any one of [ 1 ] to [ 5 ], wherein an in-plane phase difference value of the retardation film at a wavelength of 550nm is 80nm or more.
The polarizing plate according to any one of [ 1 ] to [ 6 ], which further comprises an adhesive layer on the opposite side of the retardation film to the polarizing film side.
[ 8 ] A display device comprising the polarizing plate and the display element described in [ 7 ],
the polarizing plate is laminated on the display element via the adhesive layer.
Effects of the invention
According to the present invention, it is possible to provide a polarizing plate which is excellent in scratch resistance and can suppress the occurrence of cracks in a retardation film even when stored for a long period of time in a normal temperature and normal humidity environment after a heat durability test.
Drawings
Fig. 1 is a schematic cross-sectional view showing a polarizing plate according to an embodiment of the present invention.
Detailed Description
Hereinafter, preferred embodiments of the polarizing plate and the display device will be described with reference to the drawings.
(polarizing plate)
Fig. 1 is a schematic cross-sectional view showing a polarizing plate according to the present embodiment. The polarizing plate 1 includes: the dichroic dye is formed by adsorbing and aligning a polarizing film 11 formed by a polyvinyl alcohol resin film (hereinafter, sometimes referred to as a "PVA resin film"), protective films 12 and 13 provided with a hard coat layer (hereinafter, sometimes referred to as an "HC layer") on a base film, and a retardation film 21 having a tensile elastic modulus of 3000MPa or less at a temperature of 23 ℃. As shown in fig. 1, in the polarizing plate 1, 2 or more protective films 12 and 13 are laminated on the 1 st surface 11a side of the polarizing film 11, and a retardation film 21 is laminated on the 2 nd surface 11b side of the polarizing film 11 opposite to the 1 st surface 11a side.
As described above, the polarizing plate 1 has 2 or more protective films 12 and 13 including HC layers laminated on the 1 st surface 11a side of the polarizing film 11. This can increase the pencil hardness of the surface of the polarizing plate 1 on the protective films 12 and 13 side, and thus can impart excellent scratch resistance to the polarizing plate 1.
After the heat durability test at a temperature of 105 ℃ for 500 hours, the polarizing plate 1 was kept at a temperature of 23 ℃ and a relative humidity of 55% for about 1 month at room temperature and humidity, and was able to suppress occurrence of cracks (breakage) in the retardation film 21. The reason for this can be presumed as follows. If the polarizing plate 1 is cooled and kept in a normal temperature and normal humidity environment after the heating durability test, moisture (water vapor) in the atmosphere is easily introduced into the polarizing plate. The moisture introduced into the polarizing plate becomes a cause of the dimensional change of the polarizing film including the PVA-based resin film. It is considered that if a force generated by a dimensional change of the polarizing film acts on the retardation film, cracks (cracks) may occur in the retardation film. On the other hand, since the polarizing plate 1 has 2 or more protective films 12 and 13 laminated on the 1 st surface 11a side of the polarizing film 11, the amount of moisture introduced into the polarizing plate 1 can be reduced, and further, the dimensional change of the polarizing film 11 can be suppressed. Therefore, it is presumed that the force acting on the retardation film 21 provided on the 2 nd surface 11b side of the polarizing film 11 can be reduced, and the occurrence of cracks in the retardation film 21 can be suppressed.
The films constituting the polarizing plate 1 may be laminated via the lamination layers 31 to 33 as shown in fig. 1. The bonding layers 31 to 33 are layers using an adhesive or a binder. The bonding layer 31 for bonding the protective film 12 and the protective film 13 is preferably a layer using an adhesive. The bonding layer 32 for bonding the protective film 13 to the polarizing film 11 and the bonding layer 33 for bonding the polarizing film 11 to the retardation film 21 are each preferably layers using an adhesive.
The polarizing plate 1 may further have a functional layer such as an antistatic layer, another retardation layer other than the retardation film 21, another protective layer other than the protective films 12, 13 for protecting the surface of the polarizing film 11, and the like.
The polarizing plate 1 can be used as an optical element constituting a display device. Accordingly, the polarizing plate 1 may have an adhesive layer 35 (fig. 1) for attaching the polarizing plate 1 to a display element or the like of a display device. The polarizing plate 1 may further include a release film that covers and protects the adhesive layer 35 and is releasable from the adhesive layer 35.
(display device)
The display device may include the polarizing plate 1 and a display element such as a liquid crystal cell or an organic Electroluminescence (EL) element. In the display device, the polarizing plate 1 may be disposed such that the 2 nd surface 11b side of the polarizing film 11 is the display element side. The polarizing plate 1 may be laminated on the display element via the adhesive layer 35 shown in fig. 1, and may be laminated on the display element via an adhesive or an adhesive without the adhesive layer 35. Examples of the display device include a liquid crystal display device and an organic EL device.
Hereinafter, the film and the layer constituting the polarizing plate 1 will be described in detail.
(polarizing film)
The polarizing film 11 is an absorption type polarizing film having a property of absorbing linearly polarized light having a vibration plane parallel to an absorption axis thereof and transmitting linearly polarized light having a vibration plane orthogonal to the absorption axis (parallel to a transmission axis). As the polarizing film 11, a film in which a dichroic dye is adsorbed and oriented on a uniaxially stretched PVA-based resin film can be suitably used.
The thickness of the polarizing film 11 is usually 50 μm or less, preferably 5 μm or more and 30 μm or less, more preferably 5 μm or more and 25 μm or less, and still more preferably 5 μm or more and 20 μm or less. By setting the thickness of the polarizing film 11 to these ranges, it is possible to prevent breakage, cracking, or the like at the time of manufacturing the polarizing film 11 while maintaining operability, and to achieve high optical characteristics. By setting the thickness of the polarizing film to 20 μm or less, the decrease in visibility when placed under a high-temperature environment can be further suppressed.
The polarizing film 11 can be produced, for example, by a method including a step of stretching a PVA-based resin film; a step of adsorbing a dichroic dye by dyeing the PVA-based resin film with the dichroic dye; a step of treating the PVA-based resin film having the dichroic dye adsorbed thereon with a crosslinking liquid such as an aqueous boric acid solution; and a step of washing with water after the step of treating with the crosslinking liquid.
As the PVA-based resin film, a film obtained by forming a film of a polyvinyl alcohol-based resin (hereinafter, sometimes referred to as "PVA-based resin") can be used. The PVA-based resin may be a resin obtained by saponifying a polyvinyl acetate-based resin. The polyvinyl acetate resin includes polyvinyl acetate which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other copolymerizable monomers. Examples of the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and (meth) acrylamides having an ammonium group. In the present specification, the term "(meth) acrylic" means at least one selected from acrylic and methacrylic. The same applies to "(meth) acryl", "(meth) acrylate", and the like.
The saponification degree of the PVA-based resin is usually 85mol% or more and 100mol% or less, preferably 98mol% or more. The PVA-based resin may be modified, and for example, polyvinyl formal or polyvinyl acetal modified with an aldehyde may be used. The average polymerization degree of the PVA-based resin is usually 1000 to 10000, preferably 1500 to 5000. The average polymerization degree of the PVA-based resin can be determined in accordance with JIS K6726.
The method for forming the PVA-based resin into a film is not particularly limited, and a known method can be used. The thickness of the PVA-based resin film used in the raw material film at the time of producing the polarizing film is not particularly limited. For example, in order to set the thickness of the polarizing film to 25 μm or less, the thickness of the PVA-based resin film as the raw material film is preferably 40 μm or more and 75 μm or less, more preferably 45 μm or less.
The stretching of the PVA-based resin film is preferably uniaxial stretching. The uniaxial stretching may be performed before dyeing of the dichroic dye, simultaneously with dyeing, or after dyeing. In the case of uniaxial stretching after dyeing, the uniaxial stretching may be performed before or during the crosslinking treatment. In addition, uniaxial stretching may be performed in a plurality of stages of these. In the uniaxial stretching, stretching may be performed uniaxially between rolls having different peripheral speeds, or may be performed uniaxially using a hot roll. The uniaxial stretching may be a dry stretching in which stretching is performed in the atmosphere, or a wet stretching in which stretching is performed in a state in which the PVA-based resin film is swollen with a solvent or water. The stretching ratio is usually 3 to 8 times.
As a method of dyeing the PVA-based resin film with the dichroic dye, for example, a method of immersing the PVA-based resin film in an aqueous solution containing the dichroic dye is adopted. Iodine and a dichroic organic dye may be used as the dichroic dye. The PVA-based resin film is preferably immersed in water before the dyeing treatment.
As the crosslinking treatment after dyeing with the dichroic dye, a method of immersing the dyed PVA-based resin film in an aqueous solution containing boric acid is generally employed. In the case of using iodine as the dichroic dye, the aqueous solution containing boric acid preferably contains potassium iodide.
(protective film)
The protective films 12, 13 have a base film and an HC layer. The protective films 12, 13 are preferably formed with HC layers in direct contact with the base film. The HC layer is preferably provided on one side of the base film, but may be provided on both sides.
The protective films 12 and 13 laminated on the 1 st surface 11a side of the polarizing film 11 (hereinafter, 2 or more protective films laminated on the 1 st surface 11a side are collectively referred to as "protective film group") are preferably 5 or less, more preferably 3 or less, and most preferably 2. If the protective film group includes 6 or more protective films, it is difficult to adjust the curl (warp) of the polarizing plate 1. As shown in fig. 1, the protective films 12 and 13 constituting the protective film group are preferably laminated via the adhesive layer 31, and more preferably both surfaces of the adhesive layer 31 are in direct contact with the protective films 12 and 13 constituting the protective film group. The protective films 12 and 13 constituting the protective film group are each preferably arranged on the polarizing film 11 side of the polarizing plate 1 with the base film and the HC layer on the surface side (opposite side to the polarizing film 11 side) of the polarizing plate 1.
The thickness of the protective film is not particularly limited, but is usually 1 μm or more and 100 μm or less, preferably 5 μm or more and 60 μm or less, more preferably 10 μm or more and 55 μm or less, and still more preferably 15 μm or more and 50 μm or less from the viewpoints of strength and handleability.
In the protective films 12 and 13 constituting the protective film group, one or both of the material and thickness of the base film and the HC layer may be the same, or both of the material and thickness of the base film and the HC layer may be different from each other.
At least one of the protective films in the protective film group preferably has a moisture permeability of 200g/m at a temperature of 40 ℃ and a relative humidity of 90% 2 Day or more, more preferably 300g/m 2 Day or more, the upper limit is usually 5000g/m 2 Day or less, preferably 2000g/m 2 Day or less, more preferably 1000g/m 2 Day or less. In the polarizing plate 1, 1 or more protective films among the protective film group may have the above-described range of moisture permeability. By setting the moisture permeability of the protective film to the above range, the polarizing film 11 can be inhibited from being colored by a heat durability test described later.
The protective film 12 of the protective film group, which is laminated on the side closest to the polarizing film, preferably has the above-described range of moisture permeability. In the case of manufacturing the polarizing plate 1, as described later, the protective film 12 may be bonded to the polarizing film 11 using a bonding agent (adhesive or binder) such as a water-based adhesive, and then the protective film 13 may be bonded to the polarizing film by forming the bonding layer 32 by a drying process. In this case, by setting the moisture permeability of the protective film 12, which is laminated on the side closest to the polarizing film 11, in the protective film group to the above range, the moisture contained in the adhesive can be easily removed by the drying treatment.
The moisture permeability of the protective film 13 other than the protective film 12 included in the protective film group is not particularly limited as long as the protective film 12 laminated on the side closest to the polarizing film 11 among the protective film groups has the moisture permeability in the above range. The other protective film 13 may have a lower moisture permeability than the protective film 12. The moisture permeability of the other protective film 13 at a temperature of 40℃and a relative humidity of 90% is not particularly limited, but is preferably 1000g/m 2 Day or less, more preferably 500g/m 2 Day or less. The moisture permeability of the protective film 13 is preferably greater than 20g/m 2 Day, more preferably 30g/m 2 Day or more. By setting the upper limit value of the moisture permeability of the other protective film 13 to the above range, the moisture migration to the heating durability test can be suppressedThe introduction speed of the rear polarizing plate 1. As a result, it is considered that since it is easy to ensure a time for stress relaxation of the polarizing film 11, occurrence of cracks in the retardation film 21 can be suppressed. By setting the lower limit value of the moisture permeability of the other protective film 13 to the above range, it is possible to suppress the polarization film 11 from becoming multi-functionalized and colored by the heat durability test. The moisture permeability of the protective films 12, 13 can be measured by the method described in examples described later.
The moisture permeability of the protective film 12 in the above description was 200g/m 2 The moisture permeability of the other protective film 13 is 1000g/m 2 The following description will be made on the day, but even when the relationship between the moisture permeabilities is reversed, the polarizing film 11 can be inhibited from becoming multi-functionalized and colored by the heat durability test.
The base films constituting the protective films 12 and 13 are not particularly limited, but are preferably composed of a resin material excellent in transparency, mechanical strength, thermal stability, moisture barrier property, and the like. Examples of such resin materials include 1 or 2 or more types including methyl (meth) acrylate resins, polyolefin resins, cycloolefin resins, polyvinyl chloride resins, cellulose resins, styrene resins, acrylonitrile-butadiene-styrene resins, acrylonitrile-styrene resins, polyvinyl acetate resins, polyvinylidene chloride resins, polyamide resins, polyacetal resins, polycarbonate resins, modified polyphenylene ether resins, polybutylene terephthalate resins, polyethylene terephthalate resins, polysulfone resins, polyethersulfone resins, polyarylate resins, polyamideimide resins, polyimide resins, and the like. These resins may be used after any appropriate polymer modification. Examples of the polymer modification include copolymerization, crosslinking, modification of molecular terminals, stereoregularity control, and modification such as mixing involving a reaction between different polymers.
The base film of at least one protective film among the protective film group is preferably a cellulose resin film formed using a cellulose resin as a resin material. More preferably, the base film of all the protective films constituting the protective film group is a cellulose resin film.
The cellulose resin may be an organic acid ester or a mixed organic acid ester of cellulose in which a part or all of hydrogen atoms in hydroxyl groups of cellulose are substituted with acetyl groups, propionyl groups and/or butyryl groups. Examples thereof include resins containing cellulose such as acetate, propionate, butyrate and mixed esters thereof. Among them, triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate, and the like are preferable.
The resin material constituting the base film may contain an appropriate additive in a range not impairing the transparency. Examples of the additives include antioxidants, ultraviolet absorbers, antistatic agents, lubricants, nucleating agents, antifogging agents, antiblocking agents, retardation reducers, stabilizers, processing aids, plasticizers, impact aids, matting agents, antibacterial agents, and mold inhibitors. These additives may be used in an amount of 1 or more, or in an amount of more than one.
The thickness of the base film is not particularly limited, but may be, for example, 1 μm or more, 3 μm or more, 10 μm or more, or 30 μm or more, and generally 90 μm or less, 70 μm or less, 60 μm or less, or 50 μm or less. The substrate film is generally 1-layer in structure, but may have a multilayer structure of 2 or more layers.
The HC layers constituting the protective films 12, 13 are not particularly limited, but are preferably cured layers of ultraviolet curable resins formed on the base film. Examples of the ultraviolet curable resin include (meth) acrylic resins, silicone resins, polyester resins, urethane resins, amide resins, and epoxy resins. The HC layer may contain additives in order to increase the surface hardness. The additive is not particularly limited, and examples thereof include inorganic fine particles, organic fine particles, or a mixture thereof.
The thickness of the HC layer is preferably 10 μm or less, more preferably 8 μm or less, and usually 0.1 μm or more, or 1 μm or more, or 4 μm or more. If the thickness of the HC layer is greater than 10 μm, the curl (warp) of the protective films 12, 13 becomes large, and it is difficult to adjust the curl of the polarizing plate 1.
The protective films 12, 13 were prepared according to JIS K5600-5-4: 1999 "general test method for coatings-section 5: mechanical properties of the coating film-section 4: the pencil hardness test (when the HC layer side is measured by placing the substrate film having the HC layer formed thereon on a glass plate) specified in scratch hardness (pencil method) "is preferably H or more, more preferably 2H or more, and may be 3H or more, or 4H or more.
The HC layer can be formed, for example, by applying a composition for forming an HC layer (hereinafter, sometimes referred to as "composition for forming an HC layer") containing an ultraviolet curable resin and, if necessary, additives, etc., onto a base film, and curing the composition by irradiation with ultraviolet rays.
(retardation film)
The retardation film 21 is a film having a retardation, and is usually a stretched film obtained by stretching a resin film. The retardation film 21 preferably has a single-layer structure. The tensile elastic modulus of the retardation film 21 at a temperature of 23 ℃ is 3000MPa or less, 2800MPa or less, usually 1000MPa or more, or 2000MPa or more. The tensile elastic modulus can be measured by the method described in examples described below.
As the retardation film 21 having the tensile elastic modulus, for example, an olefin resin film formed using an olefin resin is mentioned. Examples of the olefinic resin include resins mainly containing structural units derived from a chain aliphatic olefin such as ethylene and propylene, or an alicyclic olefin such as norbornene or a substituent thereof (hereinafter, these may be collectively referred to as "norbornene-based monomer"). The term "mainly containing a structural unit" means that the proportion of the structural unit contained in the resin based on the mass is 50% or more. The olefin resin may be a copolymer using 2 or more monomers.
The retardation film 21 is preferably a cyclic olefin resin film formed using a cyclic olefin resin which is a resin mainly containing a structural unit derived from an alicyclic olefin. Typical examples of alicyclic olefins constituting the cycloolefin resin include norbornene monomers. Norbornene is a compound in which 1 carbon-carbon bond of norbornane is a double bond, and is named as bicyclo [2, 1] hept-2-ene according to IUPAC nomenclature. Examples of the substituent for norbornene include 3-substituent, 4-substituent and 4.5-disubstituted, and dicyclopentadiene and dimethylbridged octahydronaphthalene, with the position of the double bond of norbornene being the 1, 2-position.
The cycloolefin resin may or may not have a norbornane ring in its structural unit. Examples of the norbornene-based monomer forming the cyclic olefin-based resin having no norbornane ring in the structural unit include monomers which form a five-membered ring by ring opening, and representatively include norbornene, dicyclopentadiene, 1-or 4-methylnorbornene, 4-phenylnorbornene, and the like. When the cycloolefin resin is a copolymer, the arrangement state of the molecules is not particularly limited, and the cycloolefin resin may be a random copolymer, a block copolymer, or a graft copolymer.
More specific examples of the cycloolefin resin include a ring-opened polymer of a norbornene monomer, a ring-opened copolymer of a norbornene monomer and another monomer, a polymer modified product obtained by subjecting the ring-opened polymer to maleic acid addition, cyclopentadiene addition, and the like, and a polymer or copolymer obtained by hydrogenating the ring-opened polymer; addition polymers of norbornene monomers, addition copolymers of norbornene monomers and other monomers, and the like. Examples of other monomers used in the preparation of the copolymer include α -olefins, cycloolefins, and nonconjugated dienes. The cycloolefin resin may be a copolymer of 1 or 2 or more kinds of norbornene monomers and other alicyclic olefins. Among them, preferred as the cycloolefin resin is a resin obtained by hydrogenating a ring-opened polymer or a ring-opened copolymer using a norbornene monomer.
The commercial products of the cycloolefin resins using norbornene monomers are all represented by trade names, and examples thereof include "ZEONEX", "ZEONOR", and "ARTON" sold by JSR corporation. These cycloolefin resin FILMs and stretched FILMs thereof are commercially available, and examples thereof are "ZEONOR FILM" sold by aptes, strain, ARTON FILM "sold by JSR, strain, and" ESCENA "sold by the water chemical industry, strain.
As the retardation film 21, a film formed of a mixed resin containing 2 or more kinds of olefin resins, or a film formed of a mixed resin of an olefin resin and another thermoplastic resin may be used. For example, as a mixed resin containing 2 or more kinds of olefin resins, there is a mixture of a cyclic olefin resin and a chain aliphatic olefin resin as described above. In the case of using a mixed resin of an olefin-based resin and another thermoplastic resin, the other thermoplastic resin may be appropriately selected depending on the purpose. Specific examples of the other thermoplastic resin include polyvinyl chloride-based resins, cellulose-based resins, polystyrene-based resins, acrylonitrile/butadiene/styrene copolymer resins, acrylonitrile/styrene copolymer resins, (meth) acrylic resins, polyvinyl acetate-based resins, polyvinylidene chloride-based resins, polyamide-based resins, polyacetal-based resins, polycarbonate-based resins, modified polyphenylene ether-based resins, polybutylene terephthalate-based resins, polyethylene terephthalate-based resins, polyphenylene sulfide-based resins, polysulfone-based resins, polyethersulfone-based resins, polyetheretherketone-based resins, polyarylate-based resins, liquid crystal-based resins, polyamideimide-based resins, polyimide-based resins, polytetrafluoroethylene-based resins, and the like. These thermoplastic resins may be used each alone or in combination of 2 or more. The thermoplastic resin may be used after any appropriate polymer modification. Examples of the polymer modification include copolymerization, crosslinking, modification of molecular terminals, and stereoregularity.
When a mixed resin of an olefin resin and another thermoplastic resin is used, the content of the other thermoplastic resin is usually about 50% by weight or less, preferably about 40% by weight or less, relative to the entire resin. By setting the content of the other thermoplastic resin within this range, the retardation film 21 having a small absolute value of the photoelastic coefficient, exhibiting good wavelength dispersion characteristics, and being excellent in durability, mechanical strength, and transparency can be obtained.
The retardation film 21 may contain other components such as residual solvents, stabilizers, plasticizers, anti-aging agents, antistatic agents, and ultraviolet absorbers, as necessary. In addition, a leveling agent may be contained in order to reduce the surface roughness.
The retardation film 21 preferably has an in-plane retardation value of 80nm or more, or 90nm or more, or 100nm or more, or 300nm or less, or 200nm or less at a wavelength of 550 nm. The retardation film 21 is preferably a stretched film.
In general, the higher the in-plane phase difference value of the retardation film 21, the more uniform the molecular orientation of the retardation film 21, and therefore, there is a tendency that cracks are easily generated when an external force is applied. As described above, the polarizing plate 1 has a structure in which 2 or more protective films 12 and 13 are laminated on the 1 st surface 11a of the polarizing film 11. Therefore, even when the polarizing plate 1 including the retardation film 21 having a high in-plane retardation value as described above is held for a long period of time in a normal temperature and normal humidity environment after the heat durability test, the dimensional change of the polarizing film 11 can be suppressed, and the force acting on the retardation film 21 can be reduced concomitantly therewith, so that the occurrence of cracks in the retardation film 21 can be suppressed.
The in-plane phase difference value of the retardation film 21 can be measured by the method described in examples described later. The in-plane phase difference Re (lambda) at the wavelength lambda nm of the retardation film 21 is the in-plane phase difference of the retardation film 21 at a temperature of 23 ℃ and is obtained by the following formula (i).
Re(λ)＝(nx-ny)×d (i)
In the formula (i) of the formula (I),
nx is the refractive index in the direction in which the in-plane refractive index reaches the maximum (i.e. the slow axis direction),
ny is the refractive index in the direction orthogonal to the slow axis in-plane,
d is the thickness [ nm ] of the retardation film 21. ]
The phase difference value in the thickness direction of the phase difference film 21 may be 0 (zero), or may be the phase difference value in the thickness direction. The retardation value in the thickness direction of the retardation film 21 at a wavelength of 550nm may be, for example, 10nm or more, 20nm or more, 40nm or more, and 100nm or less, 80nm or less, or 60nm or less. The phase difference value in the thickness direction of the retardation film 21 can be measured by the method described in examples described later. The thickness-direction phase difference Rth (λ) of the retardation film 21 at the wavelength λnm is the thickness-direction phase difference of the retardation film 21 at a temperature of 23 ℃, and is obtained by the following formula (ii).
Rth(λ)＝〔{(nx+ny)/2}-nz〕×d (ii)
In the formula (ii) of the formula (I),
nx is the refractive index in the direction in which the in-plane refractive index reaches the maximum (i.e. the slow axis direction),
ny is the refractive index in the direction orthogonal to the slow axis in-plane,
nz is the refractive index in the thickness direction,
d is the thickness [ nm ] of the retardation film 21. ]
The thickness of the retardation film 21 is not particularly limited, but is preferably 15 μm or more and 80 μm or less, more preferably 18 μm or more and 45 μm or less, and most preferably 20 μm or more and 30 μm or less. When the thickness of the retardation film is less than 15 μm, handling of the film is difficult, and it is difficult to exhibit a predetermined retardation value. On the other hand, when the thickness of the retardation film is larger than 80 μm, the processability is poor, and the transparency is lowered or the weight of the obtained polarizing plate 1 tends to be increased.
The retardation film 21 can be obtained by using a resin film formed using the above resin and stretching the resin film. The resin film can be obtained by, for example, film formation by a casting method, a melt extrusion method, or the like based on a solution containing the above-mentioned olefin resin. In the case of forming a film using 2 or more kinds of mixed resins, the film forming method is not particularly limited, and examples thereof include a method of forming a film by a casting method using a homogeneous solution obtained by mixing a resin component with a solvent at a predetermined ratio and a method of forming a film by a melt extrusion method by melt mixing a resin component at a predetermined ratio.
The stretching treatment of the resin film includes known longitudinal uniaxial stretching, transverse uniaxial stretching by a tenter, simultaneous biaxial stretching, sequential biaxial stretching, and the like. The stretching treatment may be performed by appropriately adjusting the stretching ratio and stretching speed so as to obtain a desired phase difference value, and appropriately selecting various temperatures such as a preheating temperature, a stretching temperature, a heat setting temperature, and a cooling temperature at the time of stretching, and modes thereof.
In the case where the retardation film 21 is the above-described cycloolefin resin film, it can be obtained, for example, by producing a film-like material which has been subjected to a stretching treatment in advance using the above-described cycloolefin resin, and laminating a shrinkable film having a predetermined shrinkage ratio on the film-like material, and then heat-shrinking the film-like material. Thus, the retardation film 21 having high uniformity and a large phase difference value can be obtained.
(functional layer)
The polarizing plate 1 may have 1 or more antistatic layers, other retardation layers different from the retardation film 21, other protective layers different from the protective films 12 and 13 for protecting the surface of the polarizing film 11, and other functional layers.
The antistatic layer is a layer for suppressing electrification of the polarizing plate 1. The antistatic layer generally contains an antistatic agent such as an ionic compound, and may be a layer containing an antistatic agent and a resin, for example. The antistatic layer may be provided between the polarizing film 11 and the retardation film 21, between the polarizing film 11 and the protective film 12, on the opposite side of the retardation film 21 from the polarizing film 11, or the like in the polarizing plate 1, for example. The antistatic layer is preferably laminated to these films via a lamination layer.
The other phase difference layer is a layer having an in-plane phase difference value or a phase difference value in the thickness direction. The other retardation layer may be, for example, a retardation layer having a retardation value in the thickness direction at a wavelength of 550nm, and may be, for example, a positive C plate or the like. The positive C-plate is used, for example, in a case where the polarizing plate 1 is used in a liquid crystal display device of IPS mode or the like. The other retardation layer may be provided between the polarizing film 11 and the retardation film 21 or on the opposite side of the retardation film 21 from the polarizing film 11 side, for example. The other retardation layer may be a stretched film obtained by stretching a resin film, or may be a cured layer of a polymerizable liquid crystal compound. The other retardation layers may be laminated on the polarizing film 11 and the retardation film 21 via the lamination layer. In the case where the other retardation layer is a cured layer, the polymerizable liquid crystal compound applied to the polarizing film 11 or the retardation film 21 may be polymerized and cured, and may be provided in direct contact with these films.
The other protective layer is a layer for covering and protecting the 1 st surface 11a or the 2 nd surface 11b of the polarizing film 11. The other protective layer is provided on the 2 nd surface 11b side of the polarizing film 11, preferably between the polarizing film 11 and the retardation film 21 via a bonding layer.
In this case, it is preferable that the bonding layer provided between the polarizing film 11 and the other protective layer is provided so as to be in contact with the polarizing film 11 and the other protective layer, and the bonding layer provided between the other protective layer and the retardation film 21 is provided so as to be in contact with the other protective layer and the retardation film 21. As another protective layer, a film formed using a resin material described in the base film constituting the protective films 12, 13 can be given. The other protective layer preferably has no retardation, and examples thereof include a cellulose resin film having no retardation, and a cycloolefin resin film having no retardation.
(bonding layer)
Examples of the bonding layers 31 to 33 for bonding the films and layers constituting the polarizing plate 1 include a layer formed using a known adhesive or a layer formed using a known adhesive.
The adhesive is an adhesive other than a pressure-sensitive adhesive (adhesive), and examples thereof include an aqueous adhesive, an active energy ray-curable adhesive, and a thermosetting adhesive, and preferably an aqueous adhesive and an active energy ray-curable adhesive. The thickness of the adhesive layer formed using the adhesive may be, for example, 0.01 μm or more, 0.1 μm or more, 0.5 μm or more, or 1 μm or more, or 20 μm or less, 15 μm or less, 10 μm or less, or 5 μm or less.
Examples of the aqueous adhesive include adhesives containing an aqueous solution of a polyvinyl alcohol resin, aqueous two-part urethane emulsion adhesives, and the like. Among them, an aqueous adhesive containing an aqueous solution of a polyvinyl alcohol resin can be suitably used. As the polyvinyl alcohol resin, a polyvinyl alcohol homopolymer obtained by saponification of polyvinyl acetate, which is a homopolymer of vinyl acetate, a polyvinyl alcohol copolymer obtained by saponification of a copolymer of vinyl acetate and another monomer copolymerizable therewith, a modified polyvinyl alcohol polymer obtained by partial modification of hydroxyl groups thereof, or the like may be used. The aqueous adhesive may contain a crosslinking agent such as an aldehyde compound (glyoxal or the like), an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, an amine compound, a polyvalent metal salt or the like.
When an aqueous adhesive is used as the adhesive, it is preferable that a drying step for removing water contained in the aqueous adhesive is performed after lamination with the film to be laminated. After the drying step, a curing step of curing at a temperature of 20 to 45℃may be provided.
The active energy ray-curable adhesive is an adhesive containing a curable compound that cures by irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays, and is preferably an ultraviolet-curable adhesive. The curable compound may be a cationically polymerizable curable compound or a radically polymerizable curable compound. Examples of the cationically polymerizable curable compound include an epoxy compound (a compound having 1 or 2 or more epoxy groups in the molecule), an oxetane compound (a compound having 1 or 2 or more oxetane rings in the molecule), and a combination thereof. Examples of the radically polymerizable curable compound include (meth) acrylic compounds (compounds having 1 or 2 or more (meth) acryloyloxy groups in the molecule), other vinyl compounds having radically polymerizable double bonds, and combinations thereof. The cationically polymerizable curable compound may be used in combination with a radically polymerizable curable compound. The active energy ray-curable adhesive generally further contains a cationic polymerization initiator and/or a radical polymerization initiator for initiating the curing reaction of the above-mentioned curable compound.
The pressure-sensitive adhesive is a substance exhibiting adhesiveness by adhering itself to an adherend, and is called a so-called pressure-sensitive adhesive. The adhesive may be composed of an adhesive composition containing a resin such as a (meth) acrylic, rubber, urethane, ester, silicone, or polyvinyl ether as a main component. Among them, an adhesive composition containing a (meth) acrylic resin as a base polymer excellent in transparency, weather resistance, heat resistance and the like is suitable. The binder may be an active energy ray-curable or thermosetting type. The thickness of the adhesive layer formed using the adhesive is usually 3 μm or more and 30 μm or less, preferably 3 μm or more and 25 μm or less.
As the (meth) acrylic resin (base polymer) contained in the adhesive composition, for example, a polymer or copolymer containing 1 or 2 or more kinds of (meth) acrylic esters such as butyl (meth) acrylate, ethyl (meth) acrylate, isooctyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate as monomers can be suitably used. The base polymer is preferably copolymerized with a polar monomer. Examples of the polar monomer include monomers having a carboxyl group, a hydroxyl group, an amide group, an amino group, an epoxy group, and the like, such as (meth) acrylic acid, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) acrylate, acrylamide, N-dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate.
The adhesive composition may comprise only the above base polymer, but usually also contains a crosslinking agent. Examples of the crosslinking agent include a crosslinking agent that is a metal ion having a valence of 2 or more and forms a metal carboxylate between the metal ion and the carboxyl group; a crosslinking agent which is a polyamine compound and forms an amide bond with a carboxyl group; as a crosslinking agent which is a polyepoxide, a polyhydric alcohol, and forms an ester bond with a carboxyl group; as a crosslinking agent for the polyisocyanate compound and forming an amide bond with the carboxyl group. Among them, polyisocyanate compounds are preferable.
(adhesive layer)
The polarizing plate 1 may have an adhesive layer 35 for attaching the polarizing plate 1 to a display element or the like of a display device. The pressure-sensitive adhesive layer 35 is preferably provided on the opposite side of the retardation film 21 of the polarizing plate 1 from the polarizing film 11 side. The adhesive layer 35 may be formed using an adhesive. As the adhesive, an adhesive used for forming the adhesive layer can be mentioned. The thickness of the pressure-sensitive adhesive layer 35 is not particularly limited, but is usually 3 μm or more and 50 μm or less, preferably 5 μm or more and 40 μm or less, and may be 10 μm or more and 30 μm or less.
(Release film)
The polarizing plate 1 may have a release film that can be peeled off from the adhesive layer 35. The release film is used for protecting the surface of the adhesive layer 35 or for supporting the adhesive layer 35. As the release film, a film obtained by subjecting the surface of the base resin film on the side of the pressure-sensitive adhesive layer 35 to a release treatment such as silicone treatment may be mentioned. As the resin material constituting the base resin film, a film formed using the resin material described in the above base film can be given. The base resin film may have a 1-layer structure or a 2-layer or more multilayer structure.
(method for producing polarizing plate)
The method for manufacturing the polarizing plate 1 is not particularly limited, and a known method can be used. For example, the protective film 12 is laminated on the 1 st surface 11a of the polarizing film 11, the retardation film 21 is laminated on the 2 nd surface 11b of the polarizing film 11 with the aqueous adhesive, and the laminate of the protective film 12/the lamination layer 32/the polarizing film 11/the lamination layer 33/the retardation film 21 is produced by a drying step for removing water in the aqueous adhesive. In this case, when a laminate having a difference in thickness between the protective film 12 and the retardation film 21 of 30 μm or less is used, curling generated in the laminate is easily suppressed, and a flat laminate is easily obtained. Thereafter, the protective film 13 is laminated on the protective film 12 side of the laminate via the adhesive layer 31, whereby the polarizing plate 1 can be obtained. In the case where the polarizing plate 1 has 3 or more protective films on the 1 st surface 11a side of the polarizing film 11, a step of laminating the protective films may be further provided. Even when a laminate having a difference in thickness between the protective film 12 and the retardation film 21 of 30 μm or less is used as described above, curling generated in the polarizing plate 1 is easily suppressed, and a flat polarizing plate 1 is easily obtained.
In order to improve the adhesion between the films and layers (the protective films 12 and 13, the polarizing film 11, the retardation film 21, the functional layer, and the like) constituting the polarizing plate 1 and the bonding layer, the bonding surfaces of these films and layers may be subjected to a surface activation treatment. Examples of the surface activation treatment include dry treatments such as corona treatment, plasma treatment, discharge treatment (glow discharge treatment and the like), flame treatment, ozone treatment, UV ozone treatment, and ionizing active radiation treatment (ultraviolet treatment, electron beam treatment and the like); wet treatments such as ultrasonic treatment using a solvent such as water or acetone, saponification treatment, and anchor coating treatment are used. These surface activation treatments may be performed alone or in combination of 2 or more.
Examples
Hereinafter, the present invention will be described in further detail by way of examples and comparative examples, but the present invention is not limited to these examples.
[ measurement of thickness ]
The thickness of each film and each layer constituting the polarizing plate was measured using MH-15M as a digital micrometer manufactured by Nikon corporation.
[ measurement of moisture permeability ]
Moisture permeability of the protective film was in accordance with JIS K7129: 2008 appendix B was measured at 40℃in an atmosphere with a relative humidity of 90%.
[ measurement of phase Difference value ]
The retardation value of the retardation film and the retardation layer was measured by using a retardation measuring apparatus KOBA-WPR (manufactured by prince measuring instruments Co., ltd.).
[ measurement of modulus of elasticity in tension ]
Test pieces 15mm wide by 150mm long were cut out of the retardation film parallel to the slow axis and the fast axis, respectively. Then, both ends of the test piece in the longitudinal direction were clamped by upper and lower clamps of a tensile tester (AUTOGRAPH (registered trademark) AG-1S tester manufactured by Shimadzu corporation) such that the interval between the clamps was 100 mm. The film was stretched at a stretching speed of 50 mm/min at 23℃to prepare a stress-strain curve. Based on the stress-strain curve, the tensile elastic modulus at 23℃in the directions parallel to the slow and fast axes was calculated. The tensile elastic modulus having a large value among the tensile elastic moduli in directions parallel to the slow axis and the fast axis thus calculated was used as the value of the tensile elastic modulus at 23 ℃.
[ measurement of storage modulus ]
The storage modulus G' of the adhesive layers A and B was measured according to the following procedures [ I ] to [ III ].
2 samples were taken out from each adhesive layer so that the weight of each sample was 25.+ -.1 mg, and each sample was formed into a substantially spherical shape.
The formed 2 samples were adhered to the upper and lower surfaces of the I-type jig, respectively, and the upper and lower surfaces were each clamped by an L-type jig to prepare measurement samples. The measurement sample was configured as an L-type jig/adhesive layer A or an adhesive layer B/I-type jig/adhesive layer/L-type jig.
The storage modulus G' of the measurement sample was measured using a dynamic viscoelasticity measuring device "DVA-220" manufactured by IT meter control (Inc.) under the conditions of a temperature of 23 ℃, a frequency of 1Hz, and an initial strain of 1N.
[ measurement of Pencil hardness ]
The protective film is disposed on the glass plate so that the substrate film side of the protective film faces the glass plate. JIS K5600-5-4 was performed on the HC layer side of the protective film: 1999 "general test method for coatings-section 5: mechanical properties of the coating film-section 4: the pencil hardness of the protective film was measured by a pencil hardness test specified in scratch hardness (pencil method) ".
< preparation of polarizing film >
A40 μm thick PVA-based resin film comprising a PVA-based resin having an average degree of polymerization of about 2400 and a degree of saponification of 99.9 mol% or more was prepared. The PVA-based resin film was uniaxially stretched to about 5 times in a dry manner, and then immersed in pure water at a temperature of 60 ℃ for 1 minute while maintaining a stretched state. Thereafter, the PVA based resin film was immersed in an aqueous solution having a temperature of 28℃and a weight ratio of iodine/potassium iodide/water of 0.05/5/100 for 60 seconds. Thereafter, the PVA based resin film was immersed in an aqueous solution having a temperature of 72℃and a weight ratio of potassium iodide/boric acid/water of 8.5/8.5/100 for 300 seconds. Then, the mixture was washed with pure water at 26℃for 20 seconds, and then dried at 65 ℃.
In this manner, a polarizing film having a thickness of 15 μm was obtained in which iodine as a dichroic dye was adsorbed and oriented to the PVA-based resin film.
< preparation of protective film (1)
The following components were mixed to prepare a composition for forming an HC layer.
PET 30.0 parts by mass
Irgacure 907.0 parts by mass
MEK 81.8 parts by mass
The PET30 is a mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate (manufactured by japan chemical Co., ltd.).
Irgacure 907 is a photopolymerization initiator (manufactured by BASF corporation).
MEK is methyl ethyl ketone.
The substrate film (cellulose acylate film TD40, manufactured by fuji film (ltd.), width 1340mm, film thickness 40 μm) wound in a roll shape was wound out, the HC layer forming composition was applied by a die coating method using a slit die at a conveying speed of 30 m/min, and dried at 60 ℃ for 150 seconds to form a coating layer. Thereafter, under a nitrogen purge, an air-cooled metal halide lamp (manufactured by EYE GRAPHICAS Co., ltd.) was used at an output of 160W/cm at an oxygen concentration of about 0.1% at an illuminance of 400mW/cm 2 An irradiation amount of 120mJ/cm 2 The coating layer is cured by ultraviolet rays to form an HC layer. The thickness of the coating layer was adjusted so that the thickness of the HC layer was 7. Mu.m. In this manner, a protective film (1) having an HC layer on one surface of the base film was obtained, and the protective film (1) was wound. The moisture permeability of the protective film (1) is 250g/m 2 Day. The pencil hardness of the protective film (1) was 2H.
< preparation of protective film (2)
The protective film (2) was obtained by the same procedure as the production of the protective film (1), except that the thickness of the coating layer was adjusted so that the thickness of the HC layer was 5. Mu.m. The moisture permeability of the protective film (2) is 350g/m 2 Day. The pencil hardness of the protective film (2) was 3H.
< preparation of protective film (3) >)
The protective film (3) was obtained by the same procedure as the production of the protective film (1), except that the thickness of the coating layer was adjusted so that the thickness of the HC layer was 3. Mu.m. The moisture permeability of the protective film (3) is 500g/m 2 Day. The pencil hardness of the protective film (3) was 3H.
< preparation of phase-difference laminate comprising phase-difference film and other phase-difference layer >
A retardation film and other retardation layers were produced in accordance with the descriptions in paragraphs [0106] to [0109] of International publication No. 2018/207798. Specifically, an unstretched cycloolefin polymer FILM (trade name "ARTON FILM" manufactured by JSR corporation) was uniaxially stretched to obtain a retardation FILM having a thickness of 24 μm. The tensile elastic modulus of the obtained retardation film at a temperature of 23℃was measured and found to be 2742MPa. In addition, the in-plane phase difference Re (550) at the wavelength of 550nm of the retardation film was 110nm, and the thickness-direction phase difference Rth (550) at the wavelength of 550nm was 55nm.
Then, a composition containing a rod-like liquid crystalline compound was applied to one surface of the retardation film obtained by the above-described operation to form another retardation layer, thereby obtaining a retardation laminate. The in-plane phase difference Re (550) at the wavelength of 550nm of the other phase difference layer was 0nm, and the thickness-direction phase difference Rth (550) at the wavelength of 550nm was-100 nm.
< preparation of polyvinyl alcohol-based adhesive (PVA-based adhesive)
50g of an acetoacetyl group-containing modified PVA-based resin (Gosenex Z-410, manufactured by Mitsubishi chemical Co., ltd.) was dissolved in 950g of pure water, heated at 90℃for 2 hours, and then cooled to room temperature to obtain a polyvinyl alcohol solution. Then, polyvinyl alcohol solution, maleic acid, glyoxal, and pure water were mixed so that the respective compounds had the following concentrations, and a PVA-based adhesive was prepared.
Polyvinyl alcohol concentration 3.0 wt%
Maleic acid concentration 0.01 wt%
Glyoxal concentration 0.15 wt%
< preparation of adhesive layer A and adhesive layer B >
As the adhesive layer A, a commercially available sheet-like acrylic adhesive having a thickness of 5 μm (storage modulus at 23 ℃ C.: 0.06 MPa) was prepared.
As the adhesive layer B, a commercially available sheet-like acrylic adhesive having a thickness of 25 μm (storage modulus at 23 ℃ C. Of 0.06 MPa) was prepared.
[ example 1 ]
The protective film (1) obtained by the above-described operation was immersed in a 1.5mol/L aqueous NaOH solution (saponification liquid) maintained at a temperature of 55℃for 2 minutes, and then washed with water. The protective film (1) after washing was immersed in a sulfuric acid aqueous solution of 0.05mol/L at 25℃for 30 seconds, and then passed through the protective film under running water for 30 seconds, whereby the protective film (1) was brought into a neutral state. The protective film (1) was repeatedly dehydrated 3 times by an air knife, and then left in a drying zone at 70℃for 15 seconds to be dried. Thus, a saponified protective film (1) is obtained in which the HC layer and the base film are saponified (surface-activated).
A laminate (1) in which a saponified protective film (1) (hereinafter sometimes referred to as "1 st protective film (1)"), a polarizing film, and a retardation laminate were laminated via a PVA based adhesive prepared by the above-described procedure was obtained. In the laminate (1), the absorption axis of the polarizing film is parallel to the slow axis of the phase difference film. In the laminated body (1), the other retardation layer side of the retardation laminated body faces the polarizing film, and the base film side of the 1 st protective film (1) faces the polarizing film. The adhesion between the retardation laminate and the polarizing film and the adhesion between the polarizing film and the 1 st protective film (1) are practically sufficient adhesion.
Next, a saponification-treated protective film (1) that has been subjected to saponification treatment in the same manner as described above (hereinafter, sometimes referred to as "2 nd protective film (1)") is laminated via an adhesive layer a on the 1 st protective film (1) side of the laminate (1) obtained by the above-described operation. The 2 nd protective film (1) has a substrate film side as a bonding surface with the adhesive layer (A). The phase difference laminate side of the laminate (1) is subjected to corona treatment, the surface of the adhesive layer B is subjected to corona treatment, and the corona treated surface of the laminate (1) and the corona treated surface of the adhesive layer (B) are laminated. Thus, a polarizing plate (1) is obtained. In the polarizing plate (1), the 1 st protective film (1) and the 2 nd protective film (1) are disposed on the same surface side of the polarizing film, the 1 st protective film (1) is disposed at a position relatively close to the polarizing film, and the 2 nd protective film (1) is disposed at a position relatively far from the polarizing film.
[ example 2 ]
A polarizing plate (2) was obtained by the same procedure as the procedure for producing the polarizing plate (1) produced in example 1, except that a saponified protective film (2) having undergone the same saponification treatment as that of the protective film (1) was used instead of the 1 st protective film (1) and the 2 nd protective film (1).
[ example 3 ]
A polarizing plate (3) was obtained by the same procedure as the procedure for producing the polarizing plate (1) produced in example 1, except that a saponified protective film (3) having undergone the same saponification treatment as that carried out on the protective film (1) was used instead of the 1 st protective film (1) and the 2 nd protective film (1).
Comparative example 1
A comparative polarizing plate (C1) was obtained by the same procedure as the procedure for producing the polarizing plate (1) produced in example 1, except that a saponified base film (cellulose acylate film TD40, manufactured by fuji film, width 1340mm, film thickness 40 μm) subjected to the same saponification treatment as the saponification treatment performed on the protective film (1) was used instead of the 2 nd protective film (1).
Comparative example 2
A laminate (1) produced by the same procedure as in example 1 was obtained as a comparative polarizing plate (C2).
[ comparative example 3 ]
A comparative polarizing plate (C3) was obtained by the same procedure as the procedure for producing the polarizing plate (1) produced in example 1, except that a saponified base film (cellulose acylate film TD40, manufactured by fuji film, width 1340mm, film thickness 40 μm) subjected to the same saponification treatment as the saponification treatment performed on the protective film (1) was used instead of the 1 st protective film (1).
[ evaluation of crack Generation ]
For the polarizing plate obtained in the example and the comparative polarizing plate obtained in the comparative example, samples for evaluation were prepared in accordance with the following procedure, and the occurrence of cracks was evaluated. The polarizing plate or the comparative polarizing plate was cut into 200mm by 200mm sizes, and an alkali-free glass having a thickness of 0.7mm and 300mm by 300mm was bonded via an adhesive layer B to prepare a sample for evaluation.
The prepared sample for evaluation was kept in a heating environment at 105℃for 500 hours, and then cooled to 23℃at room temperature. Thereafter, after the film was kept at a temperature of 23℃and a relative humidity of 55% for 30 days in a normal-temperature and normal-humidity environment, the polarizing plate or the retardation film of the comparative polarizing plate was observed to confirm the occurrence of cracks. Then, the sample for evaluation, in which no occurrence of cracks was observed at this time, was further observed for the retardation film after 7 days (after 37 days from the start of the maintenance in the normal temperature and normal humidity environment), and the presence or absence of occurrence of cracks was confirmed. The results are shown in Table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparison ofExample 1 | Comparative example 2 | Comparative example 3 | |
| Polarizing plate or comparative polarizing plate | (1) | (2) | (3) | (C1) | (C2) | (C3) |
| Type 1 protective film ※1 | (1) | (2) | (3) | (1) | (1) | Substrate film |
| Thickness of HC layer | 7μm | 5μm | 3μm | 7μm | 7μm | - |
| Type 2 of the 2 nd protective film | (1) | (2) | (3) | Substrate film | - | (1) |
| Thickness of HC layer | 7μm | 5μm | 3μm | - | - | 7μm |
| Crack generation | ||||||
| After 30 days | Without any means for | Without any means for | Without any means for | Has the following components | Has the following components | Has the following components |
| After 37 days | Without any means for | Without any means for | Has the following components | - | - |
1: protective film disposed at a position relatively close to polarizing film
2: protective film disposed at a position relatively distant from polarizing film
Description of the reference numerals
1. Polarizing plate, 11 polarizing film, 11a 1 st surface, 11b 2 nd surface, 12, 13 protective film, 21 retardation film, 31 to 33 lamination layers, 35 adhesive layer.
Claims (8)
1. A polarizing plate is provided with:
polarizing film comprising a polyvinyl alcohol resin film and a dichroic dye adsorbed and oriented thereon,
A protective film having a hard coat layer on a base film, and
a retardation film having a tensile elastic modulus of 3000MPa or less at a temperature of 23 ℃,
more than 2 protective films are laminated on the 1 st surface side of the polarizing film,
the retardation film is laminated on the 2 nd surface side of the polarizing film opposite to the 1 st surface side.
2. The polarizing plate according to claim 1, wherein,
at least one of the 2 or more protective films laminated on the 1 st surface side has a moisture permeability of 200g/m at a temperature of 40 ℃ and a relative humidity of 90% 2 Day or more.
3. The polarizing plate according to claim 1 or 2, wherein,
of the 2 or more protective films laminated on the 1 st surface side, the protective film laminated on the side closest to the polarizing film has a moisture permeability of 200g/m at a temperature of 40 ℃ and a relative humidity of 90% 2 Day or more.
4. The polarizing plate according to any one of claims 1 to 3, wherein,
the base film of at least one of the 2 or more protective films laminated on the 1 st surface side is a cellulose resin film.
5. The polarizing plate according to any one of claims 1 to 4, wherein,
the phase difference film is a cyclic olefin resin film.
6. The polarizing plate according to any one of claims 1 to 5, wherein,
the in-plane phase difference value of the phase difference film at the wavelength of 550nm is more than 80 nm.
7. The polarizing plate according to any one of claims 1 to 6, further comprising an adhesive layer on a side of the retardation film opposite to the polarizing film side.
8. A display device having the polarizing plate and the display element according to claim 7,
the polarizing plate is laminated to the display element via the adhesive layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-038993 | 2021-03-11 | ||
| JP2021038993A JP2022138876A (en) | 2021-03-11 | 2021-03-11 | Polarizing plate |
| PCT/JP2022/009147 WO2022191033A1 (en) | 2021-03-11 | 2022-03-03 | Polarizing plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116888511A true CN116888511A (en) | 2023-10-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280016561.3A Pending CN116888511A (en) | 2021-03-11 | 2022-03-03 | Polarizing plate |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2022138876A (en) |
| KR (1) | KR20230154893A (en) |
| CN (1) | CN116888511A (en) |
| TW (1) | TW202248681A (en) |
| WO (1) | WO2022191033A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100601920B1 (en) | 2004-01-09 | 2006-07-14 | 주식회사 엘지화학 | In-plane switching liquid crystal display comprising compensation film for angular field of view using negative biaxial retardation film and + c-plate |
| JP2005345958A (en) * | 2004-06-07 | 2005-12-15 | Nitto Denko Corp | Liquid crystal panel, polarizing plate and liquid crystal display |
| JP5755674B2 (en) | 2013-03-29 | 2015-07-29 | 日東電工株式会社 | Method for producing retardation film and method for producing circularly polarizing plate |
| JP6267886B2 (en) * | 2013-07-22 | 2018-01-24 | 富士フイルム株式会社 | Liquid crystal display |
| WO2017047408A1 (en) * | 2015-09-18 | 2017-03-23 | 住友化学株式会社 | Composite polarizing plate and liquid crystal panel using same |
| JP6323477B2 (en) * | 2016-02-29 | 2018-05-16 | 住友化学株式会社 | Polarizing plate set and LCD panel |
-
2021
- 2021-03-11 JP JP2021038993A patent/JP2022138876A/en active Pending
-
2022
- 2022-03-03 KR KR1020237032982A patent/KR20230154893A/en unknown
- 2022-03-03 CN CN202280016561.3A patent/CN116888511A/en active Pending
- 2022-03-03 WO PCT/JP2022/009147 patent/WO2022191033A1/en active Application Filing
- 2022-03-08 TW TW111108390A patent/TW202248681A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| TW202248681A (en) | 2022-12-16 |
| KR20230154893A (en) | 2023-11-09 |
| JP2022138876A (en) | 2022-09-26 |
| WO2022191033A1 (en) | 2022-09-15 |
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