CN113646676A - Polarizing film, polarizing plate, and method for producing polarizing film - Google Patents
Polarizing film, polarizing plate, and method for producing polarizing film Download PDFInfo
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- CN113646676A CN113646676A CN202080025622.3A CN202080025622A CN113646676A CN 113646676 A CN113646676 A CN 113646676A CN 202080025622 A CN202080025622 A CN 202080025622A CN 113646676 A CN113646676 A CN 113646676A
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- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 24
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- OHNKSVVCUPOUDJ-UHFFFAOYSA-N 5-nitro-1h-indene Chemical compound [O-][N+](=O)C1=CC=C2CC=CC2=C1 OHNKSVVCUPOUDJ-UHFFFAOYSA-N 0.000 description 1
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Images
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polarising Elements (AREA)
Abstract
The invention provides a polarizing film having excellent durability under a high-temperature and high-humidity environment. The polarizing film of the present invention is composed of a polyvinyl alcohol resin film containing iodine, and at least one surface layer portion contains a nitrogen-containing compound.
Description
Technical Field
The present invention relates to a polarizing film, a polarizing plate, and a method for producing the polarizing film.
Background
In a liquid crystal display device, which is a typical image display device, polarizing films are arranged on both sides of a liquid crystal cell depending on an image forming method. As a method for producing a polarizing film, for example, the following methods are proposed: a polarizing film is obtained on a resin substrate by stretching a laminate having the resin substrate and a polyvinyl alcohol (PVA) -based resin layer, and then performing a dyeing treatment (for example, patent document 1). Since a polarizing film having a small thickness can be obtained by such a method, attention has been paid to a method contributing to thinning of an image display device in recent years. However, a thin polarizing film is required to have further improved durability under a high-temperature and high-humidity environment.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2001-343521
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above-described conventional problems, and a main object thereof is to provide a polarizing film and a polarizing plate having excellent durability under a high-temperature and high-humidity environment, and a method for producing such a polarizing film.
Means for solving the problems
According to 1 aspect of the present invention, there is provided a polarizing film comprising a polyvinyl alcohol resin film containing iodine, wherein at least one surface layer portion contains a nitrogen-containing compound.
In 1 embodiment, (CN) in cross-sectional analysis using time-of-flight secondary ion mass spectrometry-) And (C)2H-) Ionic strength ratio (CN)-/C2H-) The region of 0.15 or more is present at 300nm or more in the thickness direction from the surface of the surface layer portion.
In 1 embodiment, the nitrogen-containing compound includes a diazo compound.
In 1 embodiment, the polarizing film has a thickness of 8 μm or less.
According to another aspect of the present invention, there is provided a polarizing plate having: the polarizing film and a protective layer disposed on at least one side of the polarizing film.
According to still another aspect of the present invention, there is provided a method of manufacturing the polarizing film described above, including: forming a polyvinyl alcohol resin layer on one side of a long thermoplastic resin base material to form a laminate; stretching and dyeing the laminate to form a polarizing film from the polyvinyl alcohol resin layer; and contacting the polarizing film with a treatment solution containing a diazo compound.
In 1 embodiment, the above manufacturing method includes: forming a polyvinyl alcohol resin layer on one side of a long thermoplastic resin base material to form a laminate; subjecting the laminate to in-air auxiliary stretching treatment, dyeing treatment, and underwater stretching treatment in this order to form a polarizing film from the polyvinyl alcohol resin layer; and performing a drying shrinkage treatment of shrinking the laminate by 2% or more in the width direction by heating while conveying the laminate along the length direction, and bringing the polarizing film into contact with a treatment liquid containing a diazo compound after the stretching treatment in water and before or after the drying shrinkage treatment.
In 1 embodiment, the drying shrinkage treatment is performed using a heated roller.
In 1 embodiment, the temperature of the heated roller is 60 to 120 ℃.
In 1 embodiment, the polyvinyl alcohol resin layer contains a polyvinyl alcohol resin and contains an iodide or sodium chloride.
According to another aspect of the present invention, there is provided a method of manufacturing the polarizing film described above, comprising: stretching and dyeing a polyvinyl alcohol resin film to form a polarizing film; and contacting the polarizing film with a treatment solution containing a diazo compound.
In 1 embodiment, contacting the polarizing film with the treatment liquid includes applying a treatment liquid containing a diazo compound at a concentration of 0.2 wt% or more to the surface of the polarizing film.
In 1 embodiment, the contacting the polarizing film with the treatment liquid includes immersing the polarizing film in a treatment liquid containing a diazo compound at a concentration of 0.01 wt% or more.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a polarizing film having excellent durability under a high-temperature and high-humidity environment, specifically, a polarizing film in which a decrease in polarization degree under a high-temperature and high-humidity environment is suppressed can be obtained. Such a polarizing film can be obtained by including a nitrogen-containing compound in the surface layer portion.
Drawings
Fig. 1A is a schematic cross-sectional view of a polarizing film of 1 embodiment of the present invention.
Fig. 1B is a schematic cross-sectional view of a polarizing film of 1 embodiment of the present invention.
Fig. 2A is a schematic cross-sectional view of a polarizing plate according to 1 embodiment of the present invention.
Fig. 2B is a schematic cross-sectional view of a polarizing plate according to 1 embodiment of the present invention.
Fig. 3 is a schematic diagram showing an example of the drying shrinkage process using a heating roller.
Detailed Description
Embodiments of the present invention will be described below, but the present invention is not limited to these embodiments.
A. Polarizing film
The polarizing film according to the embodiment of the present invention is composed of a polyvinyl alcohol (PVA) resin film containing iodine, and at least one surface layer portion contains a nitrogen-containing compound. Fig. 1A and 1B are schematic cross-sectional views of a polarizing film according to 1 embodiment of the present invention. The polarizing film 10a shown in fig. 1A contains a nitrogen-containing compound only in one surface layer portion 12. The polarizing film 10B shown in fig. 1B contains a nitrogen-containing compound in both surface layer portions 12 and 14. The polarizing film contains a nitrogen-containing compound in at least one surface layer portion, so that the reduction of polarization degree under high temperature and high humidity is suppressed, and the durability can be improved.
The thickness of the polarizing film is preferably 8 μm or less, more preferably 7 μm or less, further preferably 5 μm or less, and particularly preferably 3 μm or less. The lower limit of the thickness of the polarizing film may be 1 μm in 1 embodiment, and may be 2 μm in another embodiment. Such a thickness can be achieved, for example, by producing a polarizing film using a laminate of a thermoplastic resin substrate and a PVA-based resin layer formed on the thermoplastic resin substrate by coating, as will be described later. When the polarizing film is made of a single PVA-based resin film, the thickness of the polarizing film may be, for example, 12 to 35 μm.
The thickness of the region in which the nitrogen-containing compound is present in the surface layer portion of the polarizing film is not limited as long as the effects of the present invention can be obtained, and may be any thickness.
In 1 embodiment, (CN) in cross-sectional analysis using time-of-flight secondary ion mass spectrometry (TOF-SIMS)-) And (C)2H-) Ionic strength ratio (CN)-/C2H-) The region of 0.15 or more is preferably 300nm or more, more preferably 350nm or more, and still more preferably 500nm or more in the thickness direction from the surface of the surface layer portion (surface of the polarizing film). The ionic strength ratio (CN)-/C2H-) The thickness of the region of 0.15 or more may be 1500nm or less, preferably 1000nm or less, for example.
Ion intensity ratio (CN) in the surface layer of the polarizing film-/C2H-) The upper limit of (b) is, for example, 0.80, and may be, for example, 0.70. Typically, the ionic strength ratio (CN) in the surface layer of the polarizing film is-/C2H-) The tendency is shown to be gradually smaller from a shallow part (e.g., surface) toward a deep part.
As the nitrogen-containing compound, a nitrogen-containing compound which can function as a crosslinking agent for the PVA-based resin is preferably used. Examples of the nitrogen-containing compound that can be used in the present invention include diazo compounds and tetrazolium compounds. In the present specification, the diazonium compound includes not only a diazonium compound having a diazo group (diazo group) in a molecule but also a diazonium compound having a diazo group (diazo group) in a molecule or a diazonium salt. The nitrogen-containing compounds may be used alone or in combination of two or more.
Specific examples of the diazo compound include diazobenzene chloride, p-aminoazobenzene, 4-diazo-4' -methoxydiphenylamine sulfate, 4-diazodiphenylamine sulfate, and 4-phenylaminobenzenediazonium sulfate. Among them, 4-diazo-4' -methoxydiphenylamine sulfate and 4-phenylaminobenzenediazonium sulfate are preferable, and 4-phenylaminobenzenediazonium sulfate is more preferable.
Specific examples of the diazonium compounds include 4,4 '-bis (diazo) diphenyl sulfate and 4, 4' -bis (diazo) methoxydiphenyl sulfate.
The polarizing film preferably exhibits absorption dichroism at any wavelength of 380nm to 780 nm. The polarizing film preferably has a monomer transmittance of 42.0% or more, more preferably 42.5% or more, and still more preferably 43.0% or more. On the other hand, the monomer transmittance is preferably 47.0% or less, more preferably 46.0% or less. The polarization degree of the polarizing film is preferably 99.95% or more. On the other hand, the degree of polarization is preferably 99.998% or less. According to the embodiments of the present invention, a high polarization degree can be maintained even under a high-temperature and high-humidity environment. In the present specification, the single transmittance, the orthogonal transmittance and the polarization degree refer to the single transmittance, the orthogonal transmittance and the polarization degree before the durability test. The monomer transmittance is typically a Y value measured by an ultraviolet-visible spectrophotometer and corrected for visual sensitivity. The single transmittance is a value obtained by converting the refractive index of one surface of the polarizing plate to 1.50 and the refractive index of the other surface to 1.53. The degree of polarization is typically determined by the following equation based on the parallel transmittance Tp and the orthogonal transmittance Tc obtained by measuring with an ultraviolet-visible spectrophotometer and performing a visual sensitivity correction.
Polarization degree (%) { (Tp-Tc)/(Tp + Tc) }1/2×100
In embodiment 1, the change Δ P in the polarization degree of the polarizing film after the durability test at 60 ℃ and 95% relative humidity for 240 hours may be preferably from-0.100% to 0.001%, more preferably from-0.050% to 0.001%, even more preferably from-0.030% to 0.001%, even more preferably from-0.020% to 0.001%. The amount of change Δ P in the degree of polarization is expressed by the following equation.
ΔP＝P240-P0
(in the formula, P240Degree of polarization after endurance test, P0The degree of polarization (degree of polarization explained in the above) before the durability test
The polarizing film may be produced using a single PVA-based resin film, or may be produced using a laminate of two or more layers including PVA-based resin layers. Specific examples of the polarizing film obtained using the laminate include a polarizing film obtained using a laminate of a thermoplastic resin substrate and a PVA-based resin layer applied to the thermoplastic resin substrate. Details of the method for producing the polarizing film will be described later in item C.
B. Polarizing plate
Fig. 2A and 2B are schematic cross-sectional views of a polarizing plate according to 1 embodiment of the present invention. The polarizing plate 100a shown in fig. 2A has: a polarizing film 10, and a 1 st protective layer 20 disposed on one side of the polarizing film 10. The polarizing plate 100B shown in fig. 2B has: the liquid crystal display device includes a polarizing film 10, a 1 st protective layer 20 disposed on one side of the polarizing film 10, and a 2 nd protective layer 30 disposed on the other side of the polarizing film 10. The polarizing film 10 is the polarizing film described in the above item a. By including the polarizing film described in item a, the polarizing plate of the present embodiment can suppress a decrease in polarization degree under high temperature and high humidity, and can exhibit excellent durability. The 1 st protective layer 20 or the 2 nd protective layer 30 may be a thermoplastic resin substrate used in the manufacture of a polarizing film. In the embodiment in which the protective layer is disposed only on one side of the polarizing film, when the polarizing film contains the nitrogen-containing compound only in one surface portion, the surface portion containing the nitrogen-containing compound may be the side on which the protective layer is disposed or the opposite side. As shown in fig. 2A, the surface portion of the polarizing film 10 opposite to the side on which the protective layer 20 is disposed is preferably the surface portion 12 containing a nitrogen-containing compound.
The 1 st and 2 nd protective layers are formed of any suitable film that can be used as a protective layer for a polarizing film. Specific examples of the material as the main component of the film include cellulose resins such as Triacetylcellulose (TAC), polyester resins, polyvinyl alcohol resins, polycarbonate resins, polyamide resins, polyimide resins, polyether sulfone resins, polysulfone resins, polystyrene resins, polynorbornene resins, polyolefin resins, (meth) acrylic resins, acetate resins, and the like transparent resins. Further, there may be mentioned thermosetting resins such as (meth) acrylic, urethane, (meth) acrylic urethane, epoxy, silicone and the like, ultraviolet-curable resins and the like. Further, for example, a glassy polymer such as a siloxane polymer can be cited. Further, the polymer film described in Japanese patent application laid-open No. 2001-343529 (WO01/37007) may be used. As a material of the film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in a side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in a side chain can be used, and for example, a resin composition having an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer can be mentioned. The polymer film may be, for example, an extrusion molded product of the resin composition.
When the polarizing plate is applied to an image display device, the thickness of the protective layer (outer protective layer) disposed on the side opposite to the display panel is typically 300 μm or less, preferably 100 μm or less, more preferably 5 μm to 80 μm, and still more preferably 10 μm to 60 μm. When the surface treatment is performed, the thickness of the outer protective layer is a thickness including the thickness of the surface treatment layer.
When the polarizing plate is applied to an image display device, the thickness of the protective layer (inner protective layer) disposed on the display panel side is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm, and still more preferably 10 μm to 60 μm. In 1 embodiment, the inner protective layer is a retardation layer having any suitable phase difference value. In this case, the in-plane retardation Re (550) of the retardation layer is, for example, 110nm to 150 nm. "Re (550)" is an in-plane retardation measured at 23 ℃ with light having a wavelength of 550nm, represented by the formula: re ═ x-ny) × d. Here, "nx" is a refractive index in a direction in which the in-plane refractive index is maximum (i.e., the slow axis direction), "ny" is a refractive index in a direction orthogonal to the slow axis in the plane (i.e., the fast axis direction), "nz" is a refractive index in the thickness direction, and "d" is the thickness (nm) of the layer (film).
C. Method for producing polarizing film
The method for producing a polarizing film of the present invention typically comprises bringing a treatment liquid containing a diazo compound into contact with at least one surface of a polarizing film. By bringing a treatment liquid containing a diazo compound into contact with the surface of the polarizing film, the diazo compound penetrates into the surface of the polarizing film, and thereby a polarizing film having excellent durability under a high-temperature and high-humidity environment as described in item a can be obtained.
C-1. method for producing polarizing film using laminate
The method for manufacturing a polarizing film according to 1 embodiment of the present invention includes: forming a polyvinyl alcohol resin layer on one side of a long thermoplastic resin base material to form a laminate; stretching and dyeing the laminate to form a polarizing film from the polyvinyl alcohol resin layer; and contacting the polarizing film with a treatment liquid containing a nitrogen-containing compound (typically a diazo compound). Preferably, the laminate is subjected to in-air stretching treatment, dyeing treatment, and stretching treatment in water in this order to form the polyvinyl alcohol resin layer into a polarizing film. The production method may further include performing a drying shrinkage treatment of shrinking the laminate in the width direction by 2% or more by heating the laminate after the stretching treatment in water while conveying the laminate in the longitudinal direction. In this case, the contact between the polarizing film and the treatment liquid may be performed after the stretching treatment in water and before the drying shrinkage treatment, or after the drying shrinkage treatment.
Production of C-1-1 laminate
As a method for producing a laminate of the thermoplastic resin substrate and the PVA-based resin layer, any appropriate method can be adopted. Preferably, the PVA-based resin layer is formed on the thermoplastic resin substrate by applying a coating solution containing a PVA-based resin to the surface of the thermoplastic resin substrate and drying the coating solution.
As a method for applying the coating liquid, any appropriate method can be adopted. Examples of the coating method include roll coating, spin coating, wire bar coating, dip coating, die coating, curtain coating, spray coating, and knife coating (comma coating). The coating and drying temperature of the coating liquid is preferably 50 ℃ or higher.
The thickness of the PVA resin layer is preferably 3 to 40 μm, and more preferably 3 to 20 μm.
Before the PVA-based resin layer is formed, the thermoplastic resin substrate may be subjected to a surface treatment (for example, corona treatment), or an easy-adhesion layer may be formed on the thermoplastic resin substrate. By performing such treatment, the adhesion between the thermoplastic resin substrate and the PVA-based resin layer can be improved.
As the thermoplastic resin substrate, any suitable thermoplastic resin film can be used. Details of the thermoplastic resin base material are described in, for example, japanese patent laid-open No. 2012-73580. The entire disclosure of this publication is incorporated herein by reference. Preferably, a polyester resin, more preferably, a polyethylene terephthalate resin can be used.
The coating liquid contains a PVA-based resin. Typically, the coating liquid is a solution obtained by dissolving a PVA-based resin in a solvent. Examples of 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, the solvent is preferably water.
As the PVA-based resin, any suitable resin can be used. For example, polyvinyl alcohol and ethylene-vinyl alcohol copolymer are listed. Polyvinyl alcohol is obtained by saponifying polyvinyl acetate. The ethylene-vinyl alcohol copolymer is obtained by saponifying an ethylene-vinyl acetate copolymer. The saponification degree of the PVA resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, and more preferably 99.0 mol% to 99.93 mol%. The degree of saponification can be determined in accordance with JIS K6726-. By using the PVA-based resin having such a saponification degree, a polarizing film having excellent durability can be obtained. If the degree of saponification is too high, gelation may occur.
The average polymerization degree of the PVA-based resin can be appropriately selected according to the purpose. The average polymerization degree is usually 1000 to 10000, preferably 1200 to 4500, and more preferably 1500 to 4300. The average degree of polymerization can be determined in accordance with JIS K6726-.
The PVA-based resin preferably contains an acetoacetyl group-modified PVA-based resin. With such a configuration, a polarizing film having a desired mechanical strength can be obtained. The amount of the acetoacetyl group-modified PVA resin is preferably 5 to 20 wt%, more preferably 8 to 12 wt% based on 100 wt% of the entire PVA resin. When the blending amount is in such a range, a polarizing film having more excellent mechanical strength can be obtained.
The concentration of the PVA-based resin in the coating liquid is preferably 3 to 20 parts by weight based on 100 parts by weight of the solvent. At such a resin concentration, a uniform coating film can be formed in close contact with the thermoplastic resin substrate.
The coating liquid preferably further contains a halide. As the halide, any suitable halide may be used. For example, iodide and sodium chloride are mentioned. Examples of the iodide include potassium iodide, sodium iodide, and lithium iodide. Among these, potassium iodide is preferable.
The amount of the halide in the coating liquid is preferably 5 to 20 parts by weight based on 100 parts by weight of the PVA-based resin, and more preferably 10 to 15 parts by weight based on 100 parts by weight of the PVA-based resin. If the amount of the halide exceeds 20 parts by weight based on 100 parts by weight of the PVA-based resin, the halide may bleed out, and the polarizing film finally obtained may be opaque.
In general, the orientation of polyvinyl alcohol molecules in a PVA-based resin is increased by stretching the PVA-based resin layer, but when the stretched PVA-based resin layer is immersed in a liquid containing water, the orientation of polyvinyl alcohol molecules may be disordered and the orientation may be reduced. In particular, when a laminate of a thermoplastic resin substrate and a PVA-based resin layer is stretched in boric acid water, the orientation degree tends to be remarkably decreased when the laminate is stretched in boric acid water at a relatively high temperature in order to stabilize the stretching of the thermoplastic resin substrate. For example, stretching of a PVA film itself in boric acid water is generally performed at 60 ℃, while stretching of a laminate of a-PET (thermoplastic resin substrate) and a PVA-based resin layer is performed at a high temperature of about 70 ℃, and in this case, the orientation of PVA at the initial stage of stretching is reduced at a stage before it rises due to underwater stretching. In contrast, by producing a laminate of a PVA-based resin layer containing a halide and a thermoplastic resin substrate and stretching the laminate at a high temperature in air (auxiliary stretching) before stretching the laminate in boric acid water, crystallization of the PVA-based resin in the PVA-based resin layer of the laminate after the auxiliary stretching can be promoted. As a result, when the PVA-based resin layer is immersed in a liquid, disorder of the orientation of the polyvinyl alcohol molecules and reduction of the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This makes it possible to improve the optical properties of the polarizing film obtained through a treatment step of immersing the laminate in a liquid, such as dyeing treatment and underwater stretching treatment.
Additives may be further compounded in the coating liquid. Examples of the additive include a plasticizer and a surfactant. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin. Examples of the surfactant include nonionic surfactants. These can be used for the purpose of further improving the uniformity, dyeability and stretchability of the PVA-based resin layer obtained.
C-1-2 auxiliary stretching treatment in air
In particular, in order to obtain high optical properties, a 2-stage stretching method combining dry stretching (auxiliary stretching) and underwater stretching (preferably boric acid underwater stretching) is selected. By introducing the auxiliary stretching as in the 2-stage stretching, the stretching can be performed while suppressing the crystallization of the thermoplastic resin substrate, the problem of the reduction in the stretchability due to the excessive crystallization of the thermoplastic resin substrate in the subsequent underwater stretching (preferably boric acid underwater stretching) can be solved, and the laminate can be stretched at a higher magnification. Further, when a PVA-based resin is coated on a thermoplastic resin substrate, in order to suppress the influence of the glass transition temperature of the thermoplastic resin substrate, the coating temperature needs to be lowered as compared with the case where the PVA-based resin is usually coated on a metal roll, and as a result, there is a problem that crystallization of the PVA-based resin is relatively lowered and sufficient optical characteristics cannot be obtained. In contrast, by introducing the auxiliary stretching, even when the PVA-based resin is applied to the thermoplastic resin, the crystallinity of the PVA-based resin can be improved, and high optical characteristics can be achieved. Further, by simultaneously improving the orientation of the PVA-based resin in advance, when the PVA-based resin is immersed in water in the subsequent dyeing step or stretching step, problems such as reduction in the orientation and dissolution of the PVA-based resin can be prevented, and high optical properties can be achieved.
The stretching method of the in-air auxiliary stretching may be fixed-end stretching (for example, a method of stretching using a tenter) or free-end stretching (for example, a method of uniaxially stretching a laminate by passing the laminate between rolls having different peripheral speeds), and the free-end stretching is actively employed for obtaining high optical characteristics. In 1 embodiment, the in-flight stretching treatment includes a heated roller stretching step of stretching the laminate by a difference in peripheral speed between heated rollers while conveying the laminate in the longitudinal direction thereof. The in-air stretching process typically includes a zone stretching process and a heated roll stretching process. The order of the area stretching step and the heating roller stretching step is not limited, and the area stretching step may be performed first or the heating roller stretching step may be performed first. The zone stretching process may be omitted. In 1 embodiment, the zone stretching step and the heating roller stretching step are performed in this order. In another embodiment, stretching is performed in a tenter stretching machine by holding the film end and extending the distance between the tenters in the flow direction (the extension of the distance between the tenters is the stretching magnification). At this time, the distance of the tenter in the width direction (the direction perpendicular to the flow direction) is set so as to be arbitrarily close to each other. The draw ratio in the flow direction can be preferably set so as to draw closer to the free end. In the case of free end stretching, the shrinkage in the width direction (1/stretching ratio)1/2To calculate.
The in-air auxiliary stretching may be performed in one stage or may be performed in multiple stages. When the stretching is performed in multiple stages, the stretching ratio is the product of the stretching ratios in the respective stages. The stretching direction in the in-air auxiliary stretching is preferably substantially the same as the stretching direction in the underwater stretching.
The stretching ratio in the air-assisted stretching is preferably 2.0 to 3.5 times. The maximum draw ratio in the combination of the in-air auxiliary drawing and the underwater drawing is preferably 5.0 times or more, more preferably 5.5 times or more, and still more preferably 6.0 times or more, with respect to the original length of the laminate. In the present specification, the "maximum stretching ratio" refers to the stretching ratio immediately before the laminate breaks, and refers to the stretching ratio at which the laminate breaks separately was observed and is lower than the value by 0.2.
The stretching temperature of the in-air auxiliary stretching may be set to any appropriate value depending on the material for forming the thermoplastic resin base material, the stretching method, and the like. The stretching temperature is preferably not less than the glass transition temperature (Tg) of the thermoplastic resin substrate, more preferably not less than the glass transition temperature (Tg) +10 ℃ of the thermoplastic resin substrate, and particularly preferably not less than Tg +15 ℃. On the other hand, the upper limit of the stretching temperature is preferably 170 ℃. By stretching at such a temperature, rapid progress of crystallization of the PVA-based resin can be suppressed, and defects caused by the crystallization (for example, inhibition of orientation of the PVA-based resin layer due to stretching) can be suppressed.
C-1-3 insolubilization treatment, dyeing treatment and crosslinking treatment
If necessary, after the in-air auxiliary stretching treatment, before the underwater stretching treatment and dyeing treatment, the insolubilization treatment is performed. The insolubilization treatment is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. The dyeing treatment is typically performed by dyeing the PVA-based resin layer with iodine. If necessary, a crosslinking treatment is performed after the dyeing treatment and before the stretching treatment in water. The crosslinking treatment is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. Details of the insolubilization treatment, the dyeing treatment and the crosslinking treatment are described in, for example, japanese patent laid-open No. 2012-73580.
C-1-4 stretching treatment in water
The underwater stretching treatment is performed by immersing the laminate in a stretching bath. By the underwater stretching treatment, the stretching can be performed at a temperature lower than the glass transition temperature (typically, about 80 ℃) of the thermoplastic resin substrate and the PVA-based resin layer, and the stretching can be performed to a high magnification while suppressing crystallization of the PVA-based resin layer. As a result, a polarizing film having excellent optical characteristics can be produced.
Any suitable method may be used for stretching the laminate. Specifically, the stretching may be performed at a fixed end or at a free end (for example, a method of passing the laminate between rollers having different peripheral speeds to perform uniaxial stretching). Free end stretching is preferably chosen. The stretching of the laminate may be performed in one stage or may be performed in multiple stages. When the stretching is performed in multiple stages, the stretching ratio (maximum stretching ratio) of the laminate described later is the product of the stretching ratios in the respective stages.
The underwater stretching is preferably performed by immersing the laminate in an aqueous boric acid solution (boric acid underwater stretching). By using the aqueous boric acid solution as the stretching bath, rigidity that resists the tension applied during stretching and water resistance that does not dissolve in water can be imparted to the PVA-based resin layer. Specifically, boric acid generates tetrahydroxyborate anions in an aqueous solution and crosslinks with the PVA-based resin through hydrogen bonds. As a result, the PVA-based resin layer can be provided with rigidity and water resistance and can be stretched well, and a polarizing film having excellent optical characteristics can be produced.
The aqueous boric acid solution is preferably obtained by dissolving boric acid and/or a borate in water as a solvent. The boric acid concentration is preferably 1 to 10 parts by weight, more preferably 2.5 to 6 parts by weight, and particularly preferably 3 to 5 parts by weight, based on 100 parts by weight of water. By setting the boric acid concentration to 1 part by weight or more, the dissolution of the PVA-based resin layer can be effectively suppressed, and a polarizing film with higher characteristics can be obtained. In addition to boric acid or a borate, an aqueous solution obtained by dissolving a boron compound such as borax, glyoxal, glutaraldehyde, or the like in a solvent may be used.
Preferably, the stretching bath (aqueous boric acid solution) is mixed with an iodide. By adding an iodide, elution of iodine adsorbed to the PVA-based resin layer can be suppressed. Specific examples of the iodide are as described above. The concentration of the iodide is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of water.
The drawing temperature (liquid temperature of the drawing bath) is preferably 40 to 85 ℃ and more preferably 60 to 75 ℃. At such a temperature, the PVA-based resin layer can be stretched to a high magnification while dissolution thereof is suppressed. Specifically, as described above, the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 60 ℃ or higher from the viewpoint of the relationship with the formation of the PVA-based resin layer. In this case, if the stretching temperature is lower than 40 ℃, there is a possibility that the thermoplastic resin substrate cannot be satisfactorily stretched even when plasticization of the thermoplastic resin substrate by water is considered. On the other hand, as the temperature of the stretching bath is higher, the solubility of the PVA-based resin layer becomes higher, and there is a fear that excellent optical characteristics cannot be obtained. The immersion time of the laminate in the stretching bath is preferably 15 seconds to 5 minutes.
The stretching ratio by underwater stretching is preferably 1.5 times or more, more preferably 3.0 times or more. The total stretch ratio of the laminate is preferably 5.0 times or more, and more preferably 5.5 times or more, based on the original length of the laminate. By achieving such a high stretching ratio, a polarizing film having very excellent optical characteristics can be produced. Such a high stretch ratio can be achieved by using an underwater stretching method (boric acid underwater stretching).
C-1-5. other treatment
It is preferable to perform the washing treatment after the stretching treatment in water and before the drying shrinkage treatment. The cleaning treatment is typically performed by immersing the PVA-based resin layer in an aqueous solution containing an iodide such as potassium iodide. The iodide concentration in the cleaning liquid is preferably 0.5 to 10 wt%, preferably 0.5 to 5 wt%, and more preferably 1 to 4 wt%. The temperature of the cleaning liquid is usually 10 to 50 ℃ and preferably 20 to 35 ℃. The immersion time is usually 1 second to 1 minute, preferably 10 seconds to 1 minute.
In the above manner, a laminate of the thermoplastic resin substrate and the polarizing film (PVA-based resin layer) can be obtained.
C-1-6 drying shrinkage treatment
The drying shrinkage treatment is performed by heating a laminate of a thermoplastic resin substrate and a polarizing film while conveying the laminate in the longitudinal direction, thereby shrinking the laminate in the width direction by 2% or more. The drying shrinkage treatment may be performed by heating the entire region by region heating, or may be performed by heating a transport roller (using a so-called hot roller) (hot roller drying method). Both are preferably used. By drying with a heating roller, the laminate can be effectively prevented from curling by heating, and a polarizing film having excellent appearance can be produced. Specifically, by drying the laminate in a state of being along the heating roller, the crystallization of the thermoplastic resin substrate can be effectively promoted to increase the crystallinity, and the crystallinity of the thermoplastic resin substrate can be favorably increased even at a low drying temperature. As a result, the thermoplastic resin substrate has increased rigidity, and is thus resistant to shrinkage of the PVA-based resin layer (polarizing film) due to drying, and curling can be suppressed. Further, since the laminate can be dried while maintaining a flat state by using the heating roller, not only curling but also wrinkles can be suppressed. In this case, the optical characteristics of the polarizing film can be improved by shrinking the laminate in the width direction by the drying shrinkage treatment. This is because the orientation of PVA and PVA/iodine complex can be effectively improved. The shrinkage in the width direction of the laminate by the drying shrinkage treatment is preferably 1% to 10%, more preferably 2% to 8%, and particularly preferably 4% to 6%.
Fig. 3 is a schematic diagram showing an example of the drying shrinkage treatment. In the drying shrinkage process, the stacked body 200 is dried while being conveyed by the conveying rollers R1 to R6 and the guide rollers G1 to G4 which are heated to a predetermined temperature. In the illustrated example, the conveying rollers R1 to R6 are disposed so as to alternately and continuously heat the surface of the PVA-based resin layer (polarizing film) and the surface of the thermoplastic resin substrate, but the conveying rollers R1 to R6 may be disposed so as to continuously heat only one surface (for example, the surface of the thermoplastic resin substrate) of the laminate 200.
The drying condition can be controlled by adjusting the heating temperature of the conveying roller (temperature of the heating roller), the number of heating rollers, the contact time with the heating roller, and the like. The temperature of the heating roller is preferably 60 to 120 ℃, more preferably 65 to 100 ℃, and particularly preferably 70 to 80 ℃. The crystallinity of the thermoplastic resin can be increased to suppress the curling well, and an optical laminate having excellent durability can be produced. The temperature of the heating roller may be measured by a contact thermometer. In the example of the figure, 6 conveying rollers are provided, but there is no particular limitation as long as there are a plurality of conveying rollers. The number of the conveying rollers is usually 2 to 40, preferably 4 to 30. The contact time (total contact time) between the laminate and the heating roller is preferably 1 to 300 seconds, more preferably 1 to 20 seconds, and still more preferably 1 to 10 seconds.
The heating roller may be disposed in a heating furnace (e.g., an oven) or may be disposed in a general production line (room temperature environment). Preferably, the heating furnace is provided with an air blowing means. By using drying by the heating roller and hot air drying in combination, a rapid temperature change between the heating rollers can be suppressed, and the shrinkage in the width direction can be easily controlled. The temperature of the hot air drying is preferably 30 to 100 ℃. The hot air drying time is preferably 1 to 300 seconds. The wind speed of the hot wind is preferably about 10m/s to 30 m/s. The wind speed is the wind speed in the heating furnace and can be measured by a digital wind speed meter of a miniature blade type.
C-1-7, contact with treatment liquid
The contact of the polarizing film with the treatment liquid containing a nitrogen-containing compound (typically, a diazo compound) may be performed at any appropriate timing. In 1 embodiment, the laminate after the underwater stretching treatment and before the drying shrinkage treatment may be brought into contact with the treatment liquid. In another embodiment, the laminate after the heat shrinking treatment may be directly subjected to contact with the treatment liquid. In these embodiments, the thermoplastic resin substrate is not peeled from the laminate and can be used as a protective layer for a polarizing film. In still another embodiment, a resin film (as a protective layer) may be bonded to the polarizing film surface of the laminate after the heat-shrinking treatment, and then the thermoplastic resin substrate may be peeled off to produce a protective layer/polarizing film laminate (polarizing plate), and the obtained polarizing plate may be brought into contact with a treatment liquid containing a nitrogen-containing compound (typically, a diazo compound).
As a method of contacting the polarizing film with the treatment liquid, any appropriate method may be used. Specifically, there are a method of immersing the polarizing film in the treatment liquid, a method of applying the treatment liquid to the polarizing film, a method of spraying the treatment liquid to the polarizing film, and the like. Preferably, a method of immersing the polarizing film in the treatment liquid or a method of applying the treatment liquid to the polarizing film can be used.
The method for applying the treatment liquid may be the method described in the section C-1-1. The impregnation may additionally be carried out by any suitable means. For example, a bath of the treatment liquid may be used instead of the cleaning bath of the cleaning treatment, or a bath of the treatment liquid may be provided separately from the cleaning bath. The washing treatment is typically performed after the stretching treatment in water and before the drying shrinkage treatment. Therefore, in the case where the bath of the treatment liquid is provided separately from the cleaning bath, the bath of the treatment liquid may be provided between the cleaning bath and the drying and shrinking treatment apparatus (that is, the contact with the treatment liquid may be performed between the cleaning treatment and the drying and shrinking treatment), or may be provided downstream of the drying and shrinking treatment apparatus (for example, the contact with the treatment liquid may be performed after the peeling of the thermoplastic resin substrate). In addition, when a bath of the treatment liquid is used instead of the cleaning bath of the cleaning treatment, the bath of the treatment liquid may be caused to function as the cleaning bath.
The treatment solution is typically a solution obtained by dissolving a diazo compound in a solvent. The diazo compound is as described in the section A. Examples of the solvent include water, isopropyl alcohol, and ethanol. These may be used alone or in combination of two or more. Among these, water is preferably used. In the case where the bath of the treatment liquid is also caused to function as the cleaning liquid as described above, the treatment liquid may further contain an iodide.
The amount of the diazo compound in the treatment liquid may be, for example, 0.01 to 3.0 wt%. When the treatment liquid is applied to the polarizing film, the amount of the treatment liquid is preferably 0.2 to 2.0 wt%, more preferably 0.3 to 1.5 wt%, and still more preferably 0.5 to 1.0 wt%. When the polarizing film is immersed in the treatment liquid, the amount is preferably 0.01 to 3.0 wt%, more preferably 0.1 to 2.0 wt%, and still more preferably 0.1 to 0.5 wt%.
The liquid temperature of the treatment liquid (when it is contacted) is, for example, 10 to 60 ℃ and preferably 20 to 40 ℃. When the polarizing film is immersed in the treatment liquid, the immersion time is, for example, 1 to 60 seconds. In the case of applying the treating liquid to the polarizing film, the amount of application is, for example, 7g/m2～15g/m2Preferably 9g/m2～11g/m2。
After contact with the polarizing film, the treatment solution is typically dried. The drying temperature is, for example, 40 to 90 ℃ and preferably 50 to 70 ℃. During the contact with the polarizing film and the drying, the diazo compound permeates into the polarizing film, whereby the polarizing film of the present invention can be obtained.
The crosslinking based on the UV treatment is preferably performed before or after drying the treatment liquid. The emission length of the UV lamp is, for example, 350nm to 450nm, preferably 380nm to 400 nm. The cumulative light quantity brought to the polarizing film is, for example, 100 to 600mJ/cm2Preferably 300 to 400mJ/cm2. By the crosslinking treatment, the polarizing film (more specifically, PVA-based resin constituting the polarizing film) is crosslinked with the diazo compound, and the water resistance of the polarizing film can be improved.
C-2. method for producing polarizing film using single PVA resin film
In item C-1, a method for producing a polarizing film using a laminate of a thermoplastic resin substrate and a PVA-based resin layer applied to the thermoplastic resin substrate was described, but the present invention is also applicable to a method for producing a polarizing film using a single PVA-based resin film. Such a manufacturing method typically includes: stretching and dyeing a PVA resin film having self-supporting properties to form a polarizing film from the polyvinyl alcohol resin film; and contacting the polarizing film with a treatment solution containing a diazo compound. More specifically, the method comprises the following steps: the PVA-based resin film in a long form is subjected to swelling, dyeing, crosslinking, and washing while being uniaxially stretched in the longitudinal direction by a roll stretcher, and finally subjected to drying treatment, and the contact with the treatment liquid can be performed by, for example, immersion in a bath of the treatment liquid which also serves as a washing bath, immersion in a bath of the treatment liquid after the washing treatment, or application of the treatment liquid after the washing treatment. The contact with the treatment liquid can be carried out in the same manner as in the item C-1 to 7.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The measurement method of each property is as follows. Unless otherwise specified, "parts" and "%" in examples and comparative examples are based on weight.
(1) Thickness of
The measurement was carried out using an interference film thickness meter (product name "MCPD-3000" available from Otsuka Denshi Co., Ltd.).
(2) Monomer transmittance, cross transmittance and degree of polarization
The polarizing films were made of a single transmittance Ts, a parallel transmittance Tp and an orthogonal transmittance Tc measured by an ultraviolet-visible spectrophotometer (LPF 200, manufactured by tsuka electronics corporation) for the polarizing plates of examples and comparative examples. These Ts, Tp and Tc are Y values measured in a 2-degree visual field (C light source) according to JIS Z8701 and corrected for visual sensitivity. From the Tp and Tc thus obtained, the degree of polarization was determined by the following equation.
Polarization degree (%) { (Tp-Tc)/(Tp + Tc) }1/2×100
Next, glass (alkali-free glass) from which the alkali component was removed was bonded to the polarizing film side of the polarizing plate via an adhesive, and the resultant was put into an oven set at a temperature of 60 ℃ and a relative humidity of 95% for 240 hours to perform an endurance test, and the polarization degree P after the endurance test was determined in the same manner as described above240。
(3) Thickness of penetrating layer of diazo compound
A cross-sectional analysis (thickness direction analysis) of the polarizing film was performed using a time-of-flight mass spectrometer (ULVAC-PHI, manufactured by inc., "trim V"). Will originate from CN-Relative to the signal intensity originating from C2H-The depth of the region with a signal intensity of 0.15 or more was determined as an infiltration layer of the diazo compound.
[ example 1]
As the thermoplastic resin base material, an amorphous ethylene terephthalate isophthalate copolymer film (thickness: 100 μm) having a long shape and a Tg of about 75 ℃ was used, and one surface of the resin base material was subjected to corona treatment.
In the following, with 9: 1 an aqueous PVA solution (coating solution) was prepared by adding 13 parts by weight of potassium iodide to 100 parts by weight of a PVA resin obtained by mixing polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl group-modified PVA (trade name "GOHSEFIMER" manufactured by Nippon synthetic chemical industries, Ltd.), and dissolving the resultant in water.
The above aqueous PVA solution was applied to the corona-treated surface of the resin substrate and dried at 60 ℃ to form a PVA-based resin layer having a thickness of 13 μm, thereby producing a laminate.
The obtained laminate was uniaxially stretched in the longitudinal direction (longitudinal direction) to 2.4 times in an oven at 130 ℃ (in-air auxiliary stretching treatment).
Next, the laminate was immersed in an insolubilization bath (an aqueous boric acid solution prepared by adding 4 parts by weight of boric acid to 100 parts by weight of water) at a liquid temperature of 40 ℃ for 30 seconds (insolubilization treatment).
Next, the polarizing film was immersed for 60 seconds (dyeing treatment) in a dyeing bath (aqueous iodine solution prepared by mixing iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water) at a liquid temperature of 30 ℃.
Next, the substrate was immersed in a crosslinking bath (an aqueous boric acid solution prepared by adding 3 parts by weight of potassium iodide to 100 parts by weight of water and 5 parts by weight of boric acid) at a liquid temperature of 40 ℃ for 30 seconds (crosslinking treatment).
Thereafter, the laminate was immersed in an aqueous boric acid solution (boric acid concentration 4 wt%, potassium iodide concentration 5 wt%) at a liquid temperature of 70 ℃ and uniaxially stretched (underwater stretching treatment) between rolls having different peripheral speeds so that the total stretching ratio was 5.5 times in the longitudinal direction (longitudinal direction).
Thereafter, the laminate was immersed in a cleaning bath (aqueous solution prepared by adding 4 parts by weight of potassium iodide to 100 parts by weight of water) at a liquid temperature of 20 ℃ (cleaning treatment).
Thereafter, the sheet was brought into contact with a heating roll made of SUS having a surface temperature of about 75 ℃ while being dried in an oven maintained at about 90 ℃ (drying shrinkage treatment). The shrinkage in the width direction of the laminate by the drying shrinkage treatment was 2%.
In this manner, a polarizing Film having a thickness of 5.0 μm (Ts: 47.0%) was formed on a resin substrate, a cycloolefin Film (product name "G-Film" manufactured by ZEON corporation) as a protective layer (protective Film) was laminated on the surface of the polarizing Film via a UV curable adhesive (thickness 1.0 μm), and thereafter the resin substrate was peeled off to obtain a polarizing plate having a structure of the protective layer/polarizing Film.
Then, the polarizing film surface of the laminate was coated at a ratio of 10g/m2The coating amount of (3) was determined by applying a treatment solution prepared by dissolving 4-phenylaminobenzenediazonium sulfate in water so that the concentration of the solution became 0.5% by weight, and drying the solution at 50 ℃ for 5 minutes.
Thereafter, 300mJ/cm was performed using a conveyor belt type UV irradiator2And exposing and performing crosslinking treatment.
In this manner, a laminate (polarizing plate) of a polarizing film having an infiltration layer of a diazo compound on the side not provided with a protective layer and a protective layer was obtained.
[ example 2]
A polarizing plate was produced in the same manner as in example 1, except that the concentration of the dyeing bath was adjusted so that the monomer transmittance (Ts) of the polarizing film before contact with the treatment liquid became 45.0%.
[ example 3]
A polarizing plate was produced in the same manner as in example 1, except that the concentration of the dyeing bath was adjusted so that the monomer transmittance (Ts) of the polarizing film before contact with the treatment liquid became 43.8%.
[ example 4]
A polarizing plate was produced in the same manner as in example 1, except that the concentration of the dyeing bath was adjusted so that the monomer transmittance (Ts) of the polarizing film before contact with the treatment liquid became 42.7%.
[ example 5]
A polarizing plate was produced in the same manner as in example 1, except that the concentration of the dyeing bath was adjusted so that the monomer transmittance (Ts) of the polarizing film before contact with the treatment liquid became 43.8%, and the concentration of 4-phenylaminobenzenediazonium sulfate in the treatment liquid was 1.0 wt%.
[ example 6]
A long roll of a PVA resin film (product name "PS 7500" manufactured by Nippon synthetic Co., Ltd.) having a thickness of 55 μm was uniaxially stretched in the longitudinal direction so that the total stretching ratio became 6.0 times by a roll stretcher, and swelling, dyeing, crosslinking and washing were performed to prepare a polarizing film having a monomer transmittance (Ts) of 43.4%. Next, the same treatment liquid as in example 1 was applied to one surface of the polarizing film in the same manner as in example 1, and drying and crosslinking treatment were performed. The cleaning treatment was performed by immersing the polarizing film in a cleaning bath (4 wt% aqueous potassium iodide solution) at a liquid temperature of 20 ℃ for 5 seconds.
Thus, a polarizing film (thickness: 23 μm) having a diazo compound-permeated layer on one surface was obtained.
[ example 7]
A laminate of a thermoplastic resin substrate/PVA-based resin layer was subjected to in-air auxiliary stretching treatment, insolubilization treatment, dyeing treatment, crosslinking treatment, and stretching treatment in water in the same manner as in example 1, except that the concentration of the dyeing bath was adjusted so that the monomer transmittance (Ts) of the polarizing film before contact with the treatment liquid became 43.7%. The laminate subjected to the underwater stretching treatment was immersed in a treatment liquid (an aqueous solution containing 0.1 wt% of 4-phenylaminobenzenediazonium sulfate and 4 wt% of potassium iodide) at a liquid temperature of 20 ℃ for 5 seconds instead of the cleaning bath, and was subjected to drying and crosslinking treatment in the same manner as in example 1.
Thereafter, the sheet was contacted with a heating roll made of SUS whose surface temperature was kept at 75 ℃ for about 2 seconds while being dried in an oven kept at 90 ℃ (drying shrinkage treatment). The shrinkage in the width direction of the laminate by the drying shrinkage treatment was 2%.
Next, a cycloolefin Film (product name "G-Film" manufactured by ZEON corporation) as a protective layer (protective Film) was laminated on the surface of the polarizing Film via a UV curable adhesive (thickness 1.0 μm), and thereafter, the resin base material was peeled off. In this manner, a laminate (polarizing plate) of a polarizing film (thickness: 5 μm) having an infiltration layer of a diazo compound on the side provided with the protective layer and the protective layer was obtained.
Comparative example 1
A laminate (polarizing plate) of a polarizing film (thickness: 5.0 μm) and a protective layer was obtained in the same manner as in example 1, except that the coating, drying and crosslinking treatment with the treatment liquid were not performed.
Comparative example 2
A polarizing plate was produced in the same manner as in example 1, except that the concentration of the dyeing bath was adjusted so that the monomer transmittance (Ts) of the polarizing film before contact with the treatment liquid became 45.0%, and coating, drying, and crosslinking treatment of the treatment liquid were not performed.
Comparative example 3
A polarizing plate was produced in the same manner as in example 1, except that the concentration of the dyeing bath was adjusted so that the monomer transmittance (Ts) of the polarizing film before contact with the treatment liquid became 43.8%, and coating, drying, and crosslinking treatment of the treatment liquid were not performed.
Comparative example 4
A polarizing plate was produced in the same manner as in example 1, except that the concentration of the dyeing bath was adjusted so that the monomer transmittance (Ts) of the polarizing film before contact with the treatment liquid became 42.8%, and that the treatment liquid was not applied, dried, and crosslinked.
Comparative example 5
A polarizing film (thickness: 23 μm) was obtained in the same manner as in example 6, except that the treatment liquid was not applied, dried, and crosslinked.
The thicknesses of Ts, Δ P and the permeation layer of the diazo compound before contacting the treatment liquid for the polarizing plates or films obtained in the above examples and comparative examples are shown in table 1.
[ Table 1]
As shown in table 1, the polarizing film of the example has a small amount of change in polarization degree under a high-temperature and high-humidity environment, and is excellent in durability. In particular, the polarizing film having a high iodine concentration and a high monomer transmittance tends to have a large amount of change in polarization degree under high temperature and high humidity, and the polarizing film of the example can effectively suppress the amount of change even when having a high monomer transmittance.
Industrial applicability
The polarizing film and the polarizing plate of the present invention are suitably used for a liquid crystal display device.
Description of the reference numerals
10 polarizing film
20 st protective layer
30 nd 2 protective layer
100 polarizing plate
Claims (13)
1. A polarizing film comprising a polyvinyl alcohol resin film containing iodine, wherein at least one surface layer portion contains a nitrogen-containing compound.
2. The polarized film of claim 1 wherein in cross-sectional analysis using time-of-flight secondary ion mass spectrometry, (CN)-) And (C)2H-) Ionic strength ratio (CN)-/C2H-) The region of 0.15 or more is present in a thickness direction of 300nm or more from the surface of the surface layer portion.
3. The polarizing film according to claim 1 or 2, wherein the nitrogen-containing compound comprises a diazo-based compound.
4. The polarizing film according to any one of claims 1 to 3, having a thickness of 8 μm or less.
5. A polarizing plate, comprising: the polarizing film according to any one of claims 1 to 4, and a protective layer disposed on at least one side of the polarizing film.
6. The method for producing a polarizing film according to any one of claims 1 to 4, which comprises:
forming a polyvinyl alcohol resin layer on one side of a long thermoplastic resin base material to form a laminate;
stretching and dyeing the laminate to form a polarizing film from the polyvinyl alcohol resin layer; and
the polarizing film is brought into contact with a treatment liquid containing a diazo compound.
7. The manufacturing method according to claim 6, comprising:
forming a polyvinyl alcohol resin layer on one side of a long thermoplastic resin base material to form a laminate;
subjecting the laminate to in-air auxiliary stretching treatment, dyeing treatment, and underwater stretching treatment in this order to form a polarizing film from the polyvinyl alcohol resin layer; and
performing a drying shrinkage treatment of shrinking by 2% or more in a width direction by heating while conveying the laminate in a longitudinal direction,
after the stretching treatment in water and before the drying shrinkage treatment or after the drying shrinkage treatment, the polarizing film is brought into contact with a treatment liquid containing a diazo compound.
8. The manufacturing method according to claim 7, wherein the drying shrinkage treatment is performed using a heated roller.
9. The manufacturing method according to claim 8, wherein the temperature of the heating roller is 60 to 120 ℃.
10. The production method according to any one of claims 6 to 9, wherein the polyvinyl alcohol resin layer contains a polyvinyl alcohol resin and contains an iodide or sodium chloride.
11. The method for producing a polarizing film according to any one of claims 1 to 3, comprising:
stretching and dyeing a polyvinyl alcohol resin film to form a polarizing film; and
the polarizing film is brought into contact with a treatment liquid containing a diazo compound.
12. The production method according to any one of claims 6 to 11, wherein contacting the polarizing film with the treatment liquid comprises applying a treatment liquid containing a diazo compound at a concentration of 0.2 wt% or more to a surface of the polarizing film.
13. The production method according to any one of claims 6 to 11, wherein contacting the polarizing film with the treatment liquid comprises immersing the polarizing film in a treatment liquid containing a diazo compound at a concentration of 0.01 wt% or more.
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| PCT/JP2020/012050 WO2020203312A1 (en) | 2019-03-29 | 2020-03-18 | Polarization film, polarization plate, and production method for said polarization film |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005171231A (en) * | 2003-11-17 | 2005-06-30 | Sumitomo Chemical Co Ltd | Polyazo compound or its salt and polarizing membrane containing the same |
| CN101056918A (en) * | 2004-11-02 | 2007-10-17 | 日本合成化学工业株式会社 | Polyvinyl alcohol film and method for producing the same |
| WO2015046249A1 (en) * | 2013-09-27 | 2015-04-02 | 日本化薬株式会社 | Dye-based polarizing element or dye-based polarizing plate |
| CN106716194A (en) * | 2014-09-29 | 2017-05-24 | 株式会社Lg化学 | Method for manufacturing polariser, and polariser and polarising plate manufactured using same |
| CN107884847A (en) * | 2016-09-29 | 2018-04-06 | 日本化药株式会社 | Polarizer, polarizer and liquid crystal display device |
| CN108699346A (en) * | 2016-02-26 | 2018-10-23 | 日本化药株式会社 | Azo-compound or its salt and polarizing coating containing azo-compound or its salt |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001343521A (en) | 2000-05-31 | 2001-12-14 | Sumitomo Chem Co Ltd | Polarizing plate and method for manufacturing the same |
| US6638679B2 (en) * | 2001-07-12 | 2003-10-28 | Kodak Polychrome Graphics, Llc | Photosensitive compositions having mixtures of alkoxy and non-alkoxy diazonium salt containing compounds |
| US6821583B2 (en) * | 2002-07-03 | 2004-11-23 | Kodak Polychrome Graphics Llc | Imageable element for single fluid ink |
| JP4744869B2 (en) * | 2003-12-24 | 2011-08-10 | 日本合成化学工業株式会社 | Polyvinyl alcohol film for polarizing film and use thereof |
| JP2008020908A (en) * | 2006-06-15 | 2008-01-31 | Mitsubishi Chemicals Corp | Pigment for anisotropic pigment film |
| JP5823545B2 (en) * | 2013-02-27 | 2015-11-25 | 富士フイルム株式会社 | Polarizer, polarizing plate using the same, liquid crystal display device, and manufacturing method of polarizing plate |
| US10534119B2 (en) * | 2015-09-22 | 2020-01-14 | Lg Chem, Ltd. | Polarizer protective film, polarizing plate and method for preparing polarizing plate |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005171231A (en) * | 2003-11-17 | 2005-06-30 | Sumitomo Chemical Co Ltd | Polyazo compound or its salt and polarizing membrane containing the same |
| CN101056918A (en) * | 2004-11-02 | 2007-10-17 | 日本合成化学工业株式会社 | Polyvinyl alcohol film and method for producing the same |
| WO2015046249A1 (en) * | 2013-09-27 | 2015-04-02 | 日本化薬株式会社 | Dye-based polarizing element or dye-based polarizing plate |
| CN106716194A (en) * | 2014-09-29 | 2017-05-24 | 株式会社Lg化学 | Method for manufacturing polariser, and polariser and polarising plate manufactured using same |
| CN108699346A (en) * | 2016-02-26 | 2018-10-23 | 日本化药株式会社 | Azo-compound or its salt and polarizing coating containing azo-compound or its salt |
| CN107884847A (en) * | 2016-09-29 | 2018-04-06 | 日本化药株式会社 | Polarizer, polarizer and liquid crystal display device |
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