JPH09184915A - Production of polarizing film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to produce a polarizing film having excellent optical performance and excellent dimensional stability against heat, etc. by treating a polyvinyl alcohol(PVA) film under a specified condition by using an aq. soln. contg. a boron compd. SOLUTION: PVA film is treated under either the conditions under which the treating temp. is specified to >=55 deg.C and the treating time to 3.5 to 6min, or the treating temp. is specified to 45 to <55 deg.C and the treating time to 6 to 30min by using the aq. soln. contg. the boron compd. The boron is incorporated at 3.5 to 5.1wt.% into the PVA film particularly in the stage for treating the film with the aq. soln. contg. the boron compd., by which a remarkable effect is exhibited. Namely, the polarizing plate which has not only the excellent optical performance, etc., but further a high contrast is obtd. and, therefore, an effect of improving visibility and making the eyes less fatiguing is obtd.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polarizing film having excellent optical performance and dimensional stability under heat resistance.

[0002]

2. Description of the Related Art In recent years, liquid crystal display devices have been used in desktop electronic calculators, electronic timepieces, word processors, instruments for automobiles and machinery, and the demand for polarizing plates has been increasing with these devices. Generally, a polarizing plate in which a protective film is formed via an adhesive layer on both sides or one side of a polarizing film having a polarizing ability is widely used, and a currently known representative polyvinyl alcohol (hereinafter, referred to as PVA) is used. As abbreviated) -based polarizing films, there are a PVA-based film obtained by dyeing iodine and a dichroic dye, and these are prepared by forming an aqueous solution of PVA, uniaxially stretching the film and dyeing it. After dyeing, uniaxially stretched and then subjected to a durability treatment with a boron compound, a protective film is further provided to protect moisture resistance, which is a drawback of the PVA-based polarizing film, and as the protective film, Cellulose acetate-based films are widely used as surface protective films because of their excellent optical transparency and non-orientation.

As a production method for improving the moisture resistance and heat and humidity resistance of the PVA-based polarizing film, for example, Japanese Patent Application Laid-Open No. 62-223704 discloses a method in which a PVA-based polarizing film is durable with an aqueous boric acid solution. 10th treatment bath
˜55 ° C., the second treatment bath is in the temperature range of 55 to 80 ° C., and in JP-A-62-226104, an inorganic salt is added to an aqueous boric acid solution which is a aging treatment liquid. Further, in JP-A-7-198939, boron atoms are added in an amount of 4.5 to 7.0 based on the total weight of the PVA-based film.
It has been proposed that two or more steps in which the content of the compound is contained by weight% be performed, and that each step be immersed in a treatment liquid having a different boron compound concentration.

[0004]

However, in the technique disclosed in the above publication, although the polarization performance and the durability are improved, the dimensional stability of the obtained polarizing film under heat is not considered at all. As a result of a detailed study by the present inventors, the technology disclosed in the publication is still unsatisfactory, and the required performance is becoming higher and higher with the recent advancement of the technology, and further high optical characteristics are obtained. Development of polarizing films and polarizing plates having excellent dimensional stability is desired. Further, in the polarizing plate obtained by the above technique, blue leak occurs in polarizing plate crossed Nicols, parallel transmittance decreases when blue leak is suppressed, and wavelengths of 400 to 5 are decreased.
It was found that the parallel transmittance / orthogonal transmittance value (contrast) is hard to increase in the 00 nm region, and the contrast decreases in the wavelength range of 550 to 780 nm. The present invention has an object to provide a method for manufacturing a polarizing film, which solves the above-mentioned problems under such a background.

[0005]

However, as a result of earnest studies by the present inventors to solve such problems, PVA
By treating the base film with an aqueous solution containing a boron compound under the following condition (1) or (2), a polarizing film having a high contrast with extremely excellent optical performance and dimensional stability is obtained. Find what you get,
The present invention has been completed. (1) The treatment temperature is 55 ° C. or higher and the treatment time is 3.5 minutes or longer and 6 minutes or shorter. (2) The processing temperature is 45 to less than 55 ° C., and the processing time is 6
Not less than 30 minutes and not more than 30 minutes. In particular, in the present invention, in the step of treating with an aqueous solution containing a boron compound, the effect of the present invention is more remarkably achieved by setting the boron content contained in the PVA-based film to 3.5 to 5.1% by weight. .

The contrast is the ratio ((A) / (B)) of the parallel transmittance (A) and the orthogonal transmittance (B) as described above, and the parallel transmittance (A) is the difference between two polarized light beams. Transmittance (%) when plates are stacked so that their orientation directions are the same
And the orthogonal transmittance (B) means the transmittance (%) when two polarizing plates are overlapped so that their orientation directions are vertical.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described specifically. The polarizing film of the present invention is a uniaxially stretched film of a PVA-based film, and PVA is generally produced by saponifying polyvinyl acetate obtained by polymerizing vinyl acetate, but the present invention is not necessarily limited to this. , A small amount of unsaturated carboxylic acid (including salts, esters, amides, nitriles, etc.), olefins, vinyl ethers, unsaturated sulfonates and the like, and may contain a component copolymerizable with vinyl acetate. The average degree of saponification in PVA is 85-
100 mol%, preferably 98 to 100 mol% is practical. As the average degree of polymerization of the PVA of the present invention, any one can be used, but it is 1500 to 10000, preferably 2600 to 7000, and more preferably 3000.
~ 5000 is advantageous.

As the method for producing the polarizing film, first, a stock solution of PVA dissolved in water or an organic solvent is cast to form a film, and the film is stretched and immersed in an aqueous solution of an iodine compound or a dichroic dye. It is dyed, simultaneously stretched and dyed, or dyed with an iodine compound or a dichroic dye and stretched, and then treated with a boron compound. Further, after dyeing, the film can be stretched in a solution of a boron compound, and can be appropriately selected and used.

Solvents used in preparing the stock solution include, for example, water and dimethyl sulfoxide (DM
Polyhydric alcohols such as SO), N-methylpyrrolidone, glycerin, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and trimethylolpropane; amines such as ethylenediamine and diethylenetriamine; and mixtures thereof.

In the above organic solvent, a small amount, for example, 5 to 30
Water may be contained by weight. PV in stock solution
The concentration of A is practically 5 to 20% by weight. The PVA film stock solution obtained using the solvent is formed into a film by any method such as a casting method and an extrusion method. As a film forming method, a dry / wet film forming method is used, that is, the solution is temporarily discharged from a die slit into the air or into an inert atmosphere such as nitrogen, helium, or argon, and then introduced into a coagulation bath. A stretched film is formed. Alternatively, the film-forming solution discharged from the spinneret may be introduced into a coagulation bath after the solvent is partially dried on a roller or a belt conveyor or the like.

The solvent used for the coagulation bath is miscible with the PVA solvent, for example, alcohols such as methanol, ethanol, propanol and butanol.
Acetone, benzene, toluene and the like can be mentioned. PVA
As a method of obtaining a system film, a so-called gel film forming method in which a solution of PVA is introduced into a coagulation bath to form a film can be implemented.

The film thickness of the raw film is 30 to 1
A thickness of 00 μm, preferably 50 to 90 μm is required. 3
If the thickness is less than 0 μm, the film cannot be stretched. The PVA unstretched film obtained as described above is then stretched, dyed and treated with a boron compound. Stretching and dyeing The boron compound treatment may be carried out separately or simultaneously, but in the present invention, it is desirable to carry out uniaxial stretching during at least one of the dyeing process and the boron compound treatment process.

It is desirable that the uniaxial stretching is 3.5 to 10 times, preferably 4.5 to 7 and particularly preferably 5 to 7 times. At this time, slight stretching (extending to the extent of preventing shrinkage in the width direction or more) may be performed in the direction perpendicular to the above. The temperature condition during stretching is 40
It is desirable to select from ~ 130 ° C. Further, the stretching ratio may be finally set in the above range, and the stretching operation may be performed not only in one stage but also in any range of the manufacturing process.

The dyeing of the film, that is, the adsorption of the polarizing element is performed by bringing the liquid containing the polarizing element into contact with the film. Usually, an aqueous solution of iodine-potassium iodide is used, the iodine concentration is 0.1 to 2 g / l, the potassium iodide concentration is 10 to 50 g / l, and the iodine / potassium iodide weight ratio is 20 to 100. Appropriate. The dyeing time is practically about 30 to 500 seconds. The temperature of the treatment bath is preferably 30 to 80C. A small amount of an organic solvent compatible with water other than the water solvent may be contained. As the contact means, any means such as dipping, coating and spraying can be applied.

The dyed film is then treated with a boron compound, and boric acid and borax are practical as the boron compound. In the present invention, in such a boron compound treatment step, it is necessary to control the treatment temperature and the treatment time as described above. Specifically, under either condition (1) or (2) below, (1) treatment temperature Is 55 ° C. or higher, and the treatment time is 3.5 minutes or longer and 6 minutes or shorter. (2) The processing temperature is 45 to less than 55 ° C., and the processing time is 6
Not less than 30 minutes and not more than 30 minutes. Treatment is the most important feature, and a polarizing film having a high degree of polarization and a high transmittance can be obtained by this method.

Preferably, (1) the treatment temperature is 55 to 65 ° C., and the treatment time is 4 minutes to 5 minutes. (2) The processing temperature is 48 to less than 55 ° C., and the processing time is 8
Minutes or more and 20 minutes or less. It is desired. In addition to the above conditions, for example, the processing temperature is 45
If the temperature is less than ℃, the tension at the time of stretching becomes high and uniform stretching becomes difficult. If the processing temperature is 55 ° C or more and the processing time is less than 3.5 minutes or exceeds 6 minutes, the optical performance of the polarizing film is deteriorated and Optical unevenness occurs and the processing temperature is 45 to 55
If the treatment time is less than 6 ° C. or more than 30 minutes at less than 0 ° C., the optical performance of the polarizing film similarly deteriorates, in-plane optical unevenness occurs, and the quality deteriorates, which is not preferable.

The boron compound is used in the form of an aqueous solution or a water-organic solvent mixture at a concentration of about 0.5 to 2 mol / l, and it is practically desirable to allow a small amount of potassium iodide to coexist in the solution. The treatment method is preferably an immersion method, but of course, a coating method and a spraying method can also be performed. By the treatment step of the boron compound, the content of boron contained in the polarizing film is 3.1.
To 5.1% by weight, preferably 4.0 to 4.7% by weight, particularly preferably 4.2 to 4.6% by weight, the effect of optical properties is remarkably exhibited, and at the time of heat resistance. It is possible to obtain a polarizing film with reduced dimensional shrinkage and excellent dimensional stability. When the boron content is less than 3.5% by weight, the dimensional shrinkage of the polarizing film is small but the optical performance is deteriorated,
If it exceeds 5.1% by weight, the dimensional shrinkage at the time of heat resistance becomes large and the effect of the present invention is not exhibited. Further, in the present invention, it is preferable to treat the PVA-based film (polarizing film) dyed as described above with an aqueous solution containing a boron compound,
It is also possible to perform the treatment with the boron compound before or at the same time as dyeing to obtain a polarizing film. If necessary, a stretching operation may be performed during the treatment with the boron compound.

Then, if necessary, washing treatment and drying treatment are carried out to obtain the polarizing film of the present invention. The washing process is performed at 5 to 30 ° C. for 2 minutes or less, and the drying process is 30 to 30 ° C.
It is performed at 80 ° C. for 30 to 500 seconds. After the drying treatment, the obtained PVA-based polarizing film of the present invention is laminated with a cellulose acetate-based protective film having excellent optical transparency and mechanical strength on both sides or one side thereof.

Examples of the cellulose acetate-based protective film include cellulose acetate-based films, acrylic films, polyester-based films, polyolefin-based films, polycarbonate-based films, polyether ether keto-based films, polysulfone-based films, and the like.
Preferably, a cellulose acetate film such as a cellulose diacetate film or a cellulose triacetate film is used.If necessary, a salicylic acid ester compound, a benzophenol compound, a benzotriazole compound, a cyanoacrylate compound may be added to the resin film. An ultraviolet absorber such as a compound or a nickel complex salt compound can be blended. Further, it is more effective if the surface of the protective film is saponified with an alkali, or subjected to plasma treatment, glow discharge treatment, corona discharge treatment, high frequency treatment, electron beam treatment, or the like. When bonding the PVA-based polarizing film and the protective film, an adhesive such as a PVA-based, urethane-based, or acrylic-based adhesive is used.

The polarizing film thus obtained exhibits excellent optical performance and very excellent dimensional stability during heat treatment because it comprises a manufacturing method in which the above-mentioned specific boron compound treatment step is carried out. Since it is a polarizing plate with higher contrast, it is useful for liquid crystal display devices, vehicle applications, various industrial instruments, household appliances, etc., and has good visibility and eyestrain etc. It also has the effect of.

Furthermore, a transparent pressure-sensitive adhesive layer can be provided on the above-mentioned polarizing plate (a polarizing film of the present invention to which a protective film is attached), if necessary, by a generally known method. As the pressure-sensitive adhesive layer, acrylates such as butyl acrylate, ethyl acrylate, methyl acrylate, 2-ethylhexyl acrylate and the like and α-monoolefin carboxylic acids such as acrylic acid, maleic acid, itaconic acid, methacrylic acid, Copolymers with crotonic acid and the like (including those to which vinyl monomers such as acrylonitrile, vinyl acetate and styrene are added) are mainly used.
It is particularly preferable because it does not hinder the polarizing characteristics of the polarizing film. However, the present invention is not limited to this, and any transparent adhesive can be used. For example, a polyvinyl ether-based or rubber-based adhesive may be used.

Further, it is possible to further provide various functional layers on one surface of the polarizing plate (the surface on which the above-mentioned adhesive is not provided). Examples of the functional layer include an antiglare layer, a hard coat layer, an antireflection layer, and the like. Examples include a half-reflection layer, a reflection layer, a light-storing layer, and an electroluminescence layer. Further, it is possible to combine two or more kinds, for example, an anti-glare layer and an anti-reflection layer, a light-storing layer and a reflection layer, a light-storing layer and a half. Examples include a combination of a reflection layer, a light storage layer and a light diffusion layer, a light storage layer and an electroluminescence layer, and a half reflection layer and an electroluminescence layer. However, it is not limited to these.

The anti-glare layer is for diffusing a reflected image of a fluorescent lamp or the like on the surface of the polarizing plate to make it easy to see the display, and for preventing the adhesion of fingerprints or the like. Melamine-based resins, urethane-based resins, acrylic-based resins, alkyd-based resins, silicone-based resins, etc. containing inorganic fillers such as silica beads of 1 to 20 μm and organic fillers such as acrylic, styrene, divinylbenzene, melamine and benzoguanamine Known thermosetting resin or polyfunctional acrylic energy ray curable resin such as ultraviolet ray or electron beam is used, and a known coating method such as bar coating, roll coating, gravure coating or air knife coating on the protective layer surface. Is applied by. The thickness of the antiglare layer is 1 to 20 μm.
It is a degree.

The hard coat layer has a surface hardness of H (pencil hardness) or more to impart scratch resistance, and specifically includes a melamine resin, a urethane resin, an acrylic resin,
A thermosetting resin such as an alkyd-based resin or a silicone-based resin or a polyfunctional acrylic resin as a main component, an energy ray-curable resin such as an ultraviolet ray or an electron beam, or a metal oxide such as SiO ₂ is used. Formed on the surface. As a method for forming the layer, known coating methods such as bar coating, roll coating, gravure coating, and air knife coating are preferably used in the case of a resin, and a vacuum evaporation method is preferably used in the case of a metal oxide. . The thickness of the hard coat layer is 1 to 20
It is about μ.

The anti-reflection layer is for suppressing the reflection of external light on the surface of the polarizing plate and making the display easier to see, and specifically, it is a fluorine resin, SiO ₂ , MgF ₂ , Zr.
Metal oxides such as O ₂ , AlO ₃ and TiO ₂ are used,
It is formed on the surface of the protective film layer. As a method for forming the layer, in the case of resin, a known coating method such as bar coating, roll coating, gravure coating, air knife coating,
In the case of a metal oxide, a vacuum deposition method is suitably adopted, and two or more metal oxides are often laminated, and the thickness of the antireflection layer is about 0.05 to 1 μm. It is also effective to use a combination of an anti-reflection layer and an anti-glare layer.

The half reflection layer is a layer for utilizing external light reflection in the daytime and utilizing transmitted light from the backlight at night for displaying a display to achieve low power consumption. Formed on the outside. Specifically, scaly mica, titanium dioxide-coated mica, plate-shaped fish scale foil, hexagonal plate-shaped basic lead carbonate, fine mica or pearl pigment such as bismuth acid chloride, fine glass beads, glass products such as ground glass particles, It has optical transparency of (meth) acrylic resin, acetate, polycarbonate, polyester, polyurethane, etc. by using an adhesive containing transparent and / or semi-transparent particles such as plastic chips, plastic crushed particles and other plastic products. The synthetic resin layer may be attached to a polarizing plate, or the film in which the transparent and / or semitransparent particles are coated on the synthetic resin layer may be attached to the polarizing plate via an adhesive. , But is not limited to this. The polarizing plate with a half-reflection layer is practically used as a lower polarizing plate of a liquid crystal panel, and a protective layer without a half-reflection layer is attached to the liquid crystal panel so that the half-reflection layer is a lower layer. You.

The reflection layer is used to display a display by utilizing external light reflection in the daytime and omit the backlight, and specifically, a cellulose acetate film such as a cellulose triacetate film or polyethylene terephthalate. A metal having a high reflectance such as aluminum or silver is vapor-deposited on a base material such as, and is bonded to a polarizing plate (one protective layer) via an adhesive. The polarizing plate with a reflective layer is practically used as a lower polarizer of a liquid crystal panel, and a protective layer having no reflective layer is bonded to the liquid crystal panel so that the reflective layer is a lower layer.

The luminous layer is for accumulating outside light in the daytime so that a display can be displayed without a backlight at night. Specifically, zinc sulfide or calcium sulfide is used as a matrix, Copper is added as an activator to this, and a green phosphor that is mixed with a flux and fired is often used, or the phosphorescent coating contains an element that emits α-rays such as radium and strontium, and β-rays. It is used as a light-emitting paint that emits a small amount of light by itself. The light-storing layer is coated on one side (one protective layer) of the polarizing plate with a binder resin such as an acrylic resin, and the polarizing plate with the light-storing layer is practically used as a lower polarizing plate of a liquid crystal panel. That is, the protective layer having no light storage layer is bonded to the liquid crystal panel. It is also effective to provide a reflective layer below the luminous layer or to provide a half-reflection layer between the luminous layer and the polarizing plate.

The electroluminescent layer is intended to reduce the weight and thickness of the backlight instead of the conventional backlight, and is practically provided on the lower layer of the lower polarizing plate of the liquid crystal panel. As an electroluminescent material,
There are an inorganic material and an organic material, and the inorganic material includes phosphor particles such as zinc sulfide, and the organic material is tris (8-quinolinolato) aluminum complex.
Bis (benzoquinolinolato) beryllium complex and the like can be mentioned. In actual use, an ITO electrode is provided on one side (the polarizing plate side) of the electroluminescent layer, and a dielectric layer and a back electrode are provided on the other side, and current is passed through the ITO electrode and the back electrode to emit light. It is also effective to provide a light storage layer or a half reflection layer between the electroluminescence layer and the polarizing plate.

The polarizing film of the present invention includes PVA, polycarbonate, polyester, polyarylate, polyimide, polyolefin, polystyrene, polysulfone, polyether sulfone, polyvinylidene fluoride / polymethylmethacrylate, liquid crystal polymer, triacetyl cellulose. It is also effective as an elliptically polarizing plate by laminating it with a retardation film such as a resin, a cyclic polyolefin, a saponified ethylene-vinyl acetate copolymer, or polyvinyl chloride.

[0031]

The present invention will be specifically described below with reference to examples. In the examples, “%” is based on weight unless otherwise specified. The degree of polarization in the present invention is represented by the following equation. [(H ₁₁ −H ₁ ) / (H ₁₁ + H ₁ )] ^1/2 × 100 (%) where H ₁₁ is such that the orientation directions of the polarizing films are the same when two polarizing film samples are superposed. so as to superimpose the spectrophotometer was measured using a state were transmittance (%), H ₁ at the time of superposition of the two samples, stacked so that the direction in which the orientation direction of the polarizing film are orthogonal to each other Transmittance measured in the combined state (%)
It is.

Example 1 PVA having an average degree of polymerization of 3800 and a degree of saponification of 99.5 mol%
Was dissolved in water to obtain a 5.0% solution. The solution was cast on a polyethylene terephthalate film and dried to obtain a raw film (80 μm). The film was attached to a chuck, iodine 0.2 g / l, potassium iodide 60 g / l
Immersion in an aqueous solution consisting of 30 seconds at 240 ° C., then for 15 minutes in an aqueous solution (temperature 53 ° C.) consisting of boric acid 50 g / l and potassium iodide 40 g / l, and at the same time 5.5 times After uniaxially stretching, it was dried at room temperature for 24 hours to obtain the polarizing film of the present invention (boron content was 4.7%). Next, a cellulose triacetate film was attached to both surfaces of the obtained polarizing film with a PVA adhesive (4% aqueous solution) to obtain a polarizing plate, and the polarization degree and transmittance of the polarizing plate were measured by a high-speed multiwavelength birefringence measuring device. (Otsuka Electronics Co., Ltd .: RETS
-2000). In addition, the polarizing plate
After standing for 500 hours, the dimensional shrinkage was measured. The dimensional shrinkage is 180 mm (MD direction) × 25
The sample was sampled in a size of mm (TD direction), the length in the MD direction (uniaxial stretching direction) before and after the heat resistance test was measured, and calculated from the following formula. Dimensional shrinkage ratio = (length in MD direction before heat resistance test-length in MD direction after heat resistance test) x 100 / length in MD direction before heat resistance test

Example 2 A polarizing film (boron content: 4.7%) was obtained in the same manner as in Example 1 except that the dipping time in the boric acid treatment was changed to 18 minutes, and the same procedure as in Example 1 was carried out. A cellulose triacetate film was attached to obtain a polarizing plate. The polarization degree, transmittance, and dimensional shrinkage of the polarizing plate were measured in the same manner as in Example 1.

Example 3 A polarizing film was obtained in the same manner as in Example 1 except that the boric acid treatment temperature was 47 ° C. and the boric acid treatment immersion time was 25 minutes (boron content was 4.7%). Further, Example 1
A cellulose triacetate film was attached in the same manner as in 1. to obtain a polarizing plate. The polarization degree, the transmittance, and the dimensional shrinkage of the polarizing plate were measured in Example 1
It measured similarly to.

Example 4 A polarizing film was obtained in the same manner as in Example 1 except that the concentration of boric acid was 35 g / l (boron content was 4.
2%), and a cellulose triacetate film was further laminated in the same manner as in Example 1 to obtain a polarizing plate. The degree of polarization of the polarizing plate, the transmittance,
The dimensional shrinkage was measured as in Example 1.

Example 5 A polarizing film was obtained in the same manner as in Example 1 except that the boric acid concentration was 60 g / l (the boron content was 5.
1%), and a cellulose triacetate film was further laminated in the same manner as in Example 1 to obtain a polarizing plate. The degree of polarization of the polarizing plate, the transmittance,
The dimensional shrinkage was measured as in Example 1.

Example 6 A polarizing film (boron content: 4.7%) was obtained in the same manner as in Example 1 except that the uniaxial stretching ratio of the PVA film was 4.5 times. Similarly, a cellulose triacetate film was attached to obtain a polarizing plate. The polarization degree, transmittance, and dimensional shrinkage of the polarizing plate were measured in the same manner as in Example 1.

Example 7 A polarizing film was obtained in the same manner as in Example 1 except that the boric acid treatment temperature was 56 ° C. and the boric acid treatment dipping time was 6 minutes (boron content was 4.7%). Further, a cellulose triacetate film was attached in the same manner as in Example 1 to obtain a polarizing plate. The polarization degree, the transmittance, and the dimensional shrinkage of the polarizing plate were measured in Example 1
It measured similarly to.

Example 8 A polarizing film was obtained in the same manner as in Example 1 except that the boric acid treatment temperature was 58 ° C. and the boric acid treatment immersion time was 4 minutes (boron content was 4.7%). Further, a cellulose triacetate film was attached in the same manner as in Example 1 to obtain a polarizing plate. The polarization degree, the transmittance, and the dimensional shrinkage of the polarizing plate were measured in Example 1
It measured similarly to.

Example 9 In Example 1, the average degree of polymerization was 2600 and the degree of saponification was 9
A polarizing film was obtained in the same manner except that 9.5% PVA was used (boron content was 4.7%), and a cellulose triacetate film was laminated in the same manner as in Example 1 to obtain a polarizing plate. . The polarization degree, the transmittance, and the dimensional shrinkage of the polarizing plate were measured in Example 1
It measured similarly to.

Example 10 In Example 1, the average degree of polymerization was 1700 and the degree of saponification was 9
A polarizing film was obtained in the same manner except that 9.5% PVA was used (boron content was 4.5%), and a cellulose triacetate film was laminated in the same manner as in Example 1 to obtain a polarizing plate. . The polarization degree, the transmittance, and the dimensional shrinkage of the polarizing plate were measured in Example 1
It measured similarly to.

Example 11 A polarizing film was obtained in the same manner as in Example 9 except that the boric acid treatment temperature was 50 ° C. and the boric acid treatment dipping time was 10 minutes (boron content: 4.6%). Further, Example 1
A cellulose triacetate film was attached in the same manner as in 1. to obtain a polarizing plate. The polarization degree, the transmittance, and the dimensional shrinkage of the polarizing plate were measured in Example 1
It measured similarly to.

Comparative Example 1 A polarizing film was obtained in the same manner as in Example 1 except that the dipping time in the boric acid treatment was 4 minutes (boron content: 4.6%). A cellulose triacetate film was attached to obtain a polarizing plate. The polarization degree, transmittance, and dimensional shrinkage of the polarizing plate were measured in the same manner as in Example 1.

Comparative Example 2 A polarizing film was obtained in the same manner as in Example 1 except that the dipping time for the boric acid treatment was 40 minutes (boron content was 4.7%). A cellulose triacetate film was attached to obtain a polarizing plate. The polarization degree, transmittance, and dimensional shrinkage of the polarizing plate were measured in the same manner as in Example 1.

Comparative Example 3 A polarizing film was obtained in the same manner as in Example 1 except that the boric acid treatment temperature was 58 ° C. (the boron content was 4.
3%), and a cellulose triacetate film was further laminated in the same manner as in Example 1 to obtain a polarizing plate. The degree of polarization of the polarizing plate, the transmittance,
The dimensional shrinkage was measured as in Example 1.

Comparative Example 4 Example 4 was repeated except that the boric acid treatment temperature was 35 ° C. As a result, the film was cut when it was stretched 5 times.

Comparative Example 5 A polarizing film (boron content: 4.5%) was obtained in the same manner as in Example 7, except that the dipping time in the boric acid treatment was changed to 2 minutes, and the same procedure as in Example 1 was performed. A cellulose triacetate film was attached to obtain a polarizing plate. The polarization degree, transmittance, and dimensional shrinkage of the polarizing plate were measured in the same manner as in Example 1.

Comparative Example 6 A polarizing film (boron content of 4.7%) was obtained in the same manner as in Example 7 except that the dipping time of the boric acid treatment was changed to 15 minutes. A cellulose triacetate film was attached to obtain a polarizing plate. The polarization degree, transmittance, and dimensional shrinkage of the polarizing plate were measured in the same manner as in Example 1. Table 1 shows the measurement results of the examples and the comparative examples.

[0049]

[Table 1] Polarization degree Transmittance Dimensional shrinkage rate Boron content (%) (%) (%) (%) Example 1 99.9 43.5 1.1 4.7 〃 2 99.9 43.7 1 0.0 4.7 〃 3 99.7 43.5 1.4 4.7 〃 4 99.9 43.5 1.0 4.2 4.2 〃 5 99.9 43.5 1.4 5.1 5.1 〃 6 99 4.8 43.5 1.0 4.7 〃 7 99.9 43.5 1.0 4.7 〃 8 99.9 43.5 1.0 4.7 〃 9 99.8 43.5 1.0 4.7 〃 10 99.7 43.5 1.0 4.5 〃 11 99.9 43.0 1.0 4.6 Comparative Example 1 99.2 43.5 1.5 4.6 4.6 〃 2 99. 0 42.7 1.4 4.7 〃 3 98.7 44.5 1.2 4.3 〃 4 * * * * 〃 5 99.4 43.5 1.2 4.7 4.7 〃 6 98.5 44 0.0 1.0 4.7 Note) *: Measurement is impossible because the film has been cut.

[0050]

EFFECT OF THE INVENTION The polarizing film of the present invention, which comprises a manufacturing method in which the above-mentioned specific boron compound treatment step is performed, exhibits excellent optical performance and very excellent dimensional stability under heat. Since it is a polarizing plate with higher contrast, it is useful for liquid crystal display devices, vehicle applications, various industrial instruments, household appliances, etc., and has good visibility and eyestrain etc. It also has the effect of.

Claims (5)

[Claims] 1. A method for producing a polarizing film, which comprises treating a polyvinyl alcohol-based film with an aqueous solution containing a boron compound under the following conditions (1) or (2). (1) The treatment temperature is 55 ° C. or higher and the treatment time is 3.5 minutes or longer and 6 minutes or shorter. (2) The processing temperature is 45 to less than 55 ° C., and the processing time is 6
Not less than 30 minutes and not more than 30 minutes. 2. The method for producing a polarizing film according to claim 1, wherein the polyvinyl alcohol-based film is a polyvinyl alcohol-based film provided with polarization performance by adsorption orientation of an iodine compound or a dichroic dye. 3. The boron content in the polyvinyl alcohol-based film in the step of treating with an aqueous solution containing a boron compound is 3.5 to 5.1% by weight. Manufacturing method of polarizing film. 4. A polyvinyl alcohol-based film is used as 4.
Stretching 5 to 7.0 times.
Or the manufacturing method of the polarizing film of 3 description. 5. The method for producing a polarizing film according to claim 1, wherein the polyvinyl alcohol film is made of a polyvinyl alcohol resin having a degree of polymerization of 2600 or more.