JP2005227650A - Manufacturing method of polarizing film, polarizing plate and optical laminate - Google Patents

Abstract

The present invention provides a method for producing a polarizing film with less scratches and wrinkles and no folding.
In a method for producing a polarizing film by treating a PVA-based film, a widening roll is used in the treatment liquid, and the maximum widening amount β of the widening roll obtained by Formula (1) is obtained by Formula (2). The widening roll is disposed at a position exceeding the expansion amount γ in the width direction of the film in the widening roll, or a widening roll having a shape exceeding the expansion amount is used.
β = B ₁ × α × r / R (1)
γ = 0.2055 × B ₁ × {exp (−0.0273 × θ ₁ ) −exp (−0.0273 × θ)} (2)
(Where B ₁ is the width of the film that contacts the roll, α is the contact angle, r is the radius of the roll, R is the radius of curvature of the roll, θ is the travel time in the liquid until the film leaves the roll, and θ ₁ is (It represents the running time in the liquid until the film contacts the roll.)
[Selection figure] None

Description

  The present invention is a method for producing a polarizing film with less scratches and wrinkles and no folding, a polarizing plate in which a protective film is laminated on at least one side of the resulting polarizing film, a retardation film, a brightness enhancement film, and a viewing angle improvement film Further, the present invention relates to an optical laminate in which any one of the transflective films and a plurality of the transflective films are bonded.

  Conventionally, a polarizing film in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol film has been used. That is, an iodine polarizing film using iodine as a dichroic dye, a dye polarizing film using a dichroic dye as a dichroic dye, and the like are known. These polarizing films are usually used as polarizing plates by attaching a protective film such as triacetyl cellulose to at least one surface, preferably both surfaces, with an adhesive made of an aqueous solution of a polyvinyl alcohol resin.

  As a method for producing a polarizing film, a nip roll and a guide roll are used. A polyvinyl alcohol film is immersed in water to swell, then dyed with the dichroic dye, stretched, and then fixed with iodine to the film. For this purpose, a method is known in which a polyvinyl alcohol film is treated with boric acid, washed with water and then dried (see, for example, Patent Document 1). At this time, the film is stretched by giving a peripheral speed difference to the nip rolls before and after the treatment bath, the film transport direction is changed by the guide rolls, and the film is introduced into and taken out of the treatment liquid.

  As the guide roll, a flat rubber roll or a spiral rubber roll whose surface is made of a rubber layer is used (for example, see Patent Document 2).

In recent years, with an increase in the quality of liquid crystal display devices in which a polarizing film is used, there is a demand for a polarizing film that has fewer flaws and wrinkles than a polarizing film obtained by a conventional method and has no folding.
JP-A-10-153709 JP 2000-147252 A

  The main problem to be solved by the present invention is to provide a method for producing a polarizing film with fewer scratches and wrinkles and no folding.

  As a result of intensive studies to produce a polarizing film with fewer scratches and wrinkles, the present inventors use a widening roll as a guide roll, and the maximum widening amount β of the widening roll is such that the film contacts the widening roll. By placing a widening roll at a position that exceeds the amount of expansion γ in the width direction of the film during use, or using a widening roll with a shape that exceeds, there are few scratches and wrinkles, and there is no folding, especially made of sponge rubber It has been found that the use of the widening roll has a great effect of reducing scratches and wrinkles and eliminating folding when it is placed in the swelling treatment liquid, and the present invention has been completed.

  That is, in the method for producing a polarizing film of the present invention, a polyvinyl alcohol film is treated in the order of swelling treatment, dyeing treatment, boric acid treatment and water washing treatment, and uniaxial stretching is performed in the boric acid treatment step and / or the previous step. In the method for producing a polarizing film, a widening roll is used as at least one guide roll in the treatment liquid, and the maximum widening amount β of the widening roll obtained by the following formula (1) and the film obtained by the following formula (2) are widened. A widening roll having a shape in which (a) a widening roll is disposed at a position where β> γ, and / or (b) a relation of β> γ, in relation to an amount of expansion γ in the width direction of the film while in contact with the roll Is a method for producing a polarizing film.

β = B ₁ × α × r / R (1)
(Wherein, film width B ₁ represents in contact with the widening roll, alpha is the contact angle of the widening roll, r is the radius of the widening roll, R represents the radius of curvature of the widening roll.)

γ = 0.2055 × B ₁ × {exp (−0.0273 × θ ₁ ) −exp (−0.0273 × θ)} (2)
(In the formula, B ₁ is the same as above, θ represents the running time in the liquid until the film leaves the widening roll, and θ ₁ represents the running time in the liquid until the film contacts the widening roll.)

Further, the widening roll is a sponge rubber roll, the hardness of the sponge is 20 to 60 degrees on the JIS Shore C scale, the density is 0.4 to 0.6 g / cm ^3, and the surface roughness is 10 to 30S. And

  The widening roll is disposed in the swelling treatment liquid.

  Furthermore, the polarizing plate of the present invention is obtained by bonding a protective film to at least one surface of the polarizing film obtained as described above. This protective film may have any function of a retardation film, a brightness enhancement film, a viewing angle improvement film, and a transflective film. Or even if it is the optical laminated body which bonded at least 1 sort (s) chosen from a phase difference plate, a brightness improvement film, a viewing angle improvement film, and a transflective plate to the said polarizing plate which bonded the protective film on the single side | surface at least. Good.

Compared to the conventional method, a polarizing film with fewer scratches and wrinkles and no folding is obtained.
In particular, by disposing a sponge rubber widening roll and further disposing a widening roll in the expansion treatment liquid, the effect of reducing scratches and wrinkles and eliminating folding is great.
By using the polarizing plate and the optical laminate of the present invention for a liquid crystal display device, a thin and high-quality liquid crystal display can be obtained.

Hereinafter, the present invention will be described in detail.
The polyvinyl alcohol resin forming the polyvinyl alcohol (PVA) film in the present invention is typically exemplified by a saponified polyvinyl acetate resin. The degree of saponification is about 85 mol% or more, preferably about 90 mol% or more, more preferably about 99 mol% to 100 mol%. Polyvinyl acetate resins include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith, such as ethylene-vinyl acetate copolymer. Examples include coalescence. Examples of other copolymerizable monomers include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids. The degree of polymerization of the polyvinyl alcohol resin is about 1000 to 10000, preferably about 1500 to 5000.

These polyvinyl alcohol resins may be modified. For example, polyvinyl formal modified with aldehydes, polyvinyl acetal, polyvinyl butyral, and the like may be used. Usually, an unstretched film of a polyvinyl alcohol-based resin film having a thickness of about 20 μm to 100 μm, preferably about 30 μm to 80 μm is used as a starting material for manufacturing a polarizing film. Industrially, the width of the film is practically about 1500 mm to 4000 mm.
The unstretched film is treated in the order of swelling treatment, dyeing treatment, boric acid treatment, and water washing treatment, and finally dried to obtain a polyvinyl alcohol polarizing film having a thickness of, for example, about 5 to 50 μm.

  The polarizing film of the present invention is a polyvinyl alcohol uniaxially stretched film obtained by adsorbing and orienting a dichroic dye, and there are roughly two production methods as the production method. One is a method in which a polyvinyl alcohol film is uniaxially stretched in air or an inert gas, followed by solution treatment in the order of swelling treatment, dyeing treatment, boric acid treatment and water washing treatment, followed by drying. Secondly, an unstretched polyvinyl alcohol film is treated with an aqueous solution in the order of swelling treatment, dyeing treatment, boric acid treatment and water washing treatment, and uniaxial stretching is performed in a wet manner in the boric acid treatment step and / or the previous step. This is a method of performing drying and finally drying.

In any method, the uniaxial stretching may be performed in one step or in two or more steps, but is preferably performed in a plurality of steps. As a stretching method, a known method can be adopted. For example, stretching between rolls in which stretching is performed with a difference in peripheral speed between two nip rolls for transporting a film, hot roll stretching as described in Japanese Patent No. 2731813 Method and tenter stretching method. The order of the steps is basically as described above, but there are no restrictions on the number of treatment baths or treatment conditions.
Needless to say, a process not described in the above process can be freely inserted for another purpose. As an example of this process, after boric acid treatment, immersion treatment (iodide treatment) with an aqueous iodide solution not containing boric acid or immersion treatment (zinc treatment) step with an aqueous solution containing zinc chloride not containing boric acid, etc. Can be mentioned.

  The swelling step is performed for the purpose of removing foreign matter from the film surface, removing the plasticizer in the film, imparting easy dyeability in the next step, and plasticizing the film. The treatment conditions are determined within a range in which these objects can be achieved and within a range in which problems such as extreme dissolution and devitrification of the base film do not occur. When the film previously stretched in gas is swollen, for example, the film is immersed in an aqueous solution of about 20 ° C. to 70 ° C., preferably about 30 ° C. to 60 ° C. The immersion time of the film is about 30 seconds to 300 seconds, more preferably about 60 seconds to 240 seconds. When the unstretched raw film is swollen from the beginning, the film is immersed in an aqueous solution of, for example, about 10 ° C to 50 ° C, preferably about 20 ° C to 40 ° C. The immersion time of the film is about 30 seconds to 300 seconds, more preferably about 60 seconds to 240 seconds.

  In the swelling treatment step, problems such as the film swelling in the width direction and wrinkling into the film are likely to occur, so a widening roll (expander roll), spiral roll, crown roll, cross guider, bend bar, tenter clip, etc. will be described later. It is preferable to arrange the film at a specific position and transport the film while removing the wrinkles of the film. In order to stabilize the film transport in the bath, the water flow in the swelling bath is controlled with an underwater shower, or an EPC device (Edge Position Control device: a device that detects the edge of the film and prevents meandering of the film) It is also useful to use these together. In this step, since the film swells and expands in the running direction of the film, it is preferable to take measures such as controlling the speed of the transport roll before and after the treatment tank in order to eliminate the slack of the film in the transport direction. In addition to pure water, the swelling treatment bath used is boric acid (described in JP-A-10-153709), chloride (described in JP-A-06-281816), inorganic acid, inorganic salt, water-soluble An aqueous solution to which an organic solvent, alcohol or the like is added in an amount of about 0.01 to 10% by weight can also be used.

  The dyeing step with the dichroic dye is performed for the purpose of adsorbing and orienting the dichroic dye on the film. The treatment conditions are determined within a range in which these objects can be achieved and within a range in which problems such as extreme dissolution and devitrification of the base film do not occur. When iodine is used as the dichroic dye, for example, at a temperature of about 10 ° C. to 45 ° C., preferably about 20 ° C. to 35 ° C., and in a weight ratio, iodine / KI / water = about 0.003 to 0.2 / The immersion treatment is performed at a concentration of about 0.1 to 10/100 for about 30 seconds to 600 seconds, preferably about 60 seconds to 300 seconds. Instead of potassium iodide, other iodides such as zinc iodide may be used. Other iodides may be used in combination with potassium iodide. Further, compounds other than iodide, such as boric acid, zinc chloride, cobalt chloride, etc. may coexist. When boric acid is added, it is distinguished from the following boric acid treatment in that it contains iodine. Any dye containing about 0.003 parts by weight or more of iodine with respect to 100 parts by weight of water can be regarded as a dyeing tank.

  When a water-soluble dichroic dye is used as the dichroic dye, for example, at a temperature of about 20 ° C. to 80 ° C., preferably about 30 ° C. to 70 ° C., and a weight ratio of dichroic dye / water = about 0.001. The immersion treatment is performed at a concentration of about 0.1 / 100 for about 30 seconds to 600 seconds, preferably about 60 seconds to 300 seconds. The aqueous solution of the dichroic dye to be used may have a dyeing assistant or the like, and may contain, for example, an inorganic salt such as sodium sulfate, a surfactant or the like. The dichroic dye may be used alone, or two or more dichroic dyes may be used at the same time.

  As described above, the film may be stretched in a dyeing tank. Stretching is performed by a method of giving a peripheral speed difference between the nip rolls before and after the dyeing tank. Similarly to the swelling step, a widening roll (expander roll), a spiral roll, a crown roll, a cross guider, a bend bar, and the like can be installed in the dyeing bath and / or at the bath entrance / exit.

The boric acid treatment is performed by immersing a polyvinyl alcohol film dyed with a dichroic dye in an aqueous solution containing about 1 to 10 parts by weight of boric acid with respect to 100 parts by weight of water. When the dichroic dye is iodine, it is preferable to contain about 1 to 30 parts by weight of iodide.
Examples of iodide include potassium iodide and zinc iodide. Further, compounds other than iodide, such as zinc chloride, cobalt chloride, zirconium chloride, sodium thiosulfate, potassium sulfite, sodium sulfate, etc. may coexist.
This boric acid treatment is carried out for water resistance, hue adjustment (preventing bluishness, etc.) by crosslinking, and the like. In the case of water resistance by cross-linking, a cross-linking agent such as glyoxal or glutaraldehyde can be used in addition to or together with boric acid, if necessary.
In addition, the boric acid treatment for water resistance may be referred to by names such as water resistance treatment, crosslinking treatment, and immobilization treatment. In addition, boric acid treatment for hue adjustment may be referred to by a name such as complementary color treatment or re-dyeing treatment.

This boric acid treatment is performed by appropriately changing the concentrations of boric acid and iodide and the temperature of the treatment bath according to the purpose.
The boric acid treatment for water resistance and the boric acid treatment for hue adjustment are not particularly distinguished, but are carried out under the following conditions.
When the raw film is swollen, dyed or treated with boric acid, and the boric acid treatment is aimed at water resistance by crosslinking, about 3 to 10 parts by weight of boric acid and 100% by weight of iodide, iodide Is carried out at a temperature of about 50 ° C. to 70 ° C., preferably about 55 ° C. to 65 ° C. The immersion time is usually about 30 to 600 seconds, preferably about 60 to 420 seconds, more preferably about 90 to 300 seconds.
In addition, when dye | staining and boric-acid treatment the film extended | stretched previously, the temperature of a boric-acid treatment bath is about 50 to 85 degreeC normally, Preferably it is about 55 to 80 degreeC.

After boric acid treatment for water resistance, boric acid treatment for hue adjustment may be performed. For example, when the dichroic dye is iodine, a boric acid treatment bath containing about 1 to 5 parts by weight of boric acid and about 3 to 30 parts by weight of iodide for 100 parts by weight of water is used for this purpose. And is usually performed at a temperature of about 10 ° C to 45 ° C. The immersion time is usually about 3 to 300 seconds, preferably about 10 to 240 seconds.
The boric acid treatment for adjusting the hue is usually performed at a lower boric acid concentration, a higher iodide concentration, and a lower temperature than the boric acid treatment for water resistance.

These boric acid treatments may be performed in a plurality of steps and are usually performed in 2 to 5 steps. In this case, the aqueous solution composition and temperature of each boric acid treatment tank to be used may be the same or different within the above range. The boric acid treatment for water resistance and the boric acid treatment for hue adjustment may be performed in a plurality of steps, respectively.
In the boric acid treatment process, the film may be stretched in the same manner as in the dyeing process. The final cumulative draw ratio is about 4.5 to 7.0 times, preferably about 5.0 to 6.5 times.

  After boric acid treatment, it is washed with water. The water washing treatment is performed, for example, by immersing a polyvinyl alcohol film treated with boric acid for water resistance and / or color tone adjustment in water, spraying water as a shower, or combining immersion and spraying. The temperature of water in the water washing treatment is usually about 2 to 40 ° C., and the immersion time is preferably about 2 to 120 seconds. Drying after washing with water is performed in a drying furnace at a temperature of about 40 to 100 ° C. for about 60 to 600 seconds.

In each step after the stretching treatment, tension control may be performed so that the tension of the film becomes substantially constant.
When stretching is completed in the dyeing process, tension control is performed in the subsequent boric acid treatment process and the water washing process. When stretching is completed in the previous process of the dyeing process, tension control is performed in subsequent processes including the dyeing process and the boric acid process.
When the boric acid treatment step is composed of a plurality of boric acid treatment steps, the film is stretched in the boric acid treatment step from the first or the first to the second step, and the next boric acid treatment step after the boric acid treatment step in which the stretching treatment is performed. Tension control is performed in each step from the acid treatment step to the water washing step, or the film is stretched in the boric acid treatment step from the first to the third step, and the boric acid next to the boric acid treatment step in which the stretching treatment is performed. Although it is preferable to perform tension control in each process from the treatment process to the water washing process, industrially. The film is stretched in the boric acid treatment process from the first or the first to the second stage, and tension control is performed in each process from the boric acid treatment process to the water washing process following the boric acid treatment process. Is more preferable.
When the above-described iodide treatment or zinc treatment is performed after the boric acid treatment, tension control is also performed for these steps.

The tension in each step may be the same or different.
The tension to the film in the tension control is not particularly limited, and is appropriately set within a range of about 150 N / m to 2000 N / m, preferably about 600 N / m to 1500 N / m per unit width. When the tension is less than about 150 N / m, wrinkles and the like are easily formed on the film. On the other hand, when the tension exceeds about 2000 N / m, problems such as film breakage and life reduction due to bearing wear occur. The tension per unit width is calculated from the film width near the entrance of the process and the tension value of the tension detector.
In addition, when tension control is performed, there are cases where the film is inevitably slightly stretched or shrunk, but in the present invention, this is not included in the stretching process.

  In the present invention, a widening roll is used as at least one guide roll in the treatment liquid, and the maximum widening amount β of the widening roll obtained by the following mathematical formula (1) and the film obtained by the following mathematical formula (2) are used as the widening roll. (A) A widening roll is disposed at a position where β> γ and / or (b) a widening roll having a shape satisfying β> γ is used. .

β = B ₁ × α × r / R (1)
(Wherein, film width B ₁ represents in contact with the widening roll, alpha is the contact angle of the widening roll, r is the radius of the widening roll, R represents the radius of curvature of the widening roll.)

γ = 0.2055 × B ₁ × {exp (−0.0273 × θ ₁ ) −exp (−0.0273 × θ)} (2)
(In the formula, B ₁ is the same as above, θ represents the running time in the liquid until the film leaves the widening roll, and θ ₁ represents the running time in the liquid until the film contacts the widening roll.)

FIG. 1 is an explanatory view of the widening roll. (A) is a plan view and (B) is a cross-sectional view.
The widening roll has a substantially arc shape, and its radius of curvature is R and its arc height is H. The radius of the widening roll is r, the contact angle of the surface where the film is in contact with the widening roll is α, and the length of the surface in contact is α · r.
Figure 2 is a plan view showing the widening status of the film, the film width in contact with the widening roll at B _1, and widening a roll contact portion, widening the film width is represented by B _2.
FIG. 3 is a schematic cross-sectional view showing an example in which widening rolls are arranged in a processing tank. The film is conveyed through the widening rolls 2 and 3 disposed in the processing rolls 6 in the air and the guide rolls 1 and 4 in the processing tank 5 and processed with the processing liquid. The film enters the processing liquid at point A, touches the widening roll 2 at point B, leaves at point C, touches the widening roll 3 at point D, leaves at point E, and leaves the processing liquid at point F. The traveling time θ in the liquid until the film leaves the widening roll about the widening roll 2 is the traveling time between A and C, and the traveling time θ _{1 in} the liquid until the film contacts the widening roll is AB. Traveling time between. The running time θ in the liquid until the film leaves the widening roll for the widening roll 3 is the running time between A and E, and the running time θ _{1 in} the liquid until the film contacts the widening roll is A to D. Traveling time between.

  β varies depending on the shape and position of the widening roll, and γ varies depending on the shape and position of the widening roll and further the film transport speed. The film transport speed is often set under other processing conditions, and the transport speed is rarely changed to satisfy β> γ. Usually, the widening roll having the expected shape is selected, the position of the widening roll is adjusted, and if it is insufficient, this is repeated, and the optimum position and / or shape of the widening roll satisfying β> γ is determined. To do.

The widening roll is preferably a sponge rubber widening roll (sponge rubber widening roll), and the hardness of the sponge is about 20 to 60 degrees, preferably about 25 to 40 degrees on the JIS Shore C scale measured by the test method of JIS K 6301. Average of the local peaks of the roughness curve with a density of about 0.4 to 0.6 g / cm ³ , preferably about 0.42 to 0.57 g / cm ³ and a surface roughness of JIS B 0601 (surface roughness). The distance S is about 10 to 30S, preferably about 15 to 25S.

The widening roll is particularly preferably used in the swelling treatment step, and in that case, it is preferable to use a sponge rubber widening roll. In the swelling treatment step, the polyvinyl alcohol film swells in both the longitudinal and width directions due to absorption of the bath solution, but particularly when the tension is applied without the swelling in the width direction ending, wrinkles and folds are generated on the roll. The use of a sponge rubber widening roll makes it possible to greatly reduce the tension applied to the film due to its light weight, and at the same time, because of the high film gripping force based on its high surface roughness, even a low tension is sufficient. The widening force can be exhibited, and the meandering prevention function, which is another role of the widening roll, is also exhibited to the maximum, so that wrinkles are reduced and folding is eliminated.
The use of the widening roll is not limited to the swelling treatment, and can be used in other treatments.

A polarizing plate is obtained by bonding a protective film with an adhesive on at least one side of the polarizing film thus produced.
As the protective film, for example, a film made of an acetyl cellulose resin such as triacetyl cellulose or diacetyl cellulose, a film made of a polyester resin such as polyethylene terephthalate, polyethylene naphthalate or polybutylene terephthalate, or a film made of a polycarbonate resin And a film made of a cycloolefin resin. Examples of commercially available thermoplastic cycloolefin resins include “Topas” (registered trademark) sold by Ticona of Germany and “Arton” (trademark) sold by JSR Co., Ltd. Registered), “ZEONOR” and “ZEONEX” (both registered trademarks) sold by Nippon Zeon Co., Ltd., and “APEL” (trademark registered) sold by Mitsui Chemicals, Inc. A film formed from such a cycloolefin-based resin is used as a protective film. For the film formation, a known method such as a solvent casting method or a melt extrusion method is appropriately used. The formed cycloolefin resin film is also commercially available, for example, “Essina” and “SCA40” sold by Sekisui Chemical Co., Ltd.

  The thickness of the protective film is preferably thin. However, if it is too thin, the strength is lowered and the processability is inferior. On the other hand, if it is too thick, the transparency is lowered and the curing time required after lamination is increased. Problems occur. Accordingly, a suitable thickness of the protective film is, for example, about 5 to 200 μm, preferably about 10 to 150 μm, and more preferably about 20 to 100 μm.

  In order to improve the adhesiveness between the adhesive and the polarizing film and / or protective film, the polarizing film and / or protective film may be subjected to corona treatment, flame treatment, plasma treatment, ultraviolet irradiation, primer coating treatment, saponification treatment, etc. A surface treatment may be applied.

The protective film may be subjected to surface treatment such as anti-glare treatment, anti-reflection treatment, hard coat treatment, antistatic treatment, and antifouling treatment alone or in combination. The protective film and / or the protective film surface protective layer may have a UV absorber such as a benzophenone compound or a benzotriazole compound, or a plasticizer such as a phenyl phosphate compound or a phthalate compound.
Such a protective film may be bonded to one side of the polarizing film or may be bonded to both sides.

  The polarizing film and the protective film are laminated using an adhesive such as a water solvent adhesive, an organic solvent adhesive, a hot melt adhesive, or a solventless adhesive. Examples of aqueous solvent adhesives include aqueous polyvinyl alcohol resins and aqueous two-component urethane emulsion adhesives, and examples of organic solvent adhesives include two-component urethane adhesives as solvent-free adhesives. For example, a one-pack type urethane adhesive may be used. When an acetylcellulose-based film whose surface to be bonded to the polarizing film is hydrophilized by saponification or the like is used as a protective film, a polyvinyl alcohol-based resin aqueous solution is suitably used as an adhesive. Polyvinyl alcohol resins used as adhesives include vinyl alcohol homopolymers obtained by saponifying polyvinyl acetate, which is a homopolymer of vinyl acetate, as well as other single quantities copolymerizable with vinyl acetate. And vinyl alcohol copolymers obtained by saponifying the copolymer with the polymer, and modified polyvinyl alcohol polymers obtained by partially modifying the hydroxyl groups. For this adhesive, a polyvalent aldehyde, a water-soluble epoxy compound, a melamine compound or the like may be used as an additive.

  The method for laminating the polarizing film and the protective film is not particularly limited. For example, an adhesive is uniformly applied to the surface of the polarizing film or the protective film, and the other film is stacked on the coated surface by a roll or the like. The method of pasting and drying is mentioned.

Usually, an adhesive agent is apply | coated at the temperature of about 15-40 degreeC after preparation, and the bonding temperature is the range of about 15-30 degreeC normally. After pasting, a drying treatment is performed to remove a solvent such as water contained in the adhesive, and the drying temperature in this case is usually about 30 to 85 ° C, preferably about 40 to 80 ° C. . Thereafter, the adhesive may be cured by curing for about 1 to 90 days under a temperature environment of about 15 to 85 ° C, preferably about 20 to 50 ° C, more preferably about 35 to 45 ° C. When this curing period is long, productivity deteriorates, so the curing period is about 1 to 30 days, preferably about 1 to 7 days.
Thus, a polarizing plate in which the protective film is bonded to one side or both sides of the polarizing film through the adhesive layer is obtained.

  In the present invention, the protective film has a function as a retardation film, a function as a brightness enhancement film, a function as a reflection film, a function as a transflective film, a function as a diffusion film, a function as an optical compensation film, etc. It can also have an optical function. In this case, for example, by laminating an optical functional film such as a retardation film, a brightness enhancement film, a reflection film, a transflective film, a diffusion film, an optical compensation film on the surface of the protective film, it has such a function. In addition, the protective film itself can be given such a function. Further, the protective film itself may have a plurality of functions such as a diffusion film having the function of a brightness enhancement film.

  For example, the protective film is subjected to a stretching process described in Japanese Patent No. 2841377, Japanese Patent No. 3094113, etc., or a process described in Japanese Patent No. 3168850, etc. The function as can be provided. In addition, by forming micropores in the above protective film by a method as described in JP 2002-169025 A or JP 2003-29030 A, two or more layers having different central wavelengths of selective reflection are formed. By superimposing these cholesteric liquid crystal layers, a function as a brightness enhancement film can be imparted. By forming a metal thin film on the above protective film by vapor deposition or sputtering, a function as a reflective film or a transflective film can be imparted. By coating the protective film with a resin solution containing fine particles, a function as a diffusion film can be imparted. Moreover, the function as an optical compensation film can be provided by coating and aligning liquid crystalline compounds, such as a discotic liquid crystalline compound, on said protective film. In addition, using an appropriate adhesive, a brightness enhancement film such as a trade name: DBEF (manufactured by 3M Co., Ltd.), a trade name: a viewing angle improving film such as a WV film (manufactured by Fuji Photo Film Co., Ltd.), a trade name : Commercially available optical functional films such as retardation films such as Sumikalite (registered trademark) (Sumitomo Chemical Co., Ltd.) may be directly bonded to the polarizing film.

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, this invention is not limited by these examples.
Example 1
A 75-μm-thick polyvinyl alcohol film (Kurarevinylone VF-PS # 7500, polymerization degree 2,400, saponification degree 99.9 mol% or more) as shown below in a swelling tank, a dyeing tank, a first boric acid treatment tank, The polarizing film was manufactured by conveying in the order of the 2-boric acid treatment tank and the washing tank.
As shown in FIG. 3, using a swelling tank, as two guide rolls in the treatment liquid, the radius r is 37.5 mm, the hardness of the sponge is 25 degrees on the JIS Shore C scale, the density is 0.42 g / cm ³ , A sponge rubber widening roll having a surface roughness of 20S was used. As a guide roll in other air and other treatment liquid, an NBR rubber roll having a radius of 35 mm, a surface roughness of 0.6 S, and a rubber hardness (JIS Shore A scale) of 80 degrees was used.

The first widening roll (2 in the figure) has a radius of curvature R: 1303 mm and an isolated height H: 35 mm, and the second widened roll (3 in the figure) has a radius of curvature R: 1813 mm and an isolated height H: 25 mm. It arrange | positioned in the position where angle (alpha) will be 1.5 rad.
The conveyance speed of the polyvinyl alcohol film is about 0.34 m / min, and the running time θ in the liquid until the film leaves the first widening roll at this time is 20 seconds, the liquid in the liquid until it contacts the first widening roll. The traveling time θ ₁ is 11 seconds, the traveling time θ in the liquid until the film leaves the second widening roll is 66 seconds, and the traveling time θ _{1 in} the liquid until the film contacts the second widening roll is 57 seconds. is there.

The treatment liquid in the swelling tank was pure water of about 30 ° C., and the polyvinyl alcohol film was transported in a tensioned state so as not to be loosened and sufficiently swollen. The immersion time is about 80 seconds.
At this time, the film width B ₁ in contact with the first widening roll was 369 mm, and the film width B ₁ in contact with the second widening roll was 407 mm.
When the maximum widening amount β of these widening rolls is obtained from Equation (1), the first widening roll is 15.9 mm, the second widening roll is 12.6 mm, and the film is in contact with the respective widening rolls. When the expansion amount γ in the width direction is determined from Equation (2), the first widening roll is 12.2 mm and the second widening roll is 3.8 mm, and β> γ for any of the expansion rolls.
When the running and surface state of the film were observed, there was no occurrence of wrinkles, folds or scratches, and a very stable stretched running state of the film was obtained.

Next, uniaxial stretching (stretching ratio: 4.0 times) was performed while immersing in an aqueous solution of iodine / potassium iodide / water in a weight ratio of 0.02 / 1.5 / 100 and dyeing. Then, it is immersed in an approximately 60 ° C. aqueous solution of potassium iodide / boric acid / water in a weight ratio of 10/5/100, and is uniaxial until the cumulative draw ratio from the raw material reaches 5.9 times while boric acid treatment. Stretching was performed. In addition, extending | stretching was performed by giving the peripheral speed difference to the nip roll arrange | positioned before and behind the processing tank.
Further, a second boric acid treatment was performed by immersing in an aqueous solution of potassium iodide / boric acid / water at a weight ratio of 10/3/100 at about 40 ° C. for about 30 seconds. After the second boric acid treatment, it was washed with pure water at about 10 ° C. for about 10 seconds. After washing with water and drying at about 60 ° C. for 2 minutes, an iodine-based polarizing film having a thickness of about 28 μm was obtained.
No scratches or wrinkles were found on the obtained polarizing film.

Polyvinyl alcohol-based adhesive was applied to both sides of the obtained polarizing film, and a protective film [Triacetylcellulose film with surface saponification treatment, “Fujitac (registered trademark) T80UNL”, manufactured by Fuji Photo Film Co., Ltd.] , Thickness 80 μm] was bonded to both sides and dried at about 60 ° C. for about 5 minutes to obtain a polarizing plate.
A polarizing plate free from scratches and wrinkles was obtained.

Comparative Example 1
The first widening roll has a radius r: 28 mm, a curvature radius R: 3008 mm, an arc height H: 15 mm, a sponge hardness of 25 degrees on a JIS Shore C scale, a density of 0.42 g / cm ³ , and a surface roughness of 20S. A polarizing film was produced in the same manner as in Example 1 except that the sponge rubber widening roll was used and the contact angle α was 1.1 rad, and the film conveyance speed was 0.68 m / min. .
Travel time theta 9 seconds of the film at this time in the liquid to leave the first widening roll, running time theta ₁ in the liquid until the contact with the first widening roll is 6 seconds, the film is a second widening The traveling time θ in the liquid until leaving the roll is 34 seconds, and the traveling time θ _{1 in} the liquid until contacting the second widening roll is 30 seconds.

The film width B ₁ in contact with the first widening roll was 360 mm, and the film width B ₁ in contact with the second widening roll was 390 mm.
When the maximum widening amount β of these widening rolls is obtained from the formula (1), the first widening roll is 3.7 mm, the second widening roll is 12.1 mm, and the film is in contact with each widening roll. When the expansion amount γ in the width direction is obtained from Equation (2), the first widening roll is 4.9 mm, the second widening roll is 3.7 mm, β <γ in the first widening roll, Is β> γ.
When the running and surface state of the film were observed, film wrinkles and folding occurred from the first widening roll, and the once generated folding was not eliminated by the second widening roll.
The obtained polarizing film showed wrinkles and folds.

It is explanatory drawing of a widening roll, (A) is a top view, (B) is sectional drawing. It is a top view which shows the widening condition of a film. It is a schematic cross section which shows the example which has arrange | positioned the widening roll in the processing tank.

Explanation of symbols

H Arc height R Curvature radius r Radius α Contact angle B ₁ Film width B in contact with the widening roll ₂ Film width widened with the widening roll 1 Guide roll 2 Widening roll 3 Widening roll 4 Guide roll 5 Treatment tank 6 Treatment liquid

Claims (6)

In the method for producing a polarizing film in which a polyvinyl alcohol film is treated in the order of swelling treatment, dyeing treatment, boric acid treatment and washing treatment, and uniaxial stretching is performed in the boric acid treatment step and / or the preceding step, at least in the treatment liquid A widening roll is used as one guide roll, and the maximum widening amount β of the widening roll obtained by the following mathematical formula (1) and expansion in the width direction of the film while the film obtained by the following mathematical formula (2) contacts the widening roll. A method for producing a polarizing film, characterized in that: (a) a widening roll is disposed at a position where β> γ, and / or (b) a widening roll having a shape satisfying β> γ is used. .
β = B ₁ × α × r / R (1)
(Wherein, film width B ₁ represents in contact with the widening roll, alpha is the contact angle of the widening roll, r is the radius of the widening roll, R represents the radius of curvature of the widening roll.)
γ = 0.2055 × B ₁ × {exp (−0.0273 × θ ₁ ) −exp (−0.0273 × θ)} (2)
(In the formula, B ₁ is the same as above, θ represents the running time in the liquid until the film leaves the widening roll, and θ ₁ represents the running time in the liquid until the film contacts the widening roll.) The widening roll is a sponge rubber roll, and the hardness of the sponge is 20 to 60 degrees on a JIS Shore C scale, the density is 0.4 to 0.6 g / cm ^3, and the surface roughness is 10 to 30S. A method for producing a polarizing film.   The manufacturing method of the polarizing film of Claim 1 which arrange | positions a widening roll in a swelling processing liquid.   The polarizing plate by which a protective film is bonded by the at least single side | surface of the polarizing film manufactured by the method of Claims 1-3.   The polarizing plate according to claim 4, wherein the protective film has a function of any one of a retardation film, a brightness enhancement film, a viewing angle improvement film, and a transflective film. An optical laminate comprising the polarizing plate according to claim 4 and at least one selected from a retardation film, a brightness enhancement film, a viewing angle improvement film, and a transflective film.

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