JP6022894B2 - Manufacturing method of polarizing plate - Google Patents

Description

  The present invention relates to a method for producing a polarizing plate.

  A polarizing plate is widely used as a polarized light supplying element and a polarized light detecting element in a liquid crystal display device. As such a polarizing plate, a polarizing film made of polyvinyl alcohol resin and a protective film made of triacetyl cellulose are conventionally used. However, in recent years, mobile devices such as notebook personal computers and mobile phones for liquid crystal display devices have been used. Thinner and lighter weights are being demanded with the development of equipment and even with large televisions.

  As a method for producing such a thin polarizing plate, a solution containing a polyvinyl alcohol-based resin is applied to the surface of a base film to provide a resin layer, and then stretched and then dyed to have a polarizer layer. There have been proposed a method for obtaining a polarizing laminate film and using it as a polarizing plate as it is, and a method for applying a protective film to the film and then removing the substrate film as a polarizing plate (for example, JP 2000-338329 A and JP 2011-212550 A).

  Further, JP 2011-212550 A discloses a base film in order to prevent the both ends of the base film from warping in a drying step after applying a solution containing a polyvinyl alcohol resin on the surface of the base film. The method of providing the uncoated part which does not apply | coat a polyvinyl alcohol-type resin solution to both ends of is described. This uncoated part is prone to problems such as undulation during stretching or subsequent winding, so it can be removed by cutting before or after the stretching process in order to obtain a roll with a good winding shape. Have been described.

JP 2000-338329 A JP 2011-212550 A

  When obtaining a laminated film having a base film and a polarizer layer by stretching, dyeing, cross-linking, etc., after providing a polyvinyl alcohol-based resin layer on the base film surface as in the prior art described above, In the laminated film, heat, tension, stretching force, etc. act in processes such as dyeing and cross-linking, and the edges may be wavy or warped. As a result, the edges of the protective film are bonded. Folds and wrinkles may occur. Due to such folds and wrinkles, for example, a partial accumulation of adhesive occurs, and the portion becomes poorly dried, which may cause problems such as blue deterioration of the polarizer layer. .

  This invention is a manufacturing method of the polarizing plate which provides a laminated film by extending | stretching, dyeing | staining, bridge | crosslinking, etc., after providing a polyvinyl alcohol-type resin layer on the base film surface, and bonding a protective film further to this laminated film. Then, it aims at providing the manufacturing method of the polarizing plate which suppresses generation | occurrence | production and the wrinkle in an edge part, and suppresses blue discoloration deterioration of a polarizer layer.

The present invention includes the following.
[1] A method for producing a polarizing plate having a polarizer layer and a protective film, comprising a lamination step of forming a polyvinyl alcohol resin layer on at least one surface of a substrate film to obtain a laminated film, and a laminated film A stretching step for uniaxial stretching, a dyeing step for dyeing a polyvinyl alcohol resin layer of a laminated film subjected to uniaxial stretching with a dichroic dye, and a polyvinyl alcohol resin layer of the laminated film subjected to dyeing include a crosslinking agent. A cross-linking step of immersing in a solution to form a polarizer layer; a pre-bonding removal step of cutting and removing both first end portions in the width direction from the cross-linked laminated film; and a first end The manufacturing method of the polarizing plate which has the bonding process which bonds a protective film on the surface on the opposite side to the surface at the side of the base film of the polarizer layer in the laminated film which removed the part.
[2] The method according to [1], further including a pre-dying removal step of cutting and removing both second ends in the width direction from the laminated film after the laminating step and before the dyeing step. the method of.
[3] The method according to [1] or [2], wherein in the laminating step, third ends that do not form a polyvinyl alcohol-based resin layer are provided at both ends in the width direction of the base film.
[4] The method according to [1], including a drying step of drying the polarizer layer after the crosslinking step and before the pre-bonding removal step.
[5] The method according to [1], including a drying step of drying the polarizer layer after the pre-bonding removal step and before the bonding step.

  According to the production method of the present invention, after providing a polyvinyl alcohol-based resin layer on the surface of the base film, a laminated film is obtained by stretching, dyeing, cross-linking, and a protective film is further bonded to the laminated film. In manufacturing the polarizing plate, it is possible to suppress the folding and wrinkle generation at the end when the protective film is bonded, and to suppress the blue deterioration of the polarizer layer.

It is a flowchart which shows the manufacturing method of the polarizing plate of this invention. It is a top perspective view showing typically the lamination film after each manufacturing process of the manufacturing method of the polarizing plate of a 1st embodiment. It is a top perspective view showing typically the lamination film after each manufacturing process of the manufacturing method of the polarizing plate of a 2nd embodiment. It is an upper surface perspective view which shows typically the laminated | multilayer film after each manufacturing process of the manufacturing method of the polarizing plate of 3rd Embodiment.

  FIG. 1 is a flowchart showing a method for producing a polarizing plate of the present invention. The production method of the present invention includes a lamination step (S10) in which a polyvinyl alcohol resin layer is formed on at least one surface of a base film to obtain a laminated film, a stretching step (S20) in which the laminated film is uniaxially stretched, A dyeing step (S30) for dyeing the stretched laminated film of the polyvinyl alcohol resin layer with a dichroic dye, and immersing the dyed laminated film of the polyvinyl alcohol resin layer in a solution containing a crosslinking agent. A cross-linking step (S40) for forming a polarizer layer by cross-linking, a pre-bonding removal step (S50) for cutting and removing both first end portions in the width direction from the cross-linked laminated film, and a first Of the polarizing plate which has the bonding process (S60) which bonds a protective film to the surface on the opposite side to the surface at the side of the base material film of the polarizer layer in the laminated | multilayer film which removed the edge part in this order. It is a production method. You may have the peeling process (S70) which peels a base film further after a bonding process (S60). In the lamination step (S10), a polyvinyl alcohol-based resin layer may be formed on both surfaces of the base film, and the protective film may be bonded to the two polarizer layers in the bonding step (S60).

  According to the production method of the present invention, by having the pre-bonding removal step (S50), it is possible to remove the end portion of the laminated film where the waviness warpage has occurred when the crosslinking step (S40) is completed. Therefore, in the bonding step (S60) of bonding the protective film to the laminated film, it is possible to suppress the folding and wrinkle generation at the end of the laminated film and the blue discoloration deterioration in the polarizer layer.

  Hereinafter, a preferred embodiment of a method for producing a polarizing plate of the present invention will be described in detail with reference to the drawings.

[First Embodiment]
FIG. 2 is a top perspective view schematically showing a laminated film after each manufacturing step in the method for manufacturing a polarizing plate of the first embodiment. First, the base film 11 is prepared as shown in FIG. Next, the lamination process (S10) forms the polyvinyl alcohol-based resin layer 12a on one surface of the base film to obtain the laminated film shown in FIG. 2 (b). Next, the laminated film shown in FIG. 2B is subjected to a stretching step (S20), a dyeing step (S30), and a cross-linking step (S40) to form the polarizer layer 12b from the resin layer 12a. A laminated film shown in FIG. Next, about the laminated film shown in FIG.2 (c), it removes before bonding which cut | disconnects by dotted line A1 and removes both the edge parts (1st edge part) 13 of the width direction which is an area | region outside dotted line A1. A process (S50) is performed and the laminated film shown in FIG.2 (d) is obtained. Then, the bonding process (S60) which bonds a protective film to the polarizer layer 12b is performed.

  In FIG.2 (c), when the wavy and the curvature of the position of dotted line A1 have arisen in the edge part of a laminated | multilayer film, all the waviness and curvature will be included in the 1st edge part 13 outside dotted line A1. It is preferable to determine this. Moreover, when the area | region in which the polyvinyl alcohol-type resin layer is not formed is contained in the edge part of laminated | multilayer film, all the area | regions in which the polyvinyl alcohol-type resin layer is not formed are the 1st edge part 13 outside the dotted line A1. It is preferable to determine so that it is contained in. The dotted line A1 that defines the region of the first end 13 is preferably determined within a region of 0.5 cm to 20 cm inward from both ends in the width direction of the laminated film, for example, a region of 1.0 cm to 15 cm It is more preferable that it be determined within the range of 1.5 cm to 10 cm.

[Second Embodiment]
FIG. 3 is a top perspective view schematically showing the laminated film after each manufacturing step in the polarizing plate manufacturing method of the second embodiment. First, a base film 21 is prepared as shown in FIG. Next, the lamination process (S10) forms the polyvinyl alcohol-based resin layer 22a on one surface of the base film to obtain the laminated film shown in FIG. In addition, the dotted line A2 is prescribed | regulated previously in the both ends of the width direction of the base film 21, and the 3rd end part 21a which does not form a polyvinyl alcohol-type resin layer in the area | region outside it is provided. Thus, by providing the 3rd end part 21a which does not form resin layer 22a, when drying resin layer 22a, the phenomenon where both ends of a substrate film warp to the resin layer 22a side can be controlled. The resin layer 22a is formed by applying a solution containing a polyvinyl alcohol resin and then drying it. The dotted line A2 that defines the region of the third end 21a is preferably determined within the region of 0.5 cm to 20 cm inward from both ends in the width direction of the base film, and within the region of 1.0 cm to 15 cm More preferably, it is determined within a region of 1.5 cm to 10 cm.

  Next, with respect to the laminated film shown in FIG. 3B, the stretching step (S20), the dyeing step (S30), and the crosslinking step (S40) are performed to form the polarizer layer 22b from the polyvinyl alcohol-based resin layer 22a. A laminated film shown in 3 (c) is obtained. Next, about the laminated film shown in FIG.3 (c), it removes before bonding which cut | disconnects by dotted line B2 and removes both the edge parts (1st edge part) 23 of the width direction which is an area | region outside dotted line B2. A process (S50) is performed and the laminated film shown in FIG.3 (d) is obtained. Then, the bonding process (S60) which bonds a protective film to the polarizer layer 22b is performed.

  In FIG.3 (c), when the wavy and the curvature have arisen in the position of dotted line B2 in the edge part of a laminated | multilayer film, all of the waviness and curvature will be included in the 1st end part 23 outside dotted line B2. It is preferable to determine this. Moreover, it is preferable to determine so that the whole area | region (3rd edge part 21a) which does not form a resin layer may be contained in the 1st edge part 23 outside a dotted line B2. The dotted line B2 that defines the region of the first end 23 is preferably determined within a region of 0.5 cm to 20 cm inward from both ends in the width direction of the laminated film, for example, a region of 1.0 cm to 15 cm. It is more preferable that it be determined within the range of 1.5 cm to 10 cm.

[Third Embodiment]
FIG. 4 is a top perspective view schematically showing a laminated film after each manufacturing step in the method for manufacturing a polarizing plate of the third embodiment. First, a base film 31 is prepared as shown in FIG. Next, by the lamination step (S10), a resin layer 32a made of polyvinyl alcohol resin is formed on one surface of the base film to obtain a laminated film shown in FIG. In addition, the dotted line A3 is prescribed | regulated previously in the both ends of the width direction of the base film 31, and the 3rd end part 31a which does not form a polyvinyl alcohol-type resin layer in the area | region outside it is provided. Thus, by providing the 3rd end part 31a which does not form the resin layer 32a, when drying the resin layer 32a, the phenomenon that the both ends of a base film warp to the resin layer 32a side can be suppressed. The resin layer 32a is formed by applying a solution containing a polyvinyl alcohol resin and then drying it. The dotted line A3 that defines the region of the third end 31a is preferably determined within the region of 0.5 cm to 20 cm inward from both ends in the width direction of the base film, and within the region of 1.0 cm to 15 cm More preferably, it is determined within a region of 1.5 cm to 10 cm.

  Next, a stretching process (S20) is performed on the laminated film shown in FIG. And about the laminated | multilayer film shown in FIG.4 (c) which is a laminated | multilayer film after extending | stretching, both the edge parts (2nd edge part) 34 of the width direction which are the area | regions outside a dotted line B3 by cut | disconnecting by dotted line B3. The pre-dye removal step (S25) to be removed is performed to obtain a laminated film shown in FIG. By having the pre-dye removal step (S25), if the end portion is wavy or warped in the previous steps, the end portion can be removed, and the stretched laminated film can be wound well. it can. Therefore, it is possible to prevent the end portion from being folded or wrinkled in the subsequent process. The dotted line B3 that defines the region of the second end 34 is preferably determined so that the entire region where the resin layer is not formed (the third end 31a) is included in the second end 34 outside the dotted line B3. . The dotted line B3 that defines the second end 34 is preferably determined within a region of 0.5 cm to 20 cm inward from both ends in the width direction of the base film, and is determined within a region of 1.0 cm to 15 cm. More preferably, it is more preferably determined within the range of 1.5 cm to 10 cm. In addition, the removal process before dyeing | staining (S25) is not limited to the aspect performed after an extending process (S20) as mentioned above, You may perform before an extending process (S20).

  Then, a dyeing process (S30) and a bridge | crosslinking process (S40) are performed, and the laminated film shown in FIG.4 (e) is obtained. And about the laminated film shown in FIG.4 (e) after dyeing | staining and bridge | crosslinking, it cut | disconnects by the dotted line C3 and both the edge parts (1st edge part) 33 of the width direction which are the area | regions outside a dotted line C3. The pasting removal process (S50) which removes is performed, and the laminated film shown in FIG.4 (f) is obtained. Then, the bonding process (S60) which bonds a protective film to the polarizer layer 32b is performed.

  In the pre-bonding removal step (S50) in the present embodiment, when the end portion is wavy or warped in the dyeing step (S30) and the crosslinking step (S40), the end portion can be removed. It is possible to prevent folds and wrinkles from occurring during bonding.

  In FIG. 4 (e), the position of the dotted line C3 is such that when the end of the laminated film is wavy or warped, all of the wavy and warped are included in the first end 33 outside the dotted line C3. It is preferable to determine this. The dotted line C3 that defines the region of the first end 33 is preferably determined within a region of 0.5 cm to 20 cm inward from both ends in the width direction of the laminated film, for example, a region of 1.0 cm to 15 cm It is more preferable that it be determined within the range of 1.5 cm to 10 cm.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to these embodiment, For example, it can also implement combining each process of the said embodiment. Hereinafter, each process common to all the embodiments will be described in detail.

[Resin Layer Forming Step (S10)]
Here, a polyvinyl alcohol-based resin layer is formed on at least one surface of the base film. Materials suitable for the base film will be described later. In the present embodiment, it is preferable to use a substrate film that can be stretched in a temperature range suitable for stretching a polyvinyl alcohol resin.

  The thickness of the resin layer to be formed is preferably more than 3 μm and not more than 30 μm, more preferably 5 to 20 μm. If it is 3 μm or less, the film becomes too thin after stretching and the dyeability is remarkably deteriorated. If it exceeds 30 μm, the thickness of the finally obtained polarizer layer may exceed 10 μm.

  The resin layer is preferably formed by applying a polyvinyl alcohol resin solution obtained by dissolving polyvinyl alcohol resin powder in a good solvent onto one surface of the base film, and evaporating the solvent to dry the resin layer. It is formed. By forming the resin layer in this way, it can be formed thin. As a method of applying a polyvinyl alcohol resin solution to a base film, a wire bar coating method, a reverse coating, a roll coating method such as gravure coating, a die coating method, a comma coating method, a lip coating method, a spin coating method, a screen coating method. A method, a fountain coating method, a dipping method, a spray method, and the like can be appropriately selected from known methods and employed. A drying temperature is 50-200 degreeC, for example, Preferably it is 60-150 degreeC. The drying time is, for example, 2 to 20 minutes.

  Moreover, in order to improve the adhesiveness of a base film and a polyvinyl alcohol-type resin, you may provide a primer layer between a base film and a resin layer. The primer layer is preferably formed from a composition containing a crosslinking agent or the like in a polyvinyl alcohol resin from the viewpoint of adhesion.

(Base film)
As the resin used for the base film, for example, thermoplastic resins excellent in transparency, mechanical strength, thermal stability, stretchability, etc. are used, and depending on their glass transition temperature (Tg) or melting point (Tm). An appropriate resin can be selected. Specific examples of thermoplastic resins include polyolefin resins, polyester resins, cyclic polyolefin resins (norbornene resins), (meth) acrylic resins, cellulose ester resins, polycarbonate resins, polyvinyl alcohol resins, vinyl acetate. Resin, polyarylate resin, polystyrene resin, polyethersulfone resin, polysulfone resin, polyamide resin, polyimide resin, and mixtures and copolymers thereof.

  The base film may be a single layer using only one kind of the above-described resin, or may be a blend of two or more kinds of resins. Of course, a multilayer film may be formed instead of a single layer.

  Examples of the polyolefin resin include polyethylene and polypropylene, which are preferable because they can be stably stretched at a high magnification. Further, an ethylene-polypropylene copolymer obtained by copolymerizing propylene with ethylene can also be used. Copolymerization can be performed with other types of monomers, and examples of other types of monomers copolymerizable with propylene include ethylene and α-olefins. As the α-olefin, an α-olefin having 4 or more carbon atoms is preferably used, and more preferably an α-olefin having 4 to 10 carbon atoms. Specific examples of the α-olefin having 4 to 10 carbon atoms include linear monoolefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene; Branched monoolefins such as 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene; vinylcyclohexane and the like. The copolymer of propylene and other monomers copolymerizable therewith may be a random copolymer or a block copolymer. The content of the structural unit derived from the other monomer in the copolymer is determined by infrared (IR) spectrum according to the method described on page 616 of “Polymer Analysis Handbook” (1995, published by Kinokuniya). It can be obtained by measuring.

  Among the above, propylene-based resins constituting the propylene-based resin film include propylene homopolymer, propylene-ethylene random copolymer, propylene-1-butene random copolymer, and propylene-ethylene-1-butene. Random copolymers are preferably used.

  The stereoregularity of the propylene resin constituting the propylene resin film is preferably substantially isotactic or syndiotactic. A propylene-based resin film made of a propylene-based resin having substantially isotactic or syndiotactic stereoregularity has relatively good handleability and excellent mechanical strength in a high-temperature environment.

  The polyester resin is a polymer having an ester bond and is mainly a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol. As the polyvalent carboxylic acid used, divalent dicarboxylic acids are mainly used, and examples thereof include terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalenedicarboxylate. In addition, divalent diol is mainly used as the polyhydric alcohol used, and examples thereof include propanediol, butanediol, neopentyl glycol, cyclohexanedimethanol and the like.

  A typical example of the polyester resin is polyethylene terephthalate which is a copolymer of terephthalic acid and ethylene glycol. Polyethylene terephthalate is a crystalline resin, but the one in a state before crystallization treatment is more easily subjected to treatment such as stretching. If necessary, it can be crystallized during stretching or by heat treatment after stretching. In addition, a copolymerized polyester whose crystallinity has been lowered (or made amorphous) by further copolymerizing another monomer with the polyethylene terephthalate skeleton is also preferably used. As examples of such resins, for example, those obtained by copolymerization of cyclohexanedimethanol, isophthalic acid or the like are preferably used. These resins are also excellent in stretchability and can be suitably used.

  Specific resins other than polyethylene terephthalate and copolymers thereof include polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexane dimethyl terephthalate, polycyclohexane dimethyl naphthalate. Phthalate, and the like. These blend resins and copolymers can also be suitably used.

  As the cyclic polyolefin resin, a norbornene resin is preferably used. Cyclic polyolefin resin is a general term for resins that are polymerized using cyclic olefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Resin. Specific examples include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, cyclic olefins and α-olefins such as ethylene and propylene (typically random copolymers), And graft polymers obtained by modifying them with an unsaturated carboxylic acid or a derivative thereof, and hydrides thereof. Specific examples of the cyclic olefin include norbornene monomers.

  Various products are commercially available as cyclic polyolefin resins. As specific examples, Topas (registered trademark) (manufactured by Ticona), Arton (registered trademark) (manufactured by JSR Corporation), ZEONOR (registered trademark) (manufactured by Nippon Zeon Corporation), ZEONEX (ZEONEX) (Registered trademark) (manufactured by ZEON CORPORATION) and Apel (registered trademark) (manufactured by Mitsui Chemicals, Inc.).

  Any appropriate (meth) acrylic resin can be adopted as the (meth) acrylic resin. For example, poly (meth) acrylic acid ester such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester -(Meth) acrylic acid copolymer, (meth) acrylic acid methyl-styrene copolymer (MS resin, etc.), polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer) And methyl methacrylate- (meth) acrylate norbornyl copolymer). Preferably, C1-6 alkyl poly (meth) acrylates, such as poly (meth) acrylate methyl, are mentioned. More preferably, as the (meth) acrylic resin, a methyl methacrylate-based resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight) is used.

  The cellulose ester resin is an ester of cellulose and a fatty acid. Specific examples of the cellulose ester resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Moreover, these copolymers and those obtained by modifying a part of the hydroxyl group with other types of substituents are also included. Among these, cellulose triacetate is particularly preferable. Many products of cellulose triacetate are commercially available, which is advantageous in terms of availability and cost. Examples of commercially available products of cellulose triacetate include Fujitac (registered trademark) TD80 (manufactured by Fuji Film Co., Ltd.), Fujitac (registered trademark) TD80UF (manufactured by Fuji Film Co., Ltd.), Fujitac (registered trademark) TD80UZ (Fuji Film ( Co., Ltd.), Fujitac (registered trademark) TD40UZ (Fuji Film Co., Ltd.), KC8UX2M (Konica Minolta Opto Co., Ltd.), KC4UY (Konica Minolta Opto Co., Ltd.), and the like.

  The polycarbonate resin is an engineering plastic made of a polymer in which monomer units are bonded via a carbonate group, and is a resin having high impact resistance, heat resistance, and flame retardancy. Moreover, since it has high transparency, it is suitably used in optical applications. In optical applications, resins called modified polycarbonates in which the polymer skeleton is modified in order to lower the photoelastic coefficient, copolymerized polycarbonates with improved wavelength dependency, and the like are commercially available and can be suitably used.

  Such polycarbonate resins are widely commercially available. For example, Panlite (registered trademark) (Teijin Chemicals Ltd.), Iupilon (registered trademark) (Mitsubishi Engineering Plastics), SD Polyca (registered trademark) (Sumitomo) Dow Co., Ltd.), Caliber (registered trademark) (Dow Chemical Co., Ltd.) and the like.

  Arbitrary appropriate additives other than said thermoplastic resin may be added to the base film. Examples of such additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, and coloring agents. . The content of the thermoplastic resin exemplified above in the base film is preferably 50 to 100% by weight, more preferably 50 to 99% by weight, still more preferably 60 to 98% by weight, and particularly preferably 70 to 97%. % By weight. This is because, if the content of the thermoplastic resin in the base film is less than 50% by weight, the high transparency inherent in the thermoplastic resin may not be sufficiently exhibited.

  Although the thickness of a base film can be determined suitably, generally 1-500 micrometers is preferable from the point of workability | operativity, such as intensity | strength and a handleability, 1-300 micrometers is more preferable, Furthermore, 5-200 micrometers is preferable. As for the thickness of a base film, 5-150 micrometers is the most preferable.

  The base film may be subjected to corona treatment, plasma treatment, flame treatment or the like on at least the surface on which the resin layer is formed in order to improve the adhesion with the resin layer. Moreover, in order to improve adhesiveness, you may form thin layers, such as a primer layer and an adhesive bond layer, on the surface of the side in which the resin layer of a base film is formed. In addition, a base film here means what does not contain an adhesive bond layer, a corona treatment layer, etc.

(Resin layer)
A polyvinyl alcohol resin is used for the resin layer. As the polyvinyl alcohol resin used in the present invention, those having a saponification degree of 90 mol% to 100 mol% are suitably used, and modified polyvinyl alcohol partially modified may be used. For example, polyvinyl alcohol resin modified with olefins such as ethylene and propylene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, alkyl esters of unsaturated carboxylic acid, acrylamide, and the like by several percent. The average degree of polymerization of the polyvinyl alcohol-based resin is not particularly limited, but is preferably 100 to 10,000, and more preferably 1500 to 10,000.

  Examples of the polyvinyl alcohol resin that gives such characteristics include PVA124 (degree of saponification: 98.0 to 99.0 mol%) and PVA117 (degree of saponification: 98.0 to 99.0 mol) manufactured by Kuraray Co., Ltd. %), PVA624 (degree of saponification: 95.0 to 96.0 mol%), PVA617 (degree of saponification: 94.5 to 95.5 mol%), etc .; for example, AH- manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 26 (degree of saponification: 97.0-98.8 mol%), AH-22 (degree of saponification: 97.5-98.5 mol%), NH-18 (degree of saponification: 98.0-99. 0 mol%), N-300 (degree of saponification: 98.0 to 99.0 mol%) and the like; for example, JF-17 (degree of saponification: 98.0 to 99.0) of Nippon Vinegar Pival Co., Ltd. Mol%), JF-17L (degree of saponification: 98.0-99.0 mol%), JF- 0 (saponification degree: 98.0 to 99.0 mol%) can be preferably used include such.

[Stretching step (S20)]
Here, the laminated film consisting of the base film and the resin layer is uniaxially stretched. Preferably, uniaxial stretching is performed so that the stretching ratio is more than 5 times and not more than 17 times. More preferably, it is uniaxially stretched so that the stretch ratio is more than 5 times and not more than 8 times. When the draw ratio is 5 times or less, the resin layer made of the polyvinyl alcohol-based resin is not sufficiently oriented, and as a result, the degree of polarization of the polarizer layer may not be sufficiently high. On the other hand, if the draw ratio exceeds 17 times, the laminated film is likely to break during stretching, and at the same time, the thickness of the stretched film becomes unnecessarily thin, and the workability and handling properties in the subsequent process may be reduced. The stretching process in the stretching step (S20) is not limited to stretching in one stage, and can be performed in multiple stages. In this case, the second and subsequent stretching processes may be performed in the stretching process (S20), but may be performed simultaneously with the processes in the dyeing process (S30) and the crosslinking process (S40). Thus, when extending | stretching in multiple steps, extending | stretching process is performed so that it may become a draw ratio exceeding 5 times combining all the steps of an extending | stretching process.

  In the stretching step (S20) in the present embodiment, a longitudinal stretching process performed in the longitudinal direction of the laminated film, a lateral stretching process stretching in the width direction, and the like can be performed. Examples of the longitudinal stretching method include an inter-roll stretching method and a compression stretching method, and examples of the transverse stretching method include a tenter method.

  In addition, as the stretching treatment, either a wet stretching method or a dry stretching method can be adopted, but the use of the dry stretching method is preferable because the temperature at which the laminated film is stretched can be selected from a wide range.

[Dyeing step (S30)]
Here, the resin layer of the laminated film after stretching is dyed with a dichroic dye. Examples of the dichroic dye include iodine and organic dyes. Examples of organic dyes include Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Spura Blue G, Spura Blue GL, Spura Orange GL, Direct Sky Blue, Direct First Orange S, First Black, etc. can be used. One kind of these dichroic substances may be used, or two or more kinds may be used in combination.

  The dyeing step is performed, for example, by immersing the entire laminated film in a solution (dyeing solution) containing the dichroic dye. As the staining solution, a solution in which the above dichroic dye is dissolved in a solvent can be used. As a solvent for the dyeing solution, water is generally used, but an organic solvent compatible with water may be further added. The concentration of the dichroic dye is preferably 0.01 to 10% by weight, more preferably 0.02 to 7% by weight, and particularly preferably 0.025 to 5% by weight.

  When iodine is used as the dichroic dye, it is preferable to further add an iodide because the dyeing efficiency can be further improved. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and iodide. Examples include titanium. The addition ratio of these iodides is preferably 0.01 to 20% by weight in the dyeing solution. Of the iodides, it is preferable to add potassium iodide. When potassium iodide is added, the ratio of iodine to potassium iodide is preferably in the range of 1: 5 to 1: 100, more preferably in the range of 1: 6 to 1:80 by weight. , Particularly preferably in the range of 1: 7 to 1:70.

  The immersion time of the laminated film in the dyeing solution is not particularly limited, but it is usually preferably in the range of 15 seconds to 15 minutes, more preferably 30 seconds to 3 minutes. Moreover, it is preferable that it is in the range of 10-60 degreeC, and, as for the temperature of a dyeing | staining solution, it is more preferable that it exists in the range of 20-40 degreeC.

  The dyeing treatment can be performed simultaneously with the stretching process, but after the stretching process is performed on the unstretched film so that the dichroic dye adsorbed on the polyvinyl alcohol-based resin can be well oriented. It is preferable to do so. At this time, it may be simply dyed what has been previously stretched at a target magnification, or may be a method in which a stretch previously stretched at a low magnification is re-stretched during dyeing to reach the target magnification in total. good. Further, when the stretching is performed during the subsequent crosslinking treatment, the stretching can be limited to a low magnification. In this case, adjustment may be made in a timely manner so as to reach the desired magnification after the crosslinking treatment.

[Crosslinking step (S40)]
Following the dyeing step (S30), the crosslinking step (S40) is performed. The crosslinking step can be performed, for example, by immersing the laminated film that has undergone the dyeing step (S30) in a solution containing a crosslinking agent (crosslinking solution). Conventionally known substances can be used as the crosslinking agent. Examples thereof include boron compounds such as boric acid and borax, glyoxal, and glutaraldehyde. One kind of these may be used, or two or more kinds may be used in combination.

  As the crosslinking solution, a solution in which a crosslinking agent is dissolved in a solvent can be used. As the solvent, for example, water can be used, but an organic solvent compatible with water may be further included. Although the density | concentration of the crosslinking agent in a crosslinking solution is not limited to this, It is preferable to exist in the range of 1-20 weight%, and it is more preferable that it is 6-15 weight%.

  Iodide may be added to the crosslinking solution. By adding iodide, the in-plane polarization characteristics of the resin layer can be made more uniform. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. Is mentioned. The iodide content is 0.05 to 15% by weight, more preferably 0.5 to 8% by weight.

  The immersion time of the laminated film in the crosslinking solution is usually preferably from 15 seconds to 20 minutes, and more preferably from 30 seconds to 15 minutes. Moreover, it is preferable that the temperature of a crosslinking solution exists in the range of 10-90 degreeC.

  In addition, a bridge | crosslinking process can also be performed simultaneously with a dyeing process by mix | blending a crosslinking agent in a dyeing solution. Moreover, what was previously extended | stretched by target magnification may be only bridge | crosslinked, and a crosslinking process and an extending | stretching process may be performed simultaneously. You may make it reach | attain the target magnification in total by extending | stretching the stretched film previously extended | stretched by the low magnification by the extending | stretching process again during a crosslinking process.

  It is preferable to perform a washing step after the crosslinking step. As the washing step, a water washing treatment can be performed. The water washing treatment can usually be performed by immersing the stretched film in pure water such as ion exchange water or distilled water. The water washing temperature is usually in the range of 3 to 50 ° C, preferably 4 to 20 ° C. The immersion time is usually 2 to 300 seconds, preferably 3 to 240 seconds.

  In the washing step, washing treatment with an iodide solution and water washing treatment may be combined, and a solution in which liquid alcohol such as methanol, ethanol, isopropyl alcohol, butanol, propanol or the like is appropriately blended may be used. Through the above steps, the resin layer has a function as a polarizer. In this specification, a resin layer having a function as a polarizer is referred to as a polarizer layer.

[Removal step before bonding (S50)]
For the cutting of the laminated film in the pre-bonding removal step (S50), a method capable of continuously treating a long length such as a roll is preferable. Although it does not specifically limit as a method, For example, the method generally called the slitter etc. can be used suitably.

  As an example of the slitter, for example, there is a method using a razor blade called a leather blade. Even with the method using the same leather blade, there is a hollow cut that slits in the air without providing a backup guide, and a groove roll method that stabilizes the meandering of the slit by inserting the blade into a roll with a groove as a backup guide is there. In addition, two circular blades called shear blades are used for slitting by applying contact pressure to the lower blade with the upper blade while rotating according to the film transport, and blades called shear blades and score blades A method of slitting by pressing it against a quenching roll or the like, and further, a method of slitting while cutting like scissors by combining two shear blades. Among them, the “groove roll method using a leather blade”, which is a method that can easily change the slit position of the film and is easy to travel, is preferably used.

  Since this pre-bonding removal step (S50) does not require a large-scale device, it is efficient to incorporate and implement it in any other step. For example, an edge removing device such as a slitter is installed immediately after the cross-linking step (S40), and after removing the end portion (first end portion) there, it can be put into the drying step as it is. Similarly, it may be installed immediately after the drying step. Of course, only the slit process may exist as another independent process, and as an example of such an independent process, for example, a slitter such as a rewinder for rewinding a roll is installed. Things. However, it is usually preferable from the viewpoint of productivity that these steps are continuous in one line, and the crosslinking step (S40), the pre-bonding removal step (S50), and the bonding step (S60) are successively performed in this order. It is preferable that it is the equipment. Moreover, it is preferable that the drying process of a polarizer exists in any one or both before and after the removal process before bonding. Any appropriate method (for example, natural drying, ventilation drying, heat drying) can be adopted as the drying step. For example, the drying temperature in the case of heat drying is usually 20 to 95 ° C., and the drying time is usually about 1 to 15 minutes.

  The main cause for the film that does not remove the end (first end) to cause a problem when the protective film is bonded is abrupt due to wave curling, warping, folding, or the like of the end that occurs in the crosslinking step (S40). There are many problems such as thickness differences, and there are many problems caused by the accumulation of the adhesive in the parts having such thickness differences (for example, blue deterioration of the polarizer due to poor drying of the pools). Moreover, when it has the area | region (3rd edge part) which does not form a resin layer in a lamination process (S10), and has not removed this area | region (3rd edge part) before or after an extending process (S20). In the stretching step (S20), the end distortion and wave curl, and further the step difference between the coated part and the non-coated part further promotes problems during bonding. From this point of view, in the pre-bonding removal step (S50), not only the third end that does not form the resin layer is removed, but also the thickness is extremely reduced by removing from the inner side slightly from the third end. It is preferable to remove different portions. Of course, when the thickness is relatively constant up to the end and it is not necessary to remove the end, the first end may be removed so as to coincide with the third end.

  About the removal process before dyeing | staining (S25) in 3rd Embodiment, it can carry out by the method similar to the above-mentioned removal process before bonding (S50).

[Bonding process (S60)]
Here, a protective film is bonded to the surface of the polarizer layer opposite to the surface on the base film side to obtain a polarizing plate. As a method of bonding a protective film, the method of bonding a polarizer layer and a protective film with an adhesive, and the method of bonding a polarizer layer surface and a protective film with an adhesive are mentioned.

(Protective film)
The protective film used in the bonding step (S50) may be a simple protective film having no optical function, or a protective film having an optical function such as a retardation film or a brightness enhancement film. The material of the protective film is not particularly limited. Examples of the film that have been widely used in the art include polyester-based resin films made of a resin such as butylene terephthalate, polycarbonate-based resin films, acrylic-based resin films, and polypropylene-based resin films.

  Examples of the cyclic polyolefin-based resin include appropriate commercial products such as Topas (registered trademark) (manufactured by Ticona), Arton (registered trademark) (manufactured by JSR Corporation), ZEONOR (registered trademark) (Nippon ZEON ( ZEONEX (registered trademark) (manufactured by Nippon Zeon Co., Ltd.), Apel (registered trademark) (manufactured by Mitsui Chemicals, Inc.) can be suitably used. When such a cyclic polyolefin resin is formed into a film, a known method such as a solvent casting method or a melt extrusion method is appropriately used. In addition, pre-filmed cyclic polyolefins such as Essina (registered trademark) (manufactured by Sekisui Chemical Co., Ltd.), SCA40 (manufactured by Sekisui Chemical Co., Ltd.), Zeonoa (registered trademark) film (manufactured by Optes Co., Ltd.), etc. A commercial product of a film made of a resin may be used.

  The cyclic polyolefin resin film may be uniaxially stretched or biaxially stretched. An arbitrary retardation value can be imparted to the cyclic polyolefin-based resin film by stretching. Stretching is usually performed continuously while unwinding the film roll, and is stretched in the heating furnace in the roll traveling direction, the direction perpendicular to the traveling direction, or both. The temperature of the heating furnace is usually in the range from the vicinity of the glass transition temperature of the cyclic polyolefin resin to the glass transition temperature + 100 ° C. The draw ratio is usually 1.1 to 6 times, preferably 1.1 to 3.5 times in one direction.

  Since the cyclic polyolefin resin film generally has poor surface activity, the surface to be bonded to the polarizer layer is subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame (flame) treatment, saponification treatment, etc. Is preferred. Among these, plasma treatment and corona treatment that can be performed relatively easily are preferable.

  Examples of the cellulose acetate-based resin film include commercially available products such as Fujitac (registered trademark) TD80 (manufactured by Fuji Film Co., Ltd.), Fujitac (registered trademark) TD80UF (manufactured by Fuji Film Co., Ltd.), and Fujitac (registered trademark). TD80UZ (Fuji Film Co., Ltd.), Fujitac (registered trademark) TD40UZ (Fuji Film Co., Ltd.), KC8UX2M (Konica Minolta Opto Co., Ltd.), KC4UY (Konica Minolta Opto Co., Ltd.) are preferably used. be able to.

  A liquid crystal layer or the like may be formed on the surface of the cellulose acetate-based resin film in order to improve viewing angle characteristics. Moreover, in order to provide a phase difference, what stretched the cellulose acetate type-resin film may be used. The cellulose acetate-based resin film is usually subjected to a saponification treatment in order to improve the adhesiveness with the polarizing film. As the saponification treatment, a method of immersing in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide can be employed.

  Optical layers such as a hard coat layer, an antiglare layer, and an antireflection layer can be formed on the surface of the protective film as described above. The method for forming these optical layers on the surface of the protective film is not particularly limited, and a known method can be used.

  The thickness of the protective film is preferably thin, from the demand for thinning, preferably 88 μm or less, and more preferably 48 μm or less. If it is too thin, the strength is lowered and the processability is poor, and therefore it is preferably 5 μm or more.

(Adhesive)
The pressure-sensitive adhesive used for bonding the protective film and the polarizer layer is usually based on an acrylic resin, styrene resin, silicone resin or the like as a base polymer, and cross-linked with an isocyanate compound, an epoxy compound, an aziridine compound, or the like. It consists of the composition which added the agent. Furthermore, it can also be set as the adhesive layer which contains microparticles | fine-particles and shows light-scattering property.

  The thickness of the pressure-sensitive adhesive layer is preferably 1 to 40 μm, but it is preferably applied thinly, and more preferably 3 to 25 μm, as long as the workability and durability characteristics are not impaired. When it is 3 to 25 μm, it has good processability and is also suitable for suppressing the dimensional change of the polarizing film. When the pressure-sensitive adhesive layer is less than 1 μm, the tackiness is lowered, and when it exceeds 40 μm, problems such as the pressure-sensitive adhesive protruding easily occur.

  In the method of bonding a protective film to a polarizer layer with an adhesive, after providing an adhesive layer on the protective film surface, it may be bonded to the polarizer layer, or an adhesive layer is provided on the polarizer layer surface. After that, you may paste a protective film here.

  The method for forming the pressure-sensitive adhesive layer is not particularly limited, and a solution containing each component including the above-mentioned base polymer is applied to the protective film surface or the polarizer layer surface, and dried to form the pressure-sensitive adhesive layer. After the formation, the protective film and the polarizer layer may be bonded together, or after the pressure-sensitive adhesive layer is formed on the separator, it may be transferred and laminated on the protective film surface or the polarizer layer surface. Further, when the pressure-sensitive adhesive layer is formed on the protective film or the polarizer layer surface, if necessary, the protective film or the polarizer layer surface, or one or both of the pressure-sensitive adhesives may be subjected to an adhesion treatment, for example, a corona treatment. .

(adhesive)
Examples of the adhesive used for bonding the protective film and the polarizer layer include a water-based adhesive using a polyvinyl alcohol-based resin aqueous solution, a water-based two-component urethane-based emulsion adhesive, and the like. When using a cellulose acetate film hydrophilized by a saponification treatment or the like as the protective film, a polyvinyl alcohol resin aqueous solution is suitably used as an aqueous adhesive for bonding to the polarizer layer. 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. A polyhydric aldehyde, a water-soluble epoxy compound, a melamine compound, a zirconia compound, a zinc compound, or the like may be added as an additive to the water-based adhesive. When such an aqueous adhesive is used, the adhesive layer obtained therefrom is usually 1 μm or less.

  The method of laminating the polarizer layer and the protective film using the water-based adhesive is not particularly limited. For example, the adhesive is uniformly applied to the surface of the polarizer layer and / or the protective film, and then applied to the coated surface. Examples include a method in which the other film is stacked and bonded with a roll or the like and dried. Usually, an adhesive agent is apply | coated at the temperature of 15-40 degreeC after the preparation, and the bonding temperature is the range of 15-30 degreeC normally.

  When using an aqueous adhesive, after laminating the polarizer layer and the protective film, the laminated film is dried in order to remove water contained in the aqueous adhesive. The temperature of the drying furnace is preferably 30 to 90 ° C. When the temperature is lower than 30 ° C., the polarizer layer surface and the protective film surface tend to be easily peeled off. If it is 90 ° C. or higher, the optical performance may be deteriorated by heat. The drying time can be 10 to 1000 seconds, and from the viewpoint of productivity, it is preferably 60 to 750 seconds, and more preferably 150 to 600 seconds.

  After drying, it may be further cured at room temperature or slightly higher temperature, for example, at a temperature of about 20 to 45 ° C. for about 12 to 600 hours. The temperature at the time of curing is generally set lower than the temperature adopted at the time of drying.

  Moreover, a photocurable adhesive can also be used as an adhesive at the time of bonding a polarizer layer and a protective film. Here, the photocurable adhesive is an adhesive that is cured by irradiating active energy rays such as ultraviolet rays. For example, the adhesive includes a polymerizable compound and a photopolymerization initiator, and includes a photoreactive resin. And those containing a binder resin and a photoreactive cross-linking agent. Examples of the polymerizable compound include photopolymerizable monomers such as a photocurable epoxy monomer, a photocurable acrylic monomer, and a photocurable urethane monomer, and oligomers derived from these monomers. Examples of the photopolymerization initiator include those containing substances that generate active species such as neutral radicals, anion radicals, and cation radicals by irradiation with active energy rays such as ultraviolet rays. As a photocurable adhesive containing a polymerizable compound and a photopolymerization initiator, those containing a photocurable epoxy monomer and a photocationic polymerization initiator are preferable.

  In addition, as above-mentioned, although the film which does not remove an edge part (1st edge part) includes the partial accumulation of the adhesive agent by folding or a wrinkle as a malfunction which arises at the time of bonding of a protective film, photocuring If this reservoir portion is heated when the adhesive is used, this portion may be yellowed and deteriorated. From the viewpoint of avoiding this yellowing deterioration, the production of the present invention in which the first end portion is removed. The method is effective.

  As a method of bonding the polarizer layer and the protective film with a photocurable adhesive, a conventionally known method can be used, for example, a casting method, a Mayer bar coating method, a gravure coating method, a comma coater method, Examples include a method of applying an adhesive on the adhesive surface of the polarizer layer and / or the protective film and superimposing the two by a doctor plate method, a die coating method, a dip coating method, a spraying method, or the like. The casting method is a method in which a polarizing film or a protective film, which is an object to be coated, is moved in a substantially vertical direction, a substantially horizontal direction, or an oblique direction between the two, and an adhesive is allowed to flow down and spread on the surface. It is.

  After the adhesive is applied to the surface of the polarizer layer or the protective film, the polarizing film and the protective film are bonded together by being sandwiched by a nip roll or the like through the adhesive application surface. In addition, there is a method in which an adhesive is dropped between the polarizer layer and the protective film in a state where the polarizer layer and the protective film are partially overlapped, and then this laminated film is pressed with a roll or the like to be uniformly spread. It can be preferably used. In this case, a metal, rubber, or the like can be used as the material of the roll. Furthermore, after dropping an adhesive agent between a polarizer layer and a protective film, the method of passing this laminated film between rolls and pressing and spreading it is also preferably employed. In this case, these rolls may be made of the same material or different materials. The thickness of the adhesive layer after being bonded using the nip roll or the like before drying or curing is preferably 5 μm or less and 0.01 μm or more.

  In order to improve adhesion, the surface of the polarizer layer and / or the protective film may be appropriately subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame (flame) treatment, saponification treatment, etc. Good. Examples of the saponification treatment include a method of immersing in an aqueous alkali solution such as sodium hydroxide or potassium hydroxide.

  When a photocurable resin is used as an adhesive, the photocurable adhesive is cured by irradiating an active energy ray after joining the polarizing film and the protective film. The light source of the active energy ray is not particularly limited, but an active energy ray having a light emission distribution at a wavelength of 400 nm or less is preferable. A microwave excitation mercury lamp, a metal halide lamp and the like are preferably used.

The light irradiation intensity to the photocurable adhesive is appropriately determined depending on the composition of the photocurable adhesive and is not particularly limited, but the irradiation intensity in the wavelength region effective for activating the polymerization initiator is 0.1 to 6000 mW / it is preferable that the cm ^2. When the irradiation intensity is 0.1 mW / cm ² or more, the reaction time does not become too long, and when it is 6000 mW / cm ² or less, the epoxy is generated by the heat radiated from the light source and the heat generated when the photo-curable adhesive is cured. There is little risk of yellowing of the resin or deterioration of the polarizing film. The light irradiation time to the photocurable adhesive is not particularly limited and is applied according to the photocurable adhesive to be cured, but the integrated light amount expressed as the product of the irradiation intensity and the irradiation time. Is preferably set to be 10 to 10,000 mJ / cm ² . When the cumulative amount of light to the photocurable adhesive is 10 mJ / cm ² or more, a sufficient amount of active species derived from the polymerization initiator can be generated to allow the curing reaction to proceed more reliably, and at 10,000 mJ / cm ² or less. In some cases, irradiation time does not become too long and good productivity can be maintained. The thickness of the adhesive layer after irradiation with active energy rays is usually about 0.001 to 5 μm, preferably 0.01 μm or more and 2 μm or less, more preferably 0.01 μm or more and 1 μm or less.

  When curing a photo-curable adhesive by irradiation with active energy rays, curing should be performed under conditions that do not deteriorate the functions of the polarizing plate, such as the degree of polarization of the polarizing film, the transmittance and hue, and the transparency of the protective film. preferable.

[Peeling step (S70)]
In the manufacturing method of this invention, the peeling process (S70) of a base film can be performed after the bonding process (S60) which bonds a protective film to a polarizer layer. In the base film peeling step (S70), the base film is peeled from the laminated film. The peeling method of a base film is not specifically limited, It can peel by the method similar to the peeling process of the peeling film performed with a normal polarizing plate with an adhesive. After the pasting step (S60), it may be peeled off as it is, or after it is wound up in a roll shape, it may be peeled off by providing another peeling step.

[Example 1]
(1) Production of base film On both sides of a resin layer comprising a random copolymer of propylene / ethylene containing about 5% by weight of an ethylene unit (“Sumitomo Noblen W151” manufactured by Sumitomo Chemical Co., Ltd., melting point Tm = 138 ° C.) A base film roll having a three-layer structure in which a homopropylene propylene homopolymer (“Sumitomo Nobrene FLX80E4” manufactured by Sumitomo Chemical Co., Ltd., melting point Tm = 163 ° C.) is disposed is used as a multilayer extruder. It was produced by the coextrusion molding used. The total thickness of the obtained base film roll was 100 μm, and the thickness ratio (FLX80E4 / W151 / FLX80E4) of each layer was 3/4/3.

(2) Formation of primer layer Polyvinyl alcohol powder (“Z-200” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., average polymerization degree 1100, average saponification degree 99.5 mol%) was dissolved in 95 ° C. hot water, A polyvinyl alcohol aqueous solution having a concentration of 3% by weight was prepared. The resulting aqueous solution was mixed with 5 parts by weight of a crosslinking agent (“SUMIREZ RESIN 650” manufactured by Sumitomo Chemical Co., Ltd.) with respect to 6 parts by weight of polyvinyl alcohol powder. The obtained mixed aqueous solution is continuously coated on the corona-treated surface of the base film roll subjected to the corona treatment by using a gravure coater, and dried at 80 ° C. for 10 minutes to obtain a primer having a thickness of 0.2 μm. A layer was formed. This operation was also performed on the opposite side of the base film, and a film composed of “primer layer / base film / primer layer” having a primer layer on both sides was prepared.

(3) Resin layer forming step Polyvinyl alcohol powder (“PVA124” manufactured by Kuraray Co., Ltd., average polymerization degree 2400, average saponification degree 98.0-99.0 mol%) is dissolved in hot water at 95 ° C. to obtain a concentration. An 8% by weight aqueous polyvinyl alcohol solution was prepared. From the base film / primer layer / polyvinyl alcohol resin layer, the obtained aqueous solution was continuously applied onto one primer layer of the base film using a comma coater and dried at 80 ° C. for 5 minutes. A laminated film roll having a three-layer structure was prepared. The thickness of the resin layer made of a polyvinyl alcohol resin was 10.6 μm. Here, the same operation was also performed on the primer layer on the opposite side of the base film, and a resin layer made of a polyvinyl alcohol resin was provided on both sides, “polyvinyl alcohol resin layer / primer layer / base film / primer layer / A laminated film having a configuration of “polyvinyl alcohol-based resin layer” was prepared. Here, polyvinyl alcohol aqueous solution was not apply | coated in the area | region (3rd edge part) of the both ends of 1 cm from the edge of a base film.

(4) Pre-dyeing removal step and stretching step After both end portions (second end portions) of the above-mentioned laminated film roll are cut at a position 2 cm from the end to remove uncoated portions continuously (pre-dye removal step), The film was uniaxially stretched 5.8 times in the machine direction at a stretching temperature of 160 ° C. with an air-to-roll stretching apparatus to obtain a laminated film roll. The thickness of the obtained laminated film roll was 55.2 μm, and the thickness of the polyvinyl alcohol-based resin layer was 5.1 μm.

(5) Dyeing process, crosslinking process, removal process before bonding The dyeing process and the crosslinking process were performed in the following procedure for the laminated film roll after stretching. First, the laminated film is immersed in a dyeing solution at 30 ° C., which is an aqueous solution containing 30 ° C. iodine and potassium iodide, for a residence time of about 150 seconds, and the polyvinyl alcohol resin layer is dyed (dyeing step). Then, the excess iodine solution was washed away with pure water at 10 ° C. Next, it was immersed in a crosslinking solution at 72 ° C., which is an aqueous solution containing boric acid and potassium iodide, so as to have a residence time of about 600 seconds (crosslinking step). After washing with pure water at 10 ° C. for 4 seconds, both ends of this film were slit at 1.5 cm positions from the ends to remove curled portions (first ends) at both ends (before bonding) Removal step). Finally, it was dried at 80 ° C. for 300 seconds to obtain a laminated film roll.

(6) Bonding process Using the laminated film roll which passed the removal process before bonding, the polarizing plate was produced in the following procedure. First, polyvinyl alcohol powder (“KL-318” manufactured by Kuraray Co., Ltd., average polymerization degree 1800) was dissolved in hot water at 95 ° C. to prepare a polyvinyl alcohol aqueous solution having a concentration of 3% by weight. The resulting aqueous solution was mixed with 1 part by weight of a crosslinking agent (“SUMIREZ RESIN 650” manufactured by Sumitomo Chemical Co., Ltd.) with respect to 2 parts by weight of polyvinyl alcohol powder to obtain an adhesive solution.

  Next, after applying the adhesive solution on the polyvinyl alcohol resin layer present on both surfaces of the obtained laminated film roll, a protective film made of triacetyl cellulose (TAC) (manufactured by Konica Minolta Opto Co., Ltd. “ KC4UY ") is bonded from both sides, and a polarizing plate roll comprising 9 layers of protective film / adhesive layer / polarizer layer / primer layer / base material film / primer layer / polarizer layer / adhesive layer / protective film Obtained. The obtained polarizing plate was in a good state in which it was satisfactorily bonded to the end of the polarizer without any problems such as folding at the end of the polarizer, wrinkles, or blue discoloration.

[Example 2]
As the base material, a polyester base material obtained by copolymerization of three types of monomers of 1,4-cyclohexanedimethanol, terephthalic acid, and ethylene glycol was used. The thickness of the base film was 70 μm. A primer layer and a polyvinyl alcohol resin layer were provided in the same manner as in Example 1, and a laminated film having a configuration of “polyvinyl alcohol resin layer / primer layer / base film / primer layer / polyvinyl alcohol resin layer” was prepared. (Lamination process). The thickness of the primer layer was 0.2 μm, and the thickness of the polyvinyl alcohol-based resin layer was 10.4 μm. Again, the polyvinyl alcohol aqueous solution was not applied in the region (third end) at both ends of 1 cm from the end of the base film.

  After removing the area | region (2nd edge part) of both ends of 2 cm from the edge of said laminated film roll (pre-dyeing removal process), it is 4.0 in a vertical direction with the extending | stretching temperature of 110 degreeC with an air extending | stretching apparatus between rolls. The free end uniaxial stretching was performed twice (stretching step) to obtain a laminated film roll. The thickness of the obtained laminated film roll was 40.5 μm, and the thickness of the polyvinyl alcohol-based resin layer was 5.2 μm.

  The obtained laminated film was subjected to a dyeing process in the same manner as in Example 1 and washed, and then the regions (first end portions) 2 cm from the end of the laminated film were continuously removed by slits (before bonding) Removal step). Then, it dried by the same method as Example 1 and obtained the laminated film. A protective film is bonded to both surfaces of the obtained laminated film in the same manner as in Example 1 (bonding process), and protective film / adhesive layer / polarizer layer / primer layer / base film / primer layer / polarized light. A polarizing plate roll comprising 9 layers of child layer / adhesive layer / protective film was obtained. The obtained polarizing plate was in a good state in which it was satisfactorily bonded to the end of the polarizer without any problems such as folding at the end of the polarizer, wrinkles, or blue discoloration.

[Example 3]
The same laminated film roll as in Example 2 was used, but it was used without removing both ends before stretching (without performing the pre-dye removal step). A free-end uniaxial stretching was performed 4.0 times in the longitudinal direction at a stretching temperature of 110 ° C. with an air-to-roll stretching apparatus (stretching process) to obtain a longitudinally stretched laminated film roll. Since the draw ratio was low, there was no problem such as breakage, and the film could be wound as it was. The obtained laminated film was subjected to a dyeing process in the same manner as in Example 1 and washed, and then the regions (first end portions) 2 cm from the end of the laminated film were continuously removed by slits (before bonding) Removal step).

  Then, it dried by the same method as Example 1 and obtained the laminated film. A protective film is bonded to both surfaces of the obtained laminated film in the same manner as in Example 1 (bonding process), and protective film / adhesive layer / polarizer layer / primer layer / base film / primer layer / polarized light. A polarizing plate roll comprising 9 layers of child layer / adhesive layer / protective film was obtained. The obtained polarizing plate was in a good state in which it was satisfactorily bonded to the end of the polarizer without any problems such as folding at the end of the polarizer, wrinkles, or blue discoloration.

[Comparative Example 1]
Protective film / adhesive layer / polarizer layer / primer layer / substrate film / primer layer / polarizer layer / adhesive layer / protection in the same manner as in Example 1 except that the pre-bonding removal step was not performed. A polarizing plate roll consisting of 9 layers of film was obtained. The resulting polarizing plate roll has a slight blue discoloration due to the accumulation of adhesive at the film scraping portion generated from the end, and wrinkles are also generated from the end distortion partially generated in the crosslinking tank. Was.

[Comparative Example 2]
Protective film / adhesive layer / polarizer layer / primer layer / substrate film / primer layer / polarizer layer / adhesive layer / protection in the same manner as in Example 2 except that the pre-bonding removal step was not performed. A polarizing plate roll consisting of 9 layers of film was obtained. The resulting polarizing plate roll has a slight blue discoloration due to the accumulation of adhesive at the film scraping portion generated from the end, and wrinkles are also generated from the end distortion partially generated in the crosslinking tank. Was.

[Comparative Example 3]
Protective film / adhesive layer / polarizer layer / primer layer / substrate film / primer layer / polarizer layer / adhesive layer / protective film as in Comparative Example 2 except that the pre-dye removal step was not performed. A polarizing plate roll consisting of 9 layers was obtained. In the obtained polarizing plate roll, an adhesive is accumulated at the step of the boundary between the coated part / uncoated part (third end part) and a lot of blue discoloration occurs. Many wrinkles and folds occurred from the distortion.

  Table 1 summarizes the outlines of the production methods of Examples 1 to 3 and Comparative Examples 1 to 3 and the state of the edge after bonding.

  The polarizing plate produced by the production method of the present invention can be effectively applied to various display devices including liquid crystal display devices.

  11, 21, 31 Base film, 12a, 22a, 32a Resin layer, 12b, 22b, 32b Polarizer layer, 13, 23, 33 First end, 34 Second end, 21a, 31a Third end.

Claims (3)

A method for producing a polarizing plate having a polarizer layer and a protective film,
A laminating step of forming a polyvinyl alcohol resin layer by applying a polyvinyl alcohol resin solution on at least one surface of the base film to obtain a laminated film;
A stretching step of uniaxially stretching the laminated film;
A dyeing step of dyeing the polyvinyl alcohol-based resin layer of the laminated film subjected to the uniaxial stretching with a dichroic dye;
A crosslinking step in which the polyvinyl alcohol-based resin layer of the laminated film subjected to the dyeing is immersed in a solution containing a crosslinking agent to be crosslinked to form a polarizer layer;
From the laminated film subjected to the cross-linking, a pre-bonding removal step of cutting and removing both first ends in the width direction;
It has a bonding step and the substrate film side of the surface of the polarizer layer in the laminated film obtained by removing the first end portion to be bonded to the protective film using an adhesive on the opposite side, in this order Manufacturing method of polarizing plate.   The method of Claim 1 which has a drying process which dries the said polarizer layer after the said bridge | crosslinking process and before the said pre-bonding removal process.   The method of Claim 1 which has a drying process which dries the said polarizer layer after the said pre-bonding removal process and before the said bonding process.

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