JP6203143B2 - Manufacturing method of polarizing plate - Google Patents

Description

  The present invention relates to a method for producing a polarizing plate in which a protective film is bonded to at least one surface of a polarizer layer.

  The polarizing plate is widely used in image display devices such as liquid crystal display devices. As a polarizing plate, the thing of the structure which bonded the protective film to the single side | surface or both surfaces of the polarizer layer which consists of polyvinyl alcohol-type resin is common. In recent years, with the development of image display devices in mobile devices, thin televisions, and the like, there has been an increasing demand for thinner polarizing plates and thus polarizer layers.

  As a method for producing a polarizing plate comprising a thin film polarizer layer, after stretching a laminated film in which a polyvinyl alcohol resin layer is formed by coating a coating liquid containing a polyvinyl alcohol resin on a base film, The polyvinyl alcohol resin layer is subjected to a dyeing treatment for adsorbing a dichroic dye to produce a polarizing laminated film in which a polarizer layer is formed on the base film, and then the base film in the polarizer layer A method of peeling and removing a base film after pasting a protective film on the opposite surface to form a multilayer film is known (for example, Patent Documents 1 and 2).

  According to the above method, since the polyvinyl alcohol-based resin layer is formed by coating, it is easier to reduce the thickness of the polyvinyl alcohol-based resin layer than to reduce the thickness of a single-layer (single) film made of polyvinyl alcohol-based resin. Therefore, it is easy to reduce the thickness of the polarizer layer. Moreover, since the polyvinyl alcohol-type resin layer and polarizer layer of a thin film are always supported by any film during a manufacturing process, it is excellent also in the handleability of the film in a manufacturing process.

JP 2000-338329 A International Publication No. 2013/018845

  In producing a polarizing plate by the above method, the polyvinyl alcohol-based resin layer peels off from the base film in the stretching process or the dyeing process, or floats (partially peels off, and the base film and the polyvinyl alcohol-based film are separated). In order to prevent a phenomenon in which a gap is generated between the resin layer and the resin layer, it is necessary to firmly adhere the base film and the polyvinyl alcohol resin layer. However, in this case, when the base film is peeled in the step of peeling and removing the base film, problems such as cohesive failure occur in the polarizer layer and the peeled surface of the polarizer layer is likely to be whitened.

  The above-mentioned defects are caused by setting the angle formed by the peeling direction of the base film and the orientation direction of the polarizer layer to a specific angle, and preferably, at the peeling point of the base film, the multilayer film and the polarizing plate Can be effectively suppressed by the method described in Patent Document 2 in which the angle formed by the multilayer film and the base film is made smaller than the angle formed by the multilayer film and the base film. However, it is not always easy to continuously peel the base film while maintaining the conditions regarding these angles, particularly when the polarizer layer and the protective film are thin.

  Therefore, the present invention is a new one that can exfoliate and remove the substrate film cleanly while suppressing the above-mentioned problems even if the adhesion force between the substrate film and the polyvinyl alcohol-based resin layer is high enough to withstand the stretching process and the dyeing process. An object of the present invention is to provide a method for producing a polarizing plate.

The present invention provides the following method for producing a polarizing plate.
[1] A resin layer forming step of obtaining a laminated film by forming a polyvinyl alcohol-based resin layer on at least one surface of a base film;
A stretching step of stretching the laminated film to obtain a stretched film;
A dyeing step of obtaining a polarizing laminated film by dyeing a polyvinyl alcohol-based resin layer of the stretched film with a dichroic dye to form a polarizer layer;
A laminating step of obtaining a multilayer film by laminating a protective film on the surface opposite to the surface on the base film side in the polarizing laminated film;
A peeling step of peeling and removing the base film from the multilayer film to obtain a polarizing plate,
Including
In the peeling step, the multilayer film is wound around a roll on the side opposite to the base film, and when the base film is peeled from the multilayer film, The manufacturing method of a polarizing plate performed so that the surface on the opposite side to a base film may maintain the state which contacted the said roll.

  [2] When the tension of the base film after peeling is A and the tension of the multilayer film before peeling the base film is B, the base film is peeled under conditions satisfying B ≧ 10 × A. [1] The production method according to [1].

  [3] The production method according to [1], wherein the roll is a suction roll, and the base film is peeled off while the multilayer film wound around the roll is sucked by the suction roll.

  [4] The manufacturing method according to any one of [1] to [3], wherein the roll has a diameter of 200 mm or more.

  [5] The manufacturing method according to any one of [1] to [4], wherein the polarizer layer has a thickness of 10 μm or less.

  [6] The manufacturing method according to any one of [1] to [5], wherein the protective film has a thickness of 35 μm or less.

  According to the present invention, it is possible to suppress defects such as cohesive failure of the polarizer layer and whitening of the polarizer layer peeling surface that may occur in the peeling removal process of the base film, and to improve the appearance quality of the obtained polarizing plate. it can.

It is a flowchart which shows the manufacturing method of the polarizing plate which concerns on this invention. It is a schematic sectional drawing which shows an example of the laminated constitution of the laminated | multilayer film obtained at a resin layer formation process. It is a schematic sectional drawing which shows an example of the laminated constitution of the stretched film obtained at a extending process. It is a schematic sectional drawing which shows an example of the laminated constitution of the light-polarizing laminated film obtained at a dyeing process. It is a schematic sectional drawing which shows an example of the laminated constitution of the multilayer film obtained at a 1st bonding process. It is a schematic sectional drawing which shows an example of the layer structure of the polarizing plate with a single-sided protective film obtained by a peeling process. It is a schematic side view which shows the peeling method of the base film in this invention. It is a schematic sectional drawing which shows an example of the laminated constitution of the polarizing plate with a double-sided protective film obtained by a 2nd bonding process.

As FIG. 1 shows, the manufacturing method of the polarizing plate which concerns on this invention has the following process:
Resin layer forming step S10 for obtaining a laminated film by forming a polyvinyl alcohol-based resin layer on at least one surface of the base film,
Stretching step S20 to stretch the laminated film to obtain a stretched film,
Dyeing step S30 to obtain a polarizing laminated film by dyeing a polyvinyl alcohol resin layer of a stretched film with a dichroic dye to form a polarizer layer,
1st bonding process S40 which bonds a 1st protective film on the surface on the opposite side to the surface at the side of the base film in a light-polarizing laminated film, and obtains a multilayer film,
Peeling step S50 to obtain a polarizing plate (a polarizing plate with a single-sided protective film) by peeling and removing the base film from the multilayer film
Are included in this order.

  As will be described later, the method for producing a polarizing plate according to the present invention is a second laminating step in which a polarizing plate with a double-sided protective film is obtained by laminating a second protective film on the polarizer layer in the polarizing plate with a single-sided protective film. S60 can also be included. Hereinafter, each step will be described in detail with reference to the drawings.

[1] Resin layer forming step S10
With reference to FIG. 2, this step is a step of forming the laminated film 100 by forming the polyvinyl alcohol-based resin layer 6 on at least one surface of the base film 30. The polyvinyl alcohol-based resin layer 6 is a layer that becomes the polarizer layer 5 (FIG. 4) through stretching and dyeing. The polyvinyl alcohol-based resin layer 6 can be formed by applying a coating liquid containing a polyvinyl alcohol-based resin to one or both surfaces of the base film 30 and drying it. The method of forming the polyvinyl alcohol-based resin layer 6 by such coating is advantageous in that a thin polarizer layer 5 can be easily obtained. Typically, resin layer formation process S10 is continuously performed, unwinding the base film 30 from the film roll which is a wound product of the long base film 30, and conveying this. The film conveyance can be performed using a guide roll or the like.

(Base film)
The base film 30 can be composed of a thermoplastic resin, and among them, it is preferably composed of a thermoplastic resin that is excellent in transparency, mechanical strength, thermal stability, stretchability, and the like. Specific examples of such thermoplastic resins include, for example, polyolefin resins such as chain polyolefin resins and cyclic polyolefin resins (norbornene resins, etc.); polyester resins; (meth) acrylic resins; cellulose triacetate, Cellulose ester resins such as cellulose diacetate; Polycarbonate resins; Polyvinyl alcohol resins; Polyvinyl acetate resins; Polyarylate resins; Polystyrene resins; Polyethersulfone resins; Polysulfone resins; Polyamide resins; System resins; and mixtures and copolymers thereof.

  The base film 30 may have a single-layer structure made of one resin layer made of one kind or two or more kinds of thermoplastic resins, or a plurality of resin layers made of one kind or two or more kinds of thermoplastic resins. A laminated multilayer structure may be used. The base film 30 is preferably made of a resin that can be stretched at a stretching temperature suitable for stretching the polyvinyl alcohol-based resin layer 6 when the laminated film 100 is stretched in the stretching step S20 described later.

  Examples of the chain polyolefin-based resin include a homopolymer of a chain olefin such as a polyethylene resin and a polypropylene resin, and a copolymer composed of two or more chain olefins. The base film 30 made of a chain polyolefin-based resin is preferable in that it is easily stretched stably at a high magnification. Among them, the base film 30 is composed mainly of a polypropylene resin (a polypropylene resin that is a propylene homopolymer or a copolymer mainly composed of propylene), a polyethylene resin (a polyethylene resin that is an ethylene homopolymer or ethylene). It is more preferable that it consists of a copolymer.

  The copolymer mainly composed of propylene, which is one example suitably used as the thermoplastic resin constituting the base film 30, is a copolymer of propylene and another monomer copolymerizable therewith.

  Examples of other monomers copolymerizable with propylene include ethylene and α-olefin. 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, for example, linear monoolefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene; 3 -Branched monoolefins such as methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene; and vinylcyclohexane. The copolymer of propylene and other monomers copolymerizable therewith may be a random copolymer or a block copolymer.

  Content of the said other monomer is 0.1-20 weight% in a copolymer, for example, Preferably it is 0.5-10 weight%. The content of other monomers in the copolymer can be determined by measuring infrared (IR) spectrum according to the method described on page 616 of "Polymer Analysis Handbook" (1995, published by Kinokuniya Shoten). Can be sought.

  Among these, as the polypropylene resin, a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-1-butene random copolymer or a propylene-ethylene-1-butene random copolymer is preferably used.

  It is preferable that the stereoregularity of the polypropylene resin is substantially isotactic or syndiotactic. The base film 30 made of a polypropylene-based resin having substantially isotactic or syndiotactic stereoregularity has relatively good handleability and excellent mechanical strength in a high temperature environment.

  The cyclic polyolefin resin is a general term for resins that are polymerized using a 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 of cyclic polyolefin resins include ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins and chain olefins such as ethylene and propylene (typically Are random copolymers), graft polymers obtained by modifying them with unsaturated carboxylic acids or their derivatives, and hydrides thereof. Among these, norbornene resins using norbornene monomers such as norbornene and polycyclic norbornene monomers as cyclic olefins are preferably used.

  The polyester resin is a resin having an ester bond, and is generally made of a polycondensate of a polyvalent carboxylic acid or a derivative thereof and a polyhydric alcohol. As the polyvalent carboxylic acid or a derivative thereof, a divalent dicarboxylic acid or a derivative thereof can be used, and examples thereof include terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalenedicarboxylate. As the polyhydric alcohol, a divalent diol can be used, and examples thereof include ethylene glycol, propanediol, butanediol, neopentyl glycol, and cyclohexanedimethanol.

  A typical example of the polyester resin is polyethylene terephthalate which is a polycondensate 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. Further, a copolymerized polyester having a crystallinity lowered (or made amorphous) by further copolymerizing another monomer with a polyethylene terephthalate skeleton is also preferably used. Examples of such resins include those obtained by copolymerizing cyclohexanedimethanol and isophthalic acid. Since these resins are also excellent in stretchability, they can be suitably used.

  Specific examples of polyester resins other than polyethylene terephthalate and copolymers thereof include, for example, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polycyclohexanedimethyl terephthalate. Polycyclohexanedimethyl naphthalate.

The (meth) acrylic resin is a resin containing a compound having a (meth) acryloyl group as a main constituent monomer. Specific examples of (meth) acrylic resins include, for example, poly (meth) acrylic acid esters such as polymethyl methacrylate; methyl methacrylate- (meth) acrylic acid copolymer; methyl methacrylate- (meth) acrylic acid Ester copolymer; methyl methacrylate-acrylic ester- (meth) acrylic acid copolymer; (meth) methyl acrylate-styrene copolymer (MS resin etc.); methyl methacrylate and alicyclic hydrocarbon group And a copolymer (for example, methyl methacrylate-cyclohexyl methacrylate copolymer, methyl methacrylate- (meth) acrylate norbornyl copolymer). Preferably, a polymer based on a poly (meth) acrylic acid C _1-6 alkyl ester such as poly (meth) acrylic acid methyl is used, and more preferably methyl methacrylate is the main component (50-100). % Methyl methacrylate resin 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. Further, these copolymers and those in which a part of the hydroxyl group is modified with other substituents are also included. Among these, cellulose triacetate (triacetyl cellulose) is particularly preferable. Many products of cellulose triacetate are commercially available, which is advantageous in terms of availability and cost.

  The polycarbonate-based 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, flame retardancy, and transparency. The polycarbonate resin constituting the base film 30 may be a resin called a modified polycarbonate in which the polymer skeleton is modified in order to lower the photoelastic coefficient, or a copolymer polycarbonate having improved wavelength dependency.

  Among these, polypropylene resins are preferably used from the viewpoints of stretchability and heat resistance.

  The base film 30 can contain any appropriate additive in addition to the above thermoplastic resin. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, and a coloring agent. The content of the thermoplastic resin in the base film 30 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. .

  The thickness of the base film 30 is usually 1 to 500 μm, preferably 1 to 300 μm, more preferably 5 to 200 μm, and still more preferably 5 to 150 μm from the viewpoints of strength and handleability.

(Formation of polyvinyl alcohol resin layer)
The coating liquid applied to the base film 30 is preferably a polyvinyl alcohol resin solution obtained by dissolving a polyvinyl alcohol resin powder in a good solvent (for example, water). As the polyvinyl alcohol resin, a saponified polyvinyl acetate resin can be used. Examples of the polyvinyl acetate-based resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith. Examples of other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group.

  The degree of saponification of the polyvinyl alcohol-based resin can be in the range of 80.0 to 100.0 mol%, preferably in the range of 90.0 to 99.5 mol%, more preferably 94.0. It is in the range of ˜99.0 mol%. When the degree of saponification is less than 80.0 mol%, the water resistance and heat-and-moisture resistance of the polarizing plate are lowered. When a polyvinyl alcohol-based resin having a saponification degree exceeding 99.5 mol% is used, the dyeing speed of the dichroic dye becomes slow, the productivity is lowered, and a polarizing plate having sufficient polarization performance cannot be obtained. There is.

The degree of saponification is the unit ratio (mol%) of the proportion of acetate groups (acetoxy groups: —OCOCH ₃ ) contained in polyvinyl acetate resin, which is a raw material for polyvinyl alcohol resins, changed to hydroxyl groups by the saponification step. The following formula:
Saponification degree (mol%) = 100 × (number of hydroxyl groups) ÷ (number of hydroxyl groups + number of acetate groups)
Defined by The degree of saponification can be determined according to JIS K 6726-1994. The higher the degree of saponification, the higher the proportion of hydroxyl groups, and thus the lower the proportion of acetate groups that inhibit crystallization.

  The polyvinyl alcohol-based resin may be a modified polyvinyl alcohol partially modified. For example, polyvinyl alcohol resins 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 acids, acrylamide, and the like can be used. The proportion of modification is preferably less than 30 mol%, and more preferably less than 10%. When modification exceeding 30 mol% is performed, the dichroic dye is hardly adsorbed, and it is difficult to obtain a polarizing plate having sufficient polarization performance.

  The average degree of polymerization of the polyvinyl alcohol-based resin is preferably 100 to 10,000, more preferably 1500 to 8000, and further preferably 2000 to 5000. The average degree of polymerization of the polyvinyl alcohol resin can also be determined according to JIS K 6726-1994.

  The coating liquid is applied to the base film 30 by a wire bar coating method; a roll coating method such as reverse coating or gravure coating; a die coating method; a comma coating method; a lip coating method; a spin coating method; The method can be appropriately selected from a method such as a fountain coating method, a dipping method, and a spray method.

  The drying temperature and drying time of the coating layer (polyvinyl alcohol-based resin layer before drying) are set according to the type of solvent contained in the coating solution. A drying temperature is 50-200 degreeC, for example, Preferably it is 60-150 degreeC. When the solvent contains water, the drying temperature is preferably 80 ° C. or higher.

  The polyvinyl alcohol-based resin layer 6 may be formed only on one surface of the base film 30 or may be formed on both surfaces. When formed on both sides, curling of the film that may occur during the production of the polarizing laminated film 300 (see FIG. 4) can be suppressed and two polarizing plates can be obtained from one polarizing laminated film 300. It is also advantageous in terms of plate production efficiency.

  The thickness of the polyvinyl alcohol-based resin layer 6 in the laminated film 100 is preferably 3 to 30 μm, more preferably 5 to 20 μm. If the polyvinyl alcohol-based resin layer 6 has a thickness within this range, the dichroic dye has good dyeability and excellent polarization performance through a stretching step S20 and a dyeing step S30 described later, and is sufficiently thin (for example, A polarizer layer 5 (thickness of 10 μm or less) can be obtained.

  Prior to the application of the coating liquid, in order to improve the adhesion between the base film 30 and the polyvinyl alcohol resin layer 6, at least the surface of the base film 30 on the side where the polyvinyl alcohol resin layer 6 is formed is provided. Corona treatment, plasma treatment, flame (flame) treatment or the like may be performed. For the same reason, the polyvinyl alcohol-based resin layer 6 may be formed on the base film 30 via a primer layer or the like.

  The primer layer can be formed by applying a primer layer forming coating solution to the surface of the substrate film 30 and then drying it. This coating solution includes a component that exhibits a certain degree of strong adhesion to both the base film 30 and the polyvinyl alcohol-based resin layer 6, and usually includes a resin component that provides such adhesion and a solvent. . As the resin component, a thermoplastic resin excellent in transparency, thermal stability, stretchability and the like is preferably used, and examples thereof include (meth) acrylic resins and polyvinyl alcohol resins. Among these, polyvinyl alcohol resins that give good adhesion are preferably used. More preferably, it is a polyvinyl alcohol resin. As the solvent, a general organic solvent or an aqueous solvent capable of dissolving the resin component is usually used, but it is preferable to form the primer layer from a coating solution containing water as a solvent.

  In order to increase the strength of the primer layer, a crosslinking agent may be added to the primer layer forming coating solution. Specific examples of the crosslinking agent include epoxy-based, isocyanate-based, dialdehyde-based, metal-based (for example, metal salts, metal oxides, metal hydroxides, organometallic compounds), and polymer-based crosslinking agents. When a polyvinyl alcohol resin is used as the resin component for forming the primer layer, a polyamide epoxy resin, a methylolated melamine resin, a dialdehyde crosslinking agent, a metal chelate compound crosslinking agent, or the like is preferably used.

  The thickness of the primer layer is preferably about 0.05 to 1 μm, more preferably 0.1 to 0.4 μm. When it becomes thinner than 0.05 μm, the effect of improving the adhesion between the base film 30 and the polyvinyl alcohol-based resin layer 6 is small.

  The method for applying the primer layer forming coating solution to the base film 30 can be the same as the coating solution for forming the polyvinyl alcohol-based resin layer. The drying temperature of the coating layer made of the primer layer forming coating solution is, for example, 50 to 200 ° C, and preferably 60 to 150 ° C. When the solvent contains water, the drying temperature is preferably 80 ° C. or higher.

[2] Stretching step S20
With reference to FIG. 3, this process is a process of extending the laminated film 100 to obtain a stretched film 200 composed of the stretched base film 30 ′ and the polyvinyl alcohol-based resin layer 6 ′. Stretching is usually uniaxial stretching. In the stretching step S20, typically, the laminated film 100 is continuously unwound from a film roll that is a wound product of the long laminated film 100 while the long laminated film 100 is conveyed. It is carried out continuously while being conveyed. The film conveyance can be performed using a guide roll or the like.

  The stretching ratio of the laminated film 100 can be appropriately selected depending on the desired polarization characteristics, but is preferably more than 5 times and not more than 17 times, more preferably more than 5 times the original length of the laminated film 100. 8 times or less. When the draw ratio is 5 times or less, the polyvinyl alcohol-based resin layer 6 ′ is not sufficiently oriented, and the degree of polarization of the polarizer layer 5 may not be sufficiently high. On the other hand, when the draw ratio exceeds 17 times, the film is likely to be broken during stretching, and the thickness of the stretched film 200 becomes unnecessarily thin, and the workability and handleability in subsequent processes may be reduced.

  The stretching process is not limited to stretching in one stage, and can be performed in multiple stages. In this case, all of the multistage stretching processes may be performed continuously before the dyeing process S30, or the second and subsequent stretching processes may be performed simultaneously with the dyeing process and / or the crosslinking process in the dyeing process S30. Good. Thus, when performing a extending | stretching process in multistage, it is preferable to perform an extending | stretching process so that it may become a draw ratio more than 5 times combining all the stages of an extending | stretching process.

  The stretching treatment may be longitudinal stretching that extends in the film longitudinal direction (film transport direction), and may be lateral stretching or oblique stretching that extends in the film width direction. Examples of the longitudinal stretching method include inter-roll stretching using a roll, compression stretching, stretching using a chuck (clip), and the like, and examples of the lateral stretching method include a tenter method. As the stretching treatment, either a wet stretching method or a dry stretching method can be adopted. However, it is preferable to use the dry stretching method because the stretching temperature can be selected from a wide range.

  The stretching temperature is set to be equal to or higher than the temperature at which the polyvinyl alcohol-based resin layer 6 and the entire base film 30 can be stretched, and preferably the phase transition temperature (melting point or glass transition temperature) of the base film 30. It is in the range of −30 ° C. to + 30 ° C., more preferably in the range of −30 ° C. to + 5 ° C., and still more preferably in the range of −25 ° C. to + 0 ° C. When the base film 30 consists of a plurality of resin layers, the phase transition temperature means the highest phase transition temperature among the phase transition temperatures exhibited by the plurality of resin layers.

  If the stretching temperature is lower than the phase transition temperature of −30 ° C., high-strength stretching exceeding 5 times is difficult to achieve, or the fluidity of the base film 30 is too low and the stretching treatment tends to be difficult. When the stretching temperature exceeds + 30 ° C. of the phase transition temperature, the fluidity of the base film 30 is too large and stretching tends to be difficult. Since it is easier to achieve a high draw ratio of more than 5 times, the drawing temperature is within the above range, and more preferably 120 ° C. or higher.

  As a heating method of the laminated film 100 in the stretching process, a zone heating method (for example, a method in which hot air is blown and heated in a stretching zone such as a heating furnace adjusted to a predetermined temperature); There is a method of heating the roll itself; a heater heating method (a method in which infrared heaters, halogen heaters, panel heaters, etc. are installed above and below the laminated film 100 and heated by radiant heat). In the inter-roll stretching method, the zone heating method is preferable from the viewpoint of the uniformity of the stretching temperature.

  Prior to the stretching step S20, a preheat treatment step for preheating the laminated film 100 may be provided. As the preheating method, the same method as the heating method in the stretching process can be used. The preheating temperature is preferably in the range of −50 ° C. to ± 0 ° C. of the stretching temperature, and more preferably in the range of −40 ° C. to −10 ° C. of the stretching temperature.

  Moreover, you may provide a heat setting process process after the extending | stretching process in extending process S20. The heat setting treatment is a treatment in which heat treatment is performed at a temperature equal to or higher than the crystallization temperature of the polyvinyl alcohol resin while maintaining the tensioned state with the end portion of the stretched film 200 held by the clip. The crystallization of the polyvinyl alcohol-based resin layer 6 'is promoted by this heat setting treatment. The temperature of the heat setting treatment is preferably in the range of −0 ° C. to −80 ° C. of the stretching temperature, and more preferably in the range of −0 ° C. to −50 ° C. of the stretching temperature.

[3] Dyeing step S30
With reference to FIG. 4, this step is a step in which the polarizer layer 5 is formed by dyeing the polyvinyl alcohol resin layer 6 ′ of the stretched film 200 with a dichroic dye and adsorbing and orienting it. Through this step, a polarizing laminated film 300 in which the polarizer layer 5 is laminated on one side or both sides of the base film 30 ′ is obtained. The dyeing step S30 typically unwinds the stretched film 200 continuously while conveying the long stretched film 200 or from a film roll that is a wound product of the long stretched film 200. It is carried out continuously while being conveyed. The film conveyance can be performed using a guide roll or the like.

  Specific examples of the dichroic dye include iodine and dichroic organic dyes. Specific examples of the dichroic organic dye include, for example, 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, Splat Blue G, Splat Blue GL, Splat Orange GL , Direct Sky Blue, Direct First Orange S, First Black. A dichroic dye may be used individually by 1 type, and may use 2 or more types together.

  The dyeing step S30 can be performed by immersing the stretched film 200 in a liquid (dye bath) containing a dichroic dye. As the dyeing bath, 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 in the dyeing bath is preferably 0.01 to 10% by weight, and more preferably 0.02 to 7% by weight.

  When iodine is used as the dichroic dye, it is preferable to further add an iodide to the dyeing bath containing iodine because the dyeing efficiency can be improved. Examples of 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 concentration in the dyeing bath is preferably 0.01 to 20% by weight. Of the iodides, it is preferable to add potassium iodide. When potassium iodide is added, the ratio of iodine to potassium iodide is, by weight, preferably 1: 5 to 1: 100, more preferably 1: 6 to 1:80. The temperature of the dyeing bath is preferably 10 to 60 ° C, more preferably 20 to 40 ° C.

  In addition, you may perform an additional extending | stretching process further with respect to the stretched film 200 during dyeing process S30. Embodiments in this case are as follows: 1) In the stretching step S20, after the stretching process is performed at a lower ratio than the target, the stretching process is performed so that the total stretching ratio becomes the target ratio during the dyeing process in the dyeing process S30. In the case of performing the crosslinking treatment after the dyeing treatment, as described later, 2) In the drawing step S20, after the drawing treatment at a lower magnification than the target in the drawing step S20, during the dyeing treatment in the dyeing step S30 Examples include a mode in which the stretching process is performed to such an extent that the total stretching ratio does not reach the target ratio, and then the stretching process is performed during the crosslinking process so that the final total stretching ratio becomes the target ratio.

  The dyeing step S30 may include a crosslinking treatment step that is performed subsequent to the dyeing treatment. The crosslinking treatment step can be performed by immersing the stretched film after the dyeing treatment in a liquid (crosslinking bath) containing a crosslinking agent. Examples of the crosslinking agent include boron compounds such as boric acid and borax, glyoxal, and glutaraldehyde. Only 1 type may be used for a crosslinking agent and it may use 2 or more types together. As the crosslinking bath, a solution in which a crosslinking agent is dissolved in a solvent can be used. As the solvent, water can be used, but an organic solvent compatible with water may be further included. The concentration of the crosslinking agent in the crosslinking bath is preferably 1 to 20% by weight, more preferably 6 to 15% by weight.

  The crosslinking bath can further comprise iodide. By adding the iodide, the polarization characteristics in the plane of the polarizer layer 5 can be made more uniform. Specific examples of iodide are the same as described above. The concentration of iodide in the crosslinking bath is preferably 0.05 to 15% by weight, more preferably 0.5 to 8% by weight. The temperature of the crosslinking bath is preferably 10 to 90 ° C.

  The crosslinking treatment can be performed simultaneously with the dyeing treatment by blending a crosslinking agent in the dyeing bath. Moreover, you may perform the process immersed in a crosslinking bath 2 or more times using 2 or more types of crosslinking baths from which a composition differs. You may perform an extending | stretching process during a crosslinking process. The specific mode for carrying out the stretching treatment during the crosslinking treatment is as described above.

  It is preferable to perform a washing | cleaning process and a drying process after dyeing process S30 and before 1st bonding process S40 mentioned later. The washing process usually includes a water washing process. The water washing treatment can be performed by immersing the film after the dyeing treatment or after the crosslinking treatment in pure water such as ion exchange water or distilled water. The water washing temperature is usually 3 to 50 ° C, preferably 4 to 20 ° C. The washing step may be a combination of a water washing step and a washing step with an iodide solution. As a drying process performed after the washing process, any appropriate method such as natural drying, blow drying, and heat drying can be adopted. For example, in the case of heat drying, the drying temperature is usually 20 to 95 ° C.

  The thickness of the polarizer layer 5 included in the polarizing laminated film 300 is preferably 10 μm or less, more preferably 7 μm or less. When the thickness of the polarizer layer 5 is 10 μm or less, a thin polarizing plate can be obtained. The thickness of the polarizer layer 5 is usually 2 μm or more. According to the present invention, even when the polarizer layer 5 is as thin as 10 μm or less and the polarizing plate made of the polarizer layer 5 and the first protective film has no stiffness, cohesive failure occurs in the polarizer layer 5. Or the problem that the release surface of the polarizer layer 5 is whitened can be suppressed, and the base film 30 ′ can be peeled cleanly.

[4] First bonding step S40
Referring to FIG. 5, in this step, the first protective film 10 is bonded to the surface opposite to the surface on the base film 30 ′ side (that is, on the polarizer layer 5) in the polarizing laminated film 300 to form a multilayer. In this step, the film 400 is obtained. In the first bonding step S40, typically, the polarizing laminate film 300 is transported from the long polarizing laminate film 300 or from a film roll that is a wound product of the long polarizing laminate film 300. Is continuously carried out while being unwound and transported. The film conveyance can be performed using a guide roll or the like.

  When the polarizing laminated film 300 has the polarizer layers 5 on both surfaces of the base film 30 ′, the first protective films 10 are usually bonded onto the polarizer layers 5 on both surfaces. In this case, these first protective films 10 may be the same type of protective film or different types of protective films.

  The first protective film 10 can be bonded onto the polarizer layer 5 via the first adhesive layer 15. The adhesive forming the first adhesive layer 15 is an active energy ray-curable adhesive (preferably containing a curable compound that is cured by irradiation with active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays). UV curable adhesives) and aqueous adhesives in which adhesive components such as polyvinyl alcohol resins are dissolved or dispersed in water.

  When bonding the 1st protective film 10 using an active energy ray hardening adhesive, the 1st protective film 10 is put on the polarizer layer 5 through the active energy ray hardening adhesive used as the 1st adhesive layer 15. After being laminated, the adhesive layer is cured by irradiating active energy rays such as ultraviolet rays, visible light, electron beams, and X-rays. Among them, ultraviolet rays are preferable, and as a light source in this case, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp, or the like can be used. When using a water-based adhesive, the first protective film 10 may be laminated on the polarizer layer 5 via a water-based adhesive and then dried by heating.

  In bonding the first protective film 10 to the polarizer layer 5, plasma is applied to the bonding surface of the first protective film 10 and / or the polarizer layer 5 in order to improve the adhesion with the polarizer layer 5. Surface treatment (easy adhesion treatment) such as treatment, corona treatment, ultraviolet irradiation treatment, flame (flame) treatment, and saponification treatment can be performed, and among them, plasma treatment, corona treatment or saponification treatment is preferable. .

  The first protective film 10 is, for example, a polyolefin resin such as a chain polyolefin resin (polypropylene resin or the like) or a cyclic polyolefin resin (norbornene resin or the like); a cellulose ester such as cellulose triacetate or cellulose diacetate. Resin; Polyester resin such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate; polycarbonate resin; (meth) acrylic resin, etc.

  The first protective film 10 can also be a protective film having an optical function such as a retardation film and a brightness enhancement film. For example, a retardation film provided with an arbitrary retardation value by stretching a film made of the thermoplastic resin (uniaxial stretching or biaxial stretching) or by forming a liquid crystal layer or the like on the film. It can be.

  A surface treatment layer (coating layer) such as a hard coat layer, an antiglare layer, an antireflection layer, an antistatic layer and an antifouling layer is formed on the surface of the first protective film 10 opposite to the polarizer layer 5. You can also The surface treatment layer may be formed in advance on the first protective film 10 prior to the first bonding step S40, or after the first bonding step S40 or after the peeling step S50 described later. May be. The first protective film 10 contains one or more additives such as a lubricant, a plasticizer, a dispersant, a heat stabilizer, an ultraviolet absorber, an infrared absorber, an antistatic agent, and an antioxidant. Can do.

  The thickness of the first protective film 10 is preferably 90 μm or less, more preferably 50 μm or less, still more preferably 35 μm or less, and particularly preferably 30 μm or less from the viewpoint of thinning the polarizing plate. The thickness of the 1st protective film 10 is 5 micrometers or more normally from a viewpoint of intensity | strength and a handleability. According to the present invention, even if the thickness of the first protective film 10 is as thin as 35 μm or less and the polarizing plate made of the polarizer layer 5 and the first protective film 10 is not firm, the polarizer layer 5 is coherently broken. Can be prevented, and the base film 30 ′ can be peeled cleanly by suppressing the problem that the peeling surface of the polarizer layer 5 is whitened.

[5] Peeling step S50
With reference to FIG. 6, this process is a process of peeling and removing base film 30 'from multilayer film 400, and obtaining a polarizing plate (polarizing plate 500 with a single-sided protective film). When the polarizing laminated film 300 has the polarizer layers 5 on both surfaces of the base film 30 ′, and the first protective film 10 is bonded to both of the polarizer layers 5, the peeling process S 50 causes 1 Two polarizing plates 500 with a single-side protective film can be obtained from one polarizing laminated film 300. In the peeling step S50, typically, the multilayer film 400 is continuously unwound from a film roll that is a wound product of the long multilayer film 400 while the long multilayer film 400 is conveyed. It is carried out continuously while being conveyed. The film conveyance can be performed using a guide roll or the like.

  As shown in FIG. 7, in the present invention, when the roll 40 is installed on the transport path of the multilayer film 400, the multilayer film 400 is continuously transported along the transport path, and passes through the roll 40. The multilayer film 400 is on the side opposite to the base film 30 ′ (in the example of FIG. 7, the first protective film 10 side, that is, the first protective film 10 of the multilayer film 400 is on the roll 40 side). ) The substrate film 30 'is peeled off from the multilayer film 400 in the state of being wound around the roll 40. As the roll 40, a general rotatable roll used for supporting the film to be conveyed can be used.

  By setting the transport path of the base film 30 ′ after peeling so as to be different from the transport direction of the polarizing plate 500 with a single-side protective film after peeling the base film 30 ′ from the multilayer film 400, The base film 30 ′ is continuously peeled from the multilayer film 400 on the roll 40. At this time, the base film 30 ′ of the multilayer film 400 at the peeling point H of the base film 30 ′. While maintaining the state where the opposite surface (the surface on the first protective film 10 side in the example of FIG. 7) and the roll 40 are in contact, the base film 30 ′ is peeled off. That is, the base film 30 ′ is peeled from the multilayer film 400 by pulling the base film 30 ′ by applying a certain tension A to the base film 30 ′ after peeling. With this tension A, the base film 30 ′ is continuously peeled while being controlled so that the multilayer film 400 does not float from the surface of the roll 40 at the peeling point H.

  The state in which the multilayer film 400 is wound around the roll 40 is a surface opposite to the base film 30 ′ of the multilayer film 400 when passing through the roll 40 (in the example of FIG. 7, the first protective film 10 side). The surface) is in contact with the surface of the roll 40 at the surface. In this state, referring to FIG. 7, the multilayer film after peeling the base film 30 ′ when the extrapolation line in the transport direction of the multilayer film 400 before the base film 30 ′ is peeled is used as a reference. This can be achieved by setting the inclination angle φp at the peeling point H to the roll 40 side in the transport direction of the film 400 (that is, the polarizing plate 500 with a single-sided protective film) to be greater than 0 ° (less than 90 °). The inclination angle φp is preferably 20 ° or more.

  According to the above method, regardless of the angle formed by the peeling direction of the base film 30 ′ and the orientation direction of the polarizer layer 5, the multilayer film 400 and the polarizing plate 500 with a single-side protective film at the peeling point H Regardless of the relationship between the angle formed (that is, the tilt angle φp described above) and the angle formed by the multilayer film 400 and the base film 30 ′ (the tilt angle φk shown in FIG. 7), the multilayer film 400 is changed to the base material. The film 30 ′ can be smoothly peeled, and defects such as cohesive failure of the polarizer layer 5 and whitening of the peeled surface of the polarizer layer 5 due to peeling of the base film 30 ′ can be effectively suppressed. . φk is an inclination angle at the peeling point H to the side opposite to the roll 40 side in the conveying direction of the base film 30 ′ after peeling when the extrapolation line is used as a reference.

  At the time of peeling of the base film 30 ′, the surface opposite to the base film 30 ′ of the multilayer film 400 at the peeling point H (the surface on the first protective film 10 side in the example of FIG. 7) and the roll 40 are in contact. One effective method for maintaining the maintained state is that the tension (line tension) B of the multilayer film 400 before peeling the base film 30 ′ is sufficiently higher than the tension A of the base film 30 ′ after peeling. To make it bigger. The tensions A and B preferably satisfy the relationship of B ≧ 10 × A, and more preferably satisfy the relationship of B ≧ 12 × A. By making the tension B sufficiently larger than the tension A, the state in which the multilayer film 400 is wound around the roll 40, and the surface of the multilayer film 400 opposite to the base film 30 ′ at the peeling point H and the roll 40 The base film 30 ′ can be peeled off at the peeling point H while maintaining the state in which they are in contact with each other. Note that the tension of the polarizing plate 500 with a single-side protective film obtained by peeling the base film 30 ′ is the same as the tension B of the multilayer film 400 before peeling the base film 30 ′.

  Referring to FIG. 7, the tension A is, for example, a base film after peeling by adjusting the rotational speed of the nip roll 60 disposed on the downstream side of the roll 40 on the transport path of the base film 30 ′ after peeling. It can be controlled by adjusting the conveyance speed of 30 '. The tension B can be controlled, for example, by adjusting the ratio between the rotational speed of the nip roll 50 and the rotational speed of the nip roll 70 arranged before and after the roll 40 on the transport path of the multilayer film 400 and the polarizing plate 500 with a single-side protective film.

  Other effective methods for maintaining the state in which the multilayer film 400 is wound around the roll 40 and the state where the roll 40 is in contact with the surface of the multilayer film 400 opposite to the base film 30 ′ at the peeling point H Is to use a suction roll for the roll 40. If the suction roll is used, the multilayer film 400 (and the polarizing plate 500 with a single-sided protective film) wound around the roll by suction can be brought into close contact with the roll surface, so that the above-described state can be easily maintained. The suction roll has a large number of air intake holes on the roll surface (circumferential surface), and it is conveyed by rotating the roll while adsorbing the conveyed material to the roll surface by the intake air from the air intake holes and holding the conveyed material. A roll that transports goods. When using a suction roll, the tensions A and B do not necessarily satisfy the relationship of B ≧ 10 × A.

  Still another effective for maintaining the state where the multilayer film 400 is wound around the roll 40 and the state where the roll 40 is in contact with the surface of the multilayer film 400 opposite to the base film 30 ′ at the peeling point H. The method is to perform film reinforcement by further bonding a resin film on the first protective film 10 side before the multilayer film 400 passes through the roll 40. Since the stiffness of the multilayer film 400 becomes stronger due to the film reinforcement, and it becomes difficult to deform, the multilayer film 400 is peeled off from the surface of the roll 40 at the peeling point H when peeling from the multilayer film 400 by pulling the base film 30 ′. The floating state can be suppressed. Even when this method is used, the tensions A and B do not necessarily satisfy the relationship of B ≧ 10 × A. When this method is used, the resin film bonded to the first protective film 10 side for reinforcement is kept in contact with the roll 40 at the peeling point H.

  The diameter of the roll 40 is preferably 200 mmφ or more, and more preferably 250 mmφ or more. When the diameter of the roll 40 is within this range, when the base film 30 ′ is peeled from the multilayer film 400, the surface on the opposite side of the multilayer film 400 from the base film 30 ′ and the roll 40 are separated at the peeling point H. Easy to maintain contact.

  At the peeling point H, the position of the peeling point H is such that the surface of the multilayer film 400 opposite to the base film 30 ′ can be kept in contact with the roll 40 and the base film 30 ′ can be peeled stably. It is preferable to install a sensor for detecting this. By installing the sensor, the base film 30 ′ is peeled off from the surface of the roll 40 before the multilayer film 400 is wound around the roll 40, or the multilayer film 400 is unwound from the roll 40. Then, it can prevent that base film 30 'peels in the state which floated from the surface of the roll 40. FIG. For example, a reference position of the separation point is set in advance, one sensor is installed upstream from the reference position by a predetermined distance, and another sensor is installed downstream from the reference position by a predetermined distance. If the sensor on the side detects the peel point, the peel point moves downstream, and if the sensor on the downstream side detects the peel point, the peel point moves to the upstream side. The operating conditions are automatically adjusted to come close to the position. The operating conditions include the transport speed of the multilayer film 400 and the polarizing plate 500 with a single-side protective film, the transport speed of the base film 30 ′ after peeling, the tension A, and the tension B.

  The inclination angle φk at the peeling point H in the conveying direction of the base film 30 ′ after peeling is usually more than 0 °, preferably 20 ° or more, more preferably 40 ° or more. By setting the inclination angle φk to 20 ° or more, the base film 30 ′ can be easily peeled off smoothly without excessively increasing the tension A. The inclination angle φk is usually less than 90 °.

  As described above, the multilayer film 400 obtained in the first bonding step S40 is a film in which the polarizer layer 5 and the first protective film 10 are laminated on both surfaces of the base film 30 ′, that is, the first protection. It can be a film having a layer structure of film 10 / polarizer layer 5 / base film 30 ′ / polarizer layer 5 / first protective film 10 (the first adhesive layer 15 is omitted). In this case, two single-sided protective film-attached polarizing plates 500 are obtained from one multilayer film 400 through a two-stage peeling process. In the first peeling step, the film having the layer configuration of “first protective film 10 / polarizer layer 5 / base film 30 ′” is peeled from the multilayer film 400 having the above-described configuration, and a polarizing plate with a single-side protective film 500 is obtained (in the first-stage peeling step, the base film 30 ′ in FIG. 7 is replaced with the first protective film 10 / the polarizer layer 5 / the base film 30 ′). In the second peeling process, the base film 30 ′ is peeled from the peeled film having the layer structure of “first protective film 10 / polarizer layer 5 / base film 30 ′”, and further a single-side protective film The attached polarizing plate 500 is obtained.

  In either the first step or the second step, the first protective film 10 / the polarizer layer 5 / the base film 30 ′ or the base film 30 ′ is peeled using the above method according to the present invention. In addition, problems such as cohesive failure of the polarizer layer 5 and whitening of the peeled surface of the polarizer layer 5 can be effectively suppressed.

[6] Second bonding step S60
Referring to FIG. 8, this step is an arbitrary step in which the second protective film 20 is bonded onto the polarizer layer 5 in the polarizing plate 500 with a single-side protective film to obtain the polarizing plate 600 with a double-side protective film. The second laminating step S60 is typically performed from a film roll that is a rolled product of the long polarizing plate 500 with a single-sided protective film while conveying the long polarizing plate 500 with a single-sided protective film. The protective film-equipped polarizing plate 500 is continuously unwound and continuously conveyed. The film conveyance can be performed using a guide roll or the like.

  The second protective film 20 can be bonded onto the polarizer layer 5 via the second adhesive layer 25. About the structure and material of the 2nd protective film 20 and the 2nd adhesive layer 25, and the bonding method of the 2nd protective film 20, the 1st protective film 10, the 1st adhesive layer 15, and the 1st protective film 10, respectively. The description about the pasting method is quoted.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these examples.

<Example 1>
(1) Primer layer forming step Polyvinyl alcohol powder (“Z-200” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., average polymerization degree 1100, saponification degree 99.5 mol%) is 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 a crosslinking agent (“Smiles Resin 650” manufactured by Taoka Chemical Co., Ltd.) at a ratio of 5 parts by weight to 6 parts by weight of the polyvinyl alcohol powder to form a primer layer forming coating solution. Got.

  Next, the corona treatment was performed on one side of the substrate film (unstretched polypropylene film, melting point: 163 ° C.) having a thickness of 90 μm continuously, and then the corona treatment surface was subjected to the above using a small-diameter gravure coater. The primer layer-forming coating solution was continuously applied and dried at 80 ° C. for 10 minutes to form a primer layer having a thickness of 0.2 μm.

(2) Production of laminated film (resin layer forming step)
Polyvinyl alcohol powder (“PVA124” manufactured by Kuraray Co., Ltd., average polymerization degree 2400, saponification degree 98.0 to 99.0 mol%) was dissolved in hot water at 95 ° C., and a polyvinyl alcohol aqueous solution having a concentration of 8% by weight. This was used as a coating liquid for forming a polyvinyl alcohol resin layer.

  While continuously transporting the base film having the primer layer prepared in (1) above, the above-mentioned coating solution for forming a polyvinyl alcohol-based resin layer was continuously applied to the surface of the primer layer using a lip coater. Then, the polyvinyl alcohol-type resin layer was formed on the primer layer by drying at 80 degreeC for 20 minutes, and the laminated film which consists of a base film / primer layer / polyvinyl alcohol-type resin layer was obtained.

(3) Production of stretched film (first stretching step)
While continuously transporting the laminated film produced in (2) above, 5.8-fold free end uniaxial stretching was performed at 160 ° C. using a floating longitudinal uniaxial stretching device to obtain a stretched film. The thickness of the stretched polyvinyl alcohol resin layer was 5.0 μm.

(4) Production of polarizing laminated film (dyeing process)
While continuously transporting the stretched film prepared in (3) above, a dyeing bath at 26 ° C. containing iodine and potassium iodide (0.35 parts by weight iodine and 100 parts by weight potassium iodide per 100 parts by weight of water) The polyvinyl alcohol resin layer was dyed continuously.

  Next, the residence time is 300 seconds in a 78 ° C. crosslinking bath containing boric acid and potassium iodide (9.5 parts by weight of boric acid and 5 parts by weight of potassium iodide per 100 parts by weight of water). Cross-linking treatment was performed by continuous immersion. Then, it wash | cleaned for 10 second with 8 degreeC pure water, and obtained the polarizing laminated film which has a polarizer layer on a base film by making it dry at 40-50 degreeC for 200 second.

(5) Production of multilayer film (bonding process)
While continuously transporting a cyclic polyolefin resin film having a thickness of 15 μm (“ZF14” manufactured by Nippon Zeon Co., Ltd.), a curable compound that is a cationic polymerizable epoxy compound and a photocationic polymerization initiator on one side thereof UV curable adhesive (“KR-70T” manufactured by ADEKA Co., Ltd.) containing sucrose is continuously applied using a small-diameter gravure coater so that the thickness of the adhesive layer after curing is 1.0 μm. Then, the polarizing laminated film produced by said (4) was continuously bonded by the side of the polarizer layer on the coated adhesive bond layer using the bonding roll. Thereafter, the adhesive layer was cured by irradiating ultraviolet rays with an integrated light amount of 150 mJ / cm ² from the base film side to obtain a multilayer film.

(6) Production of polarizing plate (peeling process)
Referring to FIG. 7, while continuously transporting the multilayer film 400 produced in the above (5), the multilayer film 400 is disposed on the first protective film 10 side when passing through the roll 40 (the first layer of the multilayer film 400). The first protective film 10 and the roll 40 were brought into contact at the peeling point H from the multilayer film 400 in the wound state, so that the protective film 10 was on the roll 40 side. While maintaining the state, the base film 30 ′ was continuously peeled to obtain a polarizing plate 500 with a single-sided protective film. At this time, the tension A of the base film 30 ′ after peeling and the tension B of the multilayer film 400 and the polarizing plate 500 with a single-sided protective film were as shown in Table 1. The tilt angle φp was 20 °, the tilt angle φk was 70 °, and the diameter of the roll 40 was 250 mmφ. As the roll 40, a normal roll that is not a suction roll and is used for supporting the film to be conveyed is used (indicated as "normal" in the "Roll type" column in Table 1). ). When the base film 30 ′ was continuously peeled, the peeling point H was visually observed, but the first protective film 10 and the roll 40 seemed to be kept in contact with each other. This was also confirmed from an enlarged photograph of the peeling point H.

<Examples 2-3 and Comparative Examples 1-2>
A polarizing plate 500 with a single-sided protective film was produced in the same manner as in Example 1 except that the tension A and the tension B were as shown in Table 1. However, in Example 3, a suction roll is used as the roll 40, and the base film 30 ′ is adhered to the roll surface while the multilayer film 400 wound around the roll and the polarizing plate 500 with a single-side protective film are brought into close contact with the roll surface. It peeled.

  In Comparative Examples 1 and 2, the first protective film 10 and the roll 40 were not in contact at the peeling point H, and the multilayer film 400 was lifted from the roll surface to the extent that it could be visually confirmed.

[Evaluation of peelability]
(1) Evaluation of peeling state The peeling surface (polarizer layer surface) of the polarizing plate 500 with a single-sided protective film obtained by peeling and removing the base film 30 ′ was visually observed, and the peeling state was evaluated according to the following criteria. . The results are shown in Table 1.

A: Cohesive failure and whitening are not recognized,
B1: Cohesive failure is observed,
B2: Whitening is observed.

(2) Evaluation of peeling stability The peeling stability of the base film 30 'was visually observed and evaluated according to the following criteria. The results are shown in Table 1.

A: Stable,
B: Unstable.
Here, B is also called zippering in a state in which the peeling force is fine and repeats strength at the time of peeling, and the peeling point H fluctuates back and forth or the peeling angle becomes unstable. A is the state which peeled without causing such zippering.

  5 Polarizer Layer, 6 Polyvinyl Alcohol Resin Layer, 6 ′ Stretched Polyvinyl Alcohol Resin Layer, 10 First Protective Film, 15 First Adhesive Layer, 20 Second Protective Film, 25 Second Adhesive Layer, 30 Base film, 30 'stretched base film, 40 rolls, 50, 60, 70 nip roll, 100 laminated film, 200 stretched film, 300 polarizing laminated film, 400 multilayer film, 500 polarizing plate with single-sided protective film, 600 Polarizing plate with double-sided protective film, H Peeling point.

Claims (3)

A resin layer forming step of forming a polyvinyl alcohol resin layer on at least one surface of the base film to obtain a laminated film;
A stretching step of stretching the laminated film to obtain a stretched film;
A dyeing step of obtaining a polarizing laminated film by dyeing a polyvinyl alcohol-based resin layer of the stretched film with a dichroic dye to form a polarizer layer;
A bonding step of bonding a protective film having a thickness of 35 μm or less to a surface opposite to the surface on the base film side in the polarizing laminated film to obtain a multilayer film,
A peeling step of peeling and removing the base film from the multilayer film to obtain a polarizing plate,
Including
In the peeling step, the multilayer film is wound around a roll on the side opposite to the base film, and when the base film is peeled from the multilayer film, There line to keep the surface of the opposite side is in contact with the roll and the substrate film,
Inclination at the peeling point toward the side opposite to the roll side in the transport direction of the base film after peeling, based on the extrapolation line in the transport direction of the multilayer film before the base film is peeled off The angle φk is greater than 0 °,
When the tension of the base film after peeling is A and the tension of the multilayer film before peeling the base film is B, the base film is peeled under conditions satisfying B ≧ 10 × A, or
The said roll is a suction roll, The manufacturing method of a polarizing plate which peels a base film, attracting | sucking the multilayer film wound around the roll with a suction roll . The roll has a diameter not less than 200 mm, the manufacturing method according to claim 1. The said polarizer layer is a manufacturing method of Claim 1 or 2 whose thickness is 10 micrometers or less.

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