JP6689349B2 - Polarizing film manufacturing method - Google Patents

Description

  The present invention relates to a method for manufacturing a polarizing film. The polarizing film obtained by the manufacturing method can form an image display device such as a liquid crystal display device (LCD), an organic EL display device, a CRT, or a PDP by itself or as an optical film in which the polarizing film is laminated.

  Liquid crystal display devices are rapidly expanding in markets such as watches, mobile phones, PDAs, notebook computers, personal computer monitors, DVD players, and TVs. The liquid crystal display device visualizes a polarization state due to switching of liquid crystal, and a polarizer is used due to its display principle. In particular, in applications such as TVs, higher brightness, higher contrast, and wider viewing angle are required, and polarizing films are also required to have higher transmittance, higher polarization degree, and higher color reproducibility.

  As a polarizer, an iodine-based polarizer having a structure in which iodine is adsorbed in polyvinyl alcohol and stretched, for example, is most commonly used because it has a high transmittance and a high degree of polarization. Such a polarizer has an extremely weak mechanical strength, and has the disadvantage that it contracts due to heat or moisture, resulting in a marked decrease in the polarization function. Therefore, the obtained polarizer is usually coated with a water-based adhesive immediately, and is used as a polarizing film in which transparent protective films are simultaneously attached to both surfaces of the polarizer via the adhesive. As the transparent protective film, triacetyl cellulose having high moisture permeability is used. On the other hand, in order to suppress the dimensional change, the moisture content of the polarizer can be lowered, or a transparent protective film having low moisture permeability can be used.

  However, when using a water-based adhesive when producing a polarizing film (so-called wet lamination), high productivity cannot be expected because a drying step is required after the polarizer and the transparent protective film are bonded together. . Further, when a transparent protective film having a low moisture permeability is used, the drying efficiency is further deteriorated and high productivity cannot be expected.

  In order to solve the above problems in wet lamination, active energy ray-curable adhesives containing no water or organic solvent have been proposed (Patent Documents 1 and 2). The active energy ray-curable adhesive is roughly classified into a photocationic polymerization type and a photoradical polymerization type. Since the active energy ray-curable adhesive does not require a drying step unlike the water-based adhesive, it is possible to increase the productivity of the polarizing film even when a low moisture-permeable transparent protective film is used.

JP, 2010-286754, A JP, 2008-233874, A

  In the wet lamination using the water-based adhesive, there was no particular problem in terms of appearance with respect to the polarizing film obtained by bonding the polarizer and the transparent protective film. That is, when a water-based adhesive is used, the polarizer and the transparent protective film are bonded together with a wet adhesive, and then the adhesive is dried to gradually remove water. For this reason, it is difficult for air bubbles to be caught in the bonding surface, and there is no problem in appearance due to the air bubbles. However, when an active energy ray-curable adhesive was used, a new problem was encountered in that the resulting polarizing film was inferior in appearance.

  The present invention is a method for producing a polarizing film in which a transparent protective film is provided on both sides of a polarizer, even when the polarizer and the transparent protective film are bonded together using an active energy ray-curable adhesive. It is an object of the present invention to provide a method capable of producing a polarizing film having a good appearance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found the following method for producing a polarizing film, and completed the present invention.

That is, the present invention is a method for producing a polarizing film, wherein the first and second transparent protective films are provided on the first and second surfaces of the polarizer,
A step (1) of applying an active energy ray-curable adhesive to the second surface of the polarizer in the one-sided protective polarizing film in which the first transparent protective film is provided on the first surface of the polarizer;
A step (2) of bonding a second transparent protective film via the active energy ray-curable adhesive,
And a step (3) of irradiating the active energy ray-curable adhesive with an active energy ray to form an adhesive layer.

  In the method for producing the polarizing film, the polarizer is a continuous web polarizing film made of a polyvinyl alcohol-based resin in which a dichroic material is oriented, and the one-sided protective polarizing film is a thermoplastic resin substrate. The present invention can be suitably applied to the case where the laminate containing the polyvinyl alcohol-based resin layer formed in (1) is obtained by being stretched in a two-stage stretching step consisting of auxiliary stretching in air and stretching in boric acid in water.

  In the step (1), the method for producing the polarizing film comprises applying the active energy ray-curable adhesive to the second surface of the polarizer in the one-sided protective polarizing film, and after 2 seconds or more has elapsed, It is preferable to perform the step (2).

  In the method for producing a polarizing film, the active energy ray-curable adhesive preferably has a viscosity of 10 to 350 cps (25 ° C.).

  In the method for producing a polarizing film, the active energy ray-curable adhesive preferably contains a radically polymerizable compound.

  In the method for producing a polarizing film, according to the step (1), before the active energy ray-curable adhesive is applied to the second surface of the polarizer in the one-sided protective polarizing film, the second surface of the polarizer is dried. It is preferable to include a step of performing treatment.

  In the manufacturing method of the polarizing film, it is preferable that the irradiation of the active energy ray in the step (3) is performed from the side of the second transparent protective film.

  In the method for producing a polarizing film, the adhesive layer formed in the step (3) preferably has a thickness of 300 nm to 1.3 μm.

  When manufacturing a polarizing film, it is very difficult to handle the polarizer due to the problem of strength. For this reason, when using an active energy ray-curable adhesive (hereinafter sometimes simply referred to as an adhesive), the adhesive is applied not to the polarizer side but to the transparent protective film side, and the polarizer and the transparent protective film. It is considered that it is preferable to bond However, since the surface of the polarizer has stripes with a pitch of several μm and unevenness of a level of several hundreds of nm, after applying an adhesive to the transparent protective film side where the surface is relatively smooth, it is attached to the polarizer. It was found that when they are combined, it is almost impossible to fill the unevenness or the stripes on the surface of the polarizer with the adhesive. Therefore, it was found that many bubbles were generated in the obtained polarizing film, resulting in poor appearance. That is, it was found that when the polarizer and the transparent protective film are attached to each other by the active energy ray-curable adhesive, the cause of the entrapment of air bubbles is influenced by the surface roughness of the polarizer.

  Therefore, in the present invention, the active energy ray-curable adhesive is applied not to the transparent protective film side but to the polarizer side. Generally, the surface roughness of the polarizer is larger than that of the transparent protective film. Therefore, rather than coating the active energy ray-curable adhesive on the transparent protective film and bonding it, it is more effective to apply the adhesive to the polarizer side and bond it, because the air bubbles trapped in the bonding surface will be dramatically increased. Can be reduced. That is, by applying an adhesive to the polarizer side, the adhesive can fill the irregularities on the surface of the polarizer to some extent, and the adhesive can be attached to the transparent protective film. The appearance can be improved.

  As described above, the polarizer is very difficult to handle, and when the adhesive is directly applied to the polarizer, there is a risk of stopping the production line. In particular, when a polarizer obtained through a stretching step is attached to a transparent protective film in a continuous line, it is the most dangerous and difficult, and is not suitable for production. In the present invention, in applying the adhesive, a one-sided protective polarizing film in which the first transparent protective film has already been provided on the first surface of the polarizer opposite to the second surface of the polarizer to be coated I am using. Since the one-sided protective polarizer is durable, the adhesive is applied directly to the second surface of the one-sided protective polarizer by directly applying the adhesive to a single polarizer that does not have transparent protective films on both sides of the polarizer. The stabilized coating can be realized as compared with the case of performing.

Below, the manufacturing method of the polarizing film of this invention is demonstrated. In the polarizing film of the present invention, the first transparent protective film is provided on one surface (first surface) of the polarizer, and the second transparent protective film is provided on the other surface (second surface). The polarizing film of the present invention is obtained by sequentially performing the steps (1) to (3).

<Step (1)>
In step (1), an active energy ray-curable adhesive is applied to the second surface of the polarizer in the one-sided protective polarizing film in which the first transparent protective film is provided on the first surface of the polarizer.

<One-sided protective polarizing film>
The one-sided protective polarizing film is such that the first transparent protective film is provided only on the first surface of the polarizer, but the first surface of the polarizer and the first transparent protective film are attached via an adhesive layer. May be combined.

  Examples of the adhesive used for the adhesion treatment between the first surface of the polarizer and the first transparent protective film include isocyanate adhesives, polyvinyl alcohol adhesives, gelatin adhesives, vinyl latex adhesives, water-based polyesters, and the like. It can be illustrated. The adhesive is usually used as an adhesive composed of an aqueous solution, and usually contains 0.5 to 60% by weight of solid content. In addition to the above, examples of the adhesive between the polarizer and the transparent protective film include active energy ray curable adhesives such as ultraviolet curable adhesives and electron beam curable adhesives. The adhesive used in the present invention may contain a metal compound filler.

  When an aqueous adhesive is used as the adhesive, the thickness of the adhesive layer is preferably about 10 to 300 nm. The thickness of the adhesive layer is more preferably 10 to 200 nm, and particularly preferably 20 to 150 nm, from the viewpoint of obtaining a uniform in-plane thickness and obtaining a sufficient adhesive force. When an active energy ray-curable adhesive is used as the adhesive, the thickness of the adhesive layer is preferably controlled within the same range as the thickness of the adhesive layer according to the second surface, which will be described later.

  When the first transparent protective film is provided on the first surface of the polarizer alone, it is difficult to directly apply the adhesive to the polarizer alone. In this case, the adhesive is applied to the first transparent protective film. It is preferable to work. On the other hand, as described in a thin polarizer described later, a thin high-performance polarizing film integrally formed on a resin base material has good handleability. Therefore, when using a thin high-performance polarizing film integrally formed on a resin substrate, applying an adhesive directly to the first surface of the polarizer has a surface roughness larger than that of the surface protection film. It is good for suppressing the entrapment of bubbles by the polarizer having.

<Polarizer>
The polarizer is not particularly limited, and various kinds can be used. Examples of the polarizer include hydrophilic polymer films such as polyvinyl alcohol film, partially formalized polyvinyl alcohol film, and ethylene / vinyl acetate copolymer partially saponified film, and dichroism of iodine or dichroic dye. Examples thereof include polyene-oriented films in which substances are adsorbed and uniaxially stretched, polyvinyl alcohol dehydration products, polyvinyl chloride dehydrochlorination products, and the like. Among these, a polarizer made of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 1 to 80 μm.

  A polarizer obtained by dyeing a polyvinyl alcohol-based film with iodine and uniaxially stretching it can be prepared, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine, dyeing it, and stretching it to 3 to 7 times its original length. If necessary, it can be immersed in an aqueous solution of potassium iodide, which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, it is possible to wash the stains and anti-blocking agent on the surface of the polyvinyl alcohol-based film, and by swelling the polyvinyl alcohol-based film, the effect of preventing unevenness such as uneven dyeing is also obtained. is there. Stretching may be performed after dyeing with iodine, stretching while dyeing, or stretching and then dyeing with iodine. Stretching can be performed in an aqueous solution of boric acid or potassium iodide or in a water bath.

<< Thin polarizer >>
As the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. It is preferable that such a thin polarizer has little thickness unevenness, excellent visibility, and excellent durability due to small dimensional change, and that the thickness of the polarizing film can be reduced.

  As the thin polarizer, typically, JP-A-51-0696644, JP-A-2000-338329, WO 2010/100917 pamphlet, PCT / JP2010 / 001460, or Japanese Patent Application No. 2010- Examples thereof include thin polarizing films described in Japanese Patent No. 269002 and Japanese Patent Application No. 2010-263692. These thin polarizing films can be obtained by a manufacturing method including a step of stretching a polyvinyl alcohol-based resin (hereinafter, also referred to as PVA-based resin) layer and a stretching resin base material in a laminate state and a dyeing step. According to this production method, even if the PVA-based resin layer is thin, the PVA-based resin layer is supported by the stretching resin base material, so that the PVA-based resin layer can be stretched without trouble such as breakage due to stretching.

  As the thin polarizing film, among the production methods including a step of stretching in a laminate state and a step of dyeing, WO 2010/100917 pamphlet, PCT / PCT / Those obtained by a production method including a step of stretching in an aqueous solution of boric acid as described in JP 2010/001460, or Japanese Patent Application Nos. 2010-269002 and 2010-263692 are preferable, and particularly preferable. Those obtained by a production method including a step of supplementary in-air stretching before stretching in an aqueous solution of boric acid described in Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692 are preferable.

  The thin high-performance polarizing film described in the above specification of PCT / JP2010 / 001460 is a thin film having a thickness of 7 μm or less, which is made of a PVA-based resin in which a dichroic material is oriented and which is integrally formed on a resin substrate. It is a high-performance polarizing film, and has optical characteristics of a single transmittance of 42.0% or more and a polarization degree of 99.95% or more.

  The thin high-performance polarizing film is such that a PVA-based resin layer is formed on a resin substrate having a thickness of at least 20 μm by coating and drying the PVA-based resin, and the generated PVA-based resin layer is dyed with a dichroic material. The PVA-based resin layer is immersed in a liquid to adsorb the dichroic substance on the PVA-based resin layer, and the PVA-based resin layer on which the dichroic substance is adsorbed is integrated with the resin base material in the aqueous boric acid solution to determine the total draw ratio It can be produced by stretching so that the length is 5 times or more.

  A method for producing a laminate film including a thin high-performance polarizing film in which a dichroic material is oriented, the method including a resin base material having a thickness of at least 20 μm, and a PVA-based resin on one surface of the resin base material. A step of producing a laminate film including a PVA-based resin layer formed by applying and drying an aqueous solution, and the above-described lamination including a resin base material and a PVA-based resin layer formed on one surface of the resin base material A body film is immersed in a dyeing solution containing a dichroic material to adsorb the dichroic material to the PVA-based resin layer contained in the laminate film; and a PVA-based resin to which the dichroic material is adsorbed A step of stretching the laminate film containing a resin layer in a boric acid aqueous solution so that the total stretching ratio is 5 times or more of the original length; and a PVA-based resin layer on which a dichroic material is adsorbed is a resin base. Stretched integrally with the material As a result, the PVA-based resin layer in which a dichroic substance is oriented is formed on one surface of the resin base material, the thickness is 7 μm or less, the single transmittance is 42.0% or more, and the polarization degree is 99.95% or more. The thin high-performance polarizing film can be produced by including the step of producing a laminate film having a thin high-functional polarizing film having the optical characteristics described above.

  In the present invention, a polarizing film having a thickness of 10 μm or less, which is a continuous web made of a PVA-based resin in which a dichroic material is oriented, and is a polyvinyl alcohol-based resin layer formed on a thermoplastic resin substrate. It is possible to use the one obtained by stretching the laminate containing the above in a two-stage stretching process consisting of auxiliary stretching in air and stretching in boric acid in water. The thermoplastic resin base material is preferably an amorphous ester-based thermoplastic resin base material or a crystalline ester-based thermoplastic resin base material.

The thin polarizing films of Japanese Patent Application No. 2010-269002 and Japanese Patent Application No. 2010-263692 described above are continuous web polarizing films made of a PVA-based resin in which a dichroic material is oriented, and are amorphous. A laminate containing a PVA-based resin layer formed on an ester-based thermoplastic resin substrate was stretched in a two-stage stretching process consisting of in-air auxiliary stretching and boric acid in water stretching to have a thickness of 10 μm or less. It is a thing. Such a thin polarizing film has P> − (10 ^0.929 T ^−42.4 −1) × 100 (where T <42.3), and P ≧, where T is the single transmittance and P is the polarization degree. It is preferable that the optical characteristics satisfy the condition of 99.9 (where T ≧ 42.3).

  Specifically, the thin polarizing film is a stretched intermediate layer formed of an oriented PVA-based resin layer by high-temperature in-air stretching of a PVA-based resin layer formed on a non-crystalline ester-based thermoplastic resin substrate of a continuous web. Coloring intermediate product comprising a PVA-based resin layer in which a dichroic material (iodine or a mixture of iodine and an organic dye is preferred) is oriented by a step of producing a product and adsorption of the dichroic material to the stretched intermediate product. Thin polarizing film including a step of producing a product and a step of producing a polarizing film having a thickness of 10 μm or less, which is composed of a PVA-based resin layer in which a dichroic material is oriented, by stretching in water with boric acid to a colored intermediate product. It can be manufactured by the manufacturing method of.

In this production method, the total stretch ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin substrate by high-temperature in-air stretching and in-boric-acid-water stretching is set to 5 times or more. desirable. The liquid temperature of the boric acid aqueous solution for drawing in boric acid in water can be 60 ° C. or higher. Before stretching the colored intermediate product in the aqueous boric acid solution, it is desirable to insolubilize the colored intermediate product. In that case, the colored intermediate product is added to the boric acid aqueous solution whose liquid temperature does not exceed 40 ° C. It is desirable to do this by dipping. The amorphous ester-based thermoplastic resin substrate is an amorphous polyethylene containing a copolymerized polyethylene terephthalate copolymerized with isophthalic acid, a copolymerized polyethylene terephthalate copolymerized with cyclohexanedimethanol or another copolymerized polyethylene terephthalate. It can be terephthalate and is preferably made of a transparent resin, and its thickness can be 7 times or more the thickness of the PVA-based resin layer to be formed. Further, the draw ratio of the in-air high temperature drawing is preferably 3.5 times or less, and the drawing temperature of the in-air high temperature drawing is preferably not less than the glass transition temperature of the PVA-based resin, specifically in the range of 95 ° C to 150 ° C. When the in-air high-temperature stretching is performed by free-end uniaxial stretching, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin substrate is preferably 5 times or more and 7.5 times or less. . When the in-air high-temperature stretching is performed by fixed-end uniaxial stretching, the total stretching ratio of the PVA-based resin layer formed on the amorphous ester-based thermoplastic resin substrate is 5 times or more and 8.5 times or less. Is preferred.
More specifically, a thin polarizing film can be manufactured by the following method.

  A base material of a continuous web of isophthalic acid-copolymerized polyethylene terephthalate (amorphous PET) in which 6 mol% of isophthalic acid is copolymerized is prepared. The glass transition temperature of amorphous PET is 75 ° C. A laminate consisting of a continuous web amorphous PET substrate and a polyvinyl alcohol (PVA) layer is prepared as follows. Incidentally, the glass transition temperature of PVA is 80 ° C.

  An amorphous PET base material having a thickness of 200 μm and a PVA aqueous solution having a concentration of 4 to 5% in which PVA powder having a polymerization degree of 1000 or more and a saponification degree of 99% or more is dissolved in water are prepared. Next, a PVA aqueous solution was applied to a 200 μm-thick amorphous PET base material and dried at a temperature of 50 to 60 ° C. to obtain a laminate in which a 7 μm-thick PVA layer was formed on the amorphous PET base material. obtain.

  A laminate containing a 7 μm thick PVA layer is subjected to the following steps including a two-step stretching step of in-air auxiliary stretching and boric acid in water stretching to manufacture a thin highly functional polarizing film having a thickness of 3 μm. The first stage in-air auxiliary stretching step integrally stretches the laminate containing the 7 μm thick PVA layer with the amorphous PET substrate to produce a stretched laminate containing the 5 μm thick PVA layer. Specifically, the stretched laminate is obtained by subjecting the laminate including the PVA layer having a thickness of 7 μm to a stretching device provided in an oven set to a stretching temperature environment of 130 ° C. so that the stretching ratio becomes 1.8 times. The free end is uniaxially stretched. By this stretching treatment, the PVA layer contained in the stretched laminate is changed to a PVA layer having a thickness of 5 μm in which PVA molecules are oriented.

  Next, in the dyeing step, a colored laminate is produced in which iodine is adsorbed on the PVA layer having a thickness of 5 μm in which PVA molecules are oriented. Specifically, in this colored laminate, the stretched laminate was immersed in a dyeing solution containing iodine and potassium iodide at a liquid temperature of 30 ° C., and the single transmittance of the PVA layer constituting the highly functional polarizing film finally produced. Is soaked as to be 40 to 44% for an arbitrary time so that iodine is adsorbed to the PVA layer contained in the stretched laminate. In this step, the dyeing solution has water as a solvent, an iodine concentration of 0.12 to 0.30% by weight, and a potassium iodide concentration of 0.7 to 2.1% by weight. The ratio of the concentrations of iodine and potassium iodide is 1: 7. By the way, potassium iodide is needed to dissolve iodine in water. More specifically, by immersing the stretched laminate in a dyeing solution having an iodine concentration of 0.30% by weight and a potassium iodide concentration of 2.1% by weight for 60 seconds, iodine was added to the 5 μm-thick PVA layer in which PVA molecules were oriented. To produce a colored laminated body.

  Furthermore, the colored laminate is further stretched integrally with the amorphous PET substrate by the second step in a boric acid in-water stretching step to produce an optical film laminate including a PVA layer constituting a highly functional polarizing film having a thickness of 3 μm. To do. Specifically, the optical film laminate is stretched by subjecting the colored laminate to a stretching device provided in a treatment device set to a boric acid aqueous solution containing boric acid and potassium iodide and having a liquid temperature range of 60 to 85 ° C. The free end was uniaxially stretched so that the magnification was 3.3 times. More specifically, the liquid temperature of the boric acid aqueous solution is 65 ° C. It also has a boric acid content of 4 parts by weight for 100 parts by weight of water and a potassium iodide content of 5 parts by weight for 100 parts by weight of water. In this step, the colored laminate having an adjusted iodine adsorption amount is first immersed in a boric acid aqueous solution for 5 to 10 seconds. Then, the colored laminate is directly passed between a plurality of sets of rolls having different peripheral speeds, which are stretching devices provided in the processing device, and the stretching ratio is freely increased to 3.3 times in 30 to 90 seconds. It is uniaxially stretched. By this stretching treatment, the PVA layer included in the colored laminate is changed to a PVA layer having a thickness of 3 μm in which the adsorbed iodine is highly oriented in one direction as a polyiodine ion complex. This PVA layer constitutes the high-performance polarizing film of the optical film laminate.

  Although it is not an essential step in the production of the optical film laminate, the optical film laminate was taken out from the aqueous boric acid solution by the washing step and attached to the surface of the 3 μm thick PVA layer formed on the amorphous PET substrate. It is preferable to wash boric acid with an aqueous potassium iodide solution. Thereafter, the washed optical film laminate is dried by a drying process with warm air at 60 ° C. The cleaning step is a step for eliminating a poor appearance such as boric acid precipitation.

  Similarly, although it is not an essential step in the production of the optical film laminate, an adhesive is applied to the surface of the PVA layer having a thickness of 3 μm formed on the amorphous PET substrate by a laminating and / or transferring step. However, after adhering a triacetyl cellulose film having a thickness of 80 μm, the amorphous PET substrate may be peeled off, and the PVA layer having a thickness of 3 μm may be transferred to the triacetyl cellulose film having a thickness of 80 μm.

[Other processes]
The above thin polarizing film manufacturing method may include other steps in addition to the above steps. Examples of other steps include an insolubilization step, a cross-linking step, and a drying (adjusting water content) step. Other steps may be performed at any appropriate timing.
The insolubilization step is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. By applying the insolubilization treatment, water resistance can be imparted to the PVA-based resin layer. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. The liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C to 50 ° C. Preferably, the insolubilization step is performed after the laminated body is produced and before the dyeing step and the underwater stretching step.
The cross-linking step is typically performed by immersing the PVA-based resin layer in an aqueous boric acid solution. Water resistance can be imparted to the PVA-based resin layer by performing the crosslinking treatment. The concentration of the boric acid aqueous solution is preferably 1 to 4 parts by weight with respect to 100 parts by weight of water. When the crosslinking step is performed after the dyeing step, it is preferable to further add iodide. By blending iodide, elution of iodine adsorbed on the PVA-based resin layer can be suppressed. The iodide content is preferably 1 part by weight to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of iodide are as described above. The liquid temperature of the crosslinking bath (boric acid aqueous solution) is preferably 20 ° C to 50 ° C. Preferably, the cross-linking step is performed before the second in-boric-acid-water drawing step. In a preferred embodiment, the dyeing step, the cross-linking step, and the second in-boric-acid-water drawing step are performed in this order.

<First transparent protective film>
The material forming the first transparent protective film is preferably one having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like. For example, polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose-based polymers such as diacetyl cellulose and triacetyl cellulose, acrylic-based polymers such as polymethylmethacrylate, styrene such as polystyrene and acrylonitrile-styrene copolymer (AS resin). Examples thereof include a polymer and a polycarbonate polymer. Further, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymer, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers. , A polyether sulfone polymer, a polyether ether ketone polymer, a polyphenylene sulfide polymer, a vinyl alcohol polymer, a vinylidene chloride polymer, a vinyl butyral polymer, an arylate polymer, a polyoxymethylene polymer, an epoxy polymer, or the above. Blends of polymers and the like are also mentioned as examples of the polymer forming the transparent protective film. The transparent protective film may contain one or more kinds of any appropriate additive. Examples of the additive include an ultraviolet absorber, an antioxidant, a lubricant, a plasticizer, a release agent, an anti-coloring agent, a flame retardant, a nucleating agent, an antistatic agent, a pigment and a coloring agent. The content of the thermoplastic resin in the transparent protective film is preferably 50 to 100% by mass, more preferably 50 to 99% by mass, further preferably 60 to 98% by mass, and particularly preferably 70 to 97% by mass. . When the content of the thermoplastic resin in the transparent protective film is 50% by mass or less, the high transparency originally possessed by the thermoplastic resin may not be sufficiently exhibited. The first transparent protective film can be appropriately selected and used.

  The thickness of the first transparent protective film can be appropriately determined, but is generally about 1 to 500 μm in view of workability such as strength and handleability, and thin layer property. In particular, 1 to 300 μm is preferable, and 5 to 200 μm is more preferable.

<Active energy ray curable adhesive>
The active energy ray-curable adhesive according to the present invention is an adhesive that is cured by an active energy ray such as an electron beam or an ultraviolet ray, and can be used, for example, in an electron beam curable type or an ultraviolet ray curable type. As the active energy ray-curable adhesive in the present invention, an ultraviolet-curable adhesive is preferable because it can be easily tested in general-purpose equipment. On the other hand, the electron beam curing adhesive does not use a photoinitiator, so it can be used with materials that do not transmit light (such as metal films and high-concentration pigments), and has the characteristic of improving adhesion. There are equipment restrictions compared to adhesives.

  The active energy ray-curable adhesive used in the present invention may be either a cationic photopolymerization type or a photoradical polymerization type adhesive, but the active energy ray curable adhesive of the present invention is a photoradical polymerization type adhesive. Adhesives are preferably used because they cure faster and are suitable for high-speed production.

  When the photo-radical-polymerizable active energy ray-curable adhesive is used as an ultraviolet-curable adhesive, the adhesive contains (A) a radical-polymerizable compound and (B) a photo-radical generator.

<< (A) Radical Polymerizable Compound >>
The radically polymerizable compound (A) can be used without particular limitation as long as it is a compound having at least one carbon-carbon double bond-containing vinyl group, (meth) acryloyl group, or the like. In the present invention, (A) Among the radical polymerizable compound represented by the following general formula ^{_{(1): CH 2 = C}} (R 1) -CONH 2-m - (X-O-R 2) m (1)
(R ¹ represents a hydrogen atom or a methyl group, X represents a —CH ₂ — group or a —CH ₂ CH ₂ — group, and R ² represents a — (CH ₂ ) _n —H group (where n is 0, 1 Or 2), and m is 1 or 2) is preferable.

  Specific examples of the N-substituted amide-based monomer represented by the general formula (1) include, for example, N-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, Examples thereof include N-ethoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide and the like. These N-substituted amide monomers can be used alone or in combination of two or more.

  As the N-substituted amide-based monomer represented by the above general formula (1), commercially available products can also be suitably used. Specifically, for example, N-hydroxyethyl acrylamide (trade name "HEAA", manufactured by Kojin Co., Ltd.), N-methoxymethyl acrylamide (trade name "NMMA", manufactured by MRC Unitech Co., Ltd.), N-butoxymethyl acrylamide (trade name) “NBMA”, manufactured by MRC Unitech Co., Ltd., N-methoxymethylmethacrylamide (trade name “Wassmer 2MA”, manufactured by Kasano Kosan Co., Ltd.) and the like.

  As the N-substituted amide-based monomer represented by the general formula (1), N-hydroxyethyl (meth) acrylamide is suitable. The N-substituted amide-based monomer shows good adhesion to a polarizer having a low water content and a transparent protective film using a material having a low water vapor transmission rate. Hydroxyethyl acrylamide shows particularly good adhesion.

The active energy ray-curable adhesive is a monofunctional monofunctional compound having N-substituted amide-based monomers other than those represented by the general formula (1), various aromatic rings and a hydroxy group, as the radically polymerizable compound (A). It may contain (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, a compound having various (meth) acryloyl groups, and the like. However, in consideration of the adhesiveness and water resistance of the adhesive layer, the ratio of the N-substituted amide monomer represented by the general formula (1) to the total amount of the radically polymerizable compound (A) is 30 to 95. It is preferably mass% and more preferably 35 to 90 mass%.

  Examples of the N-substituted amide-based monomers other than those represented by the general formula (1) include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide. , N-isopropylacrylamide, N-butyl (meth) acrylamide, N-hexyl (meth) acrylamide, aminomethyl (meth) acrylamide, aminoethyl (meth) acrylamide, mercaptomethyl (meth) acrylamide, mercaptoethyl (meth) acrylamide , N-acryloylmorpholine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylpyrrolidine and the like.

  As the monofunctional (meth) acrylate having an aromatic ring and a hydroxy group, various monofunctional (meth) acrylates having an aromatic ring and a hydroxy group can be used. The hydroxy group may be present as a substituent of the aromatic ring, but in the present invention, it is present as an organic group (hydrocarbon group, particularly, one bound to an alkylene group) that bonds the aromatic ring and the (meth) acrylate. Those that do are preferred.

  Examples of the monofunctional (meth) acrylate having an aromatic ring and a hydroxy group include a reaction product of a monofunctional epoxy compound having an aromatic ring and (meth) acrylic acid. Examples of the monofunctional epoxy compound having an aromatic ring include phenyl glycidyl ether, t-butylphenyl glycidyl ether, and phenyl polyethylene glycol glycidyl ether. Specific examples of the monofunctional (meth) acrylate having an aromatic ring and a hydroxy group include, for example, 2-hydroxy-3-phenoxypropyl (meth) acrylate and 2-hydroxy-3-t-butylphenoxypropyl (meth). Acrylate, 2-hydroxy-3-phenyl polyethylene glycol propyl (meth) acrylate and the like can be mentioned.

  Examples of the urethane (meth) acrylate include a (meth) acrylate having an isocyanate group and a hydroxyl group at one end of a diol compound such as polyurethane diol, polyester diol, polyether diol, polyethylene glycol, and polyalkylene glycol such as polypropylene glycol. Reaction products and the like.

Examples of the compound having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate. , An alkyl (meth) acrylate having 1 to 12 carbon atoms such as lauryl (meth) acrylate; an alkoxyalkyl (meth) acrylate monomer such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; ) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, (meth ) Acrylic acid Hydroxyl group-containing monomers such as 0-hydroxydecyl, 12-hydroxylauryl (meth) acrylic acid and (4-hydroxymethylcyclohexyl) -methyl acrylate; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; acrylic acid Caprolactone adduct of styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamido-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid Sulfonic acid group-containing monomers such as; and phosphoric acid group-containing monomers such as 2-hydroxyethylacryloyl phosphate. Also, (meth) acrylamide; maleimide, N-cyclohexylmaleimide, N-phenylmaleimide, etc .; aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate. , (Meth) acrylic acid alkylaminoalkyl-based monomers such as t-butylaminoethyl (meth) acrylate and 3- (3-pyridinyl) propyl (meth) acrylate; N- (meth) acryloyloxymethylenesuccinimide and N- ( Examples thereof include nitrogen-containing monomers such as succinimide-based monomers such as (meth) acryloyl-6-oxyhexamethylenesuccinimide and N- (meth) acryloyl-8-oxyoctamethylenesuccinimide.

  When the active energy ray-curable adhesive further contains (A) a radically polymerizable compound, a monomer having two or more carbon-carbon double bonds, particularly preferably a polyfunctional (meth) acrylate-based monomer. It is preferable because the water resistance of the adhesive layer is improved. Considering the water resistance of the adhesive layer, the monomer having two or more carbon-carbon double bonds is more preferably hydrophobic. Examples of hydrophobic monomers having two or more carbon-carbon double bonds, particularly hydrophobic polyfunctional (meth) acrylate monomers include, for example, tricyclodecane dimethanol diacrylate, divinylbenzene, N, N'-methylene. Bisacrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) Acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate , 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol glycol di (meth) acrylate, glycerin di (meth) acrylate, EO-modified glycerin tri (meth) acrylate, EO-modified diglycerin tetra ( (Meth) acrylate, 2- (2-vinyloxyethoxy) ethyl (meth) acrylate, bisphenol A-EO adduct di (meth) acrylate, trimethylolpropane tri (meth) acrylate, hydroxypivalate neopentyl glycol (meth) Acrylic acid adduct, EO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, iso Anouric acid EO-modified di (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, ε-caprolactone-modified tris ((meth) acryloxyethyl) isocyanurate, 1,1-bis ((meth) acryloyloxymethyl) ethyl Examples thereof include isocyanate, a polymer of 2-hydroxyethyl (meth) acrylate and 1,6-diisocyanate hexane, and 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene.

  The ratio of the monomer having two or more carbon-carbon double bonds to the total amount of the radically polymerizable compound (A) is preferably 5 to 70% by mass, more preferably 10 to 65% by mass. . If this ratio is less than 5% by mass, sufficient water resistance may not be obtained, while if it exceeds 50% by mass, sufficient adhesion may not be obtained.

<< (B) Photoradical generator >>
The (B) photo-radical generator generates radicals by irradiating with active energy rays. Examples of the photo radical generator (B) include a hydrogen abstraction type photo radical generator and a cleavage type photo radical generator.

  Examples of the hydrogen abstraction type photoradical generator include 1-methylnaphthalene, 2-methylnaphthalene, 1-fluoronaphthalene, 1-chloronaphthalene, 2-chloronaphthalene, 1-bromonaphthalene, 2-bromonaphthalene, 1-iodonaphthalene. , 2-Iodonaphthalene, 1-naphthol, 2-naphthol, 1-methoxynaphthalene, 2-methoxynaphthalene, naphthalene derivatives such as 1,4-dicyanonaphthalene, anthracene, 1,2-benzanthracene, 9,10-dichloroanthracene , 9,10-Dibromoanthracene, 9,10-diphenylanthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2,6,9,10-tetracyanoanthracene and other anthracene derivatives, pyrene derivatives, carbazole 9-methylcarbazole, 9-phenylcarbazole, 9-prop-2-ynyl-9H-carbazole, 9-propyl-9H-carbazole, 9-vinylcarbazole, 9H-carbazole-9-ethanol, 9-methyl-3-nitro -9H-carbazole, 9-methyl-3,6-dinitro-9H-carbazole, 9-octanoylcarbazole, 9-carbazolemethanol, 9-carbazolepropionic acid, 9-carbazolepropionitrile, 9-ethyl-3,6 -Dinitro-9H-carbazole, 9-ethyl-3-nitrocarbazole, 9-ethylcarbazole, 9-isopropylcarbazole, 9- (ethoxycarbonylmethyl) carbazole, 9- (morpholinomethyl) carbazole, 9-acetylcarbazole, 9- Allyl Lubazole, 9-benzyl-9H-carbazole, 9-carbazoleacetic acid, 9- (2-nitrophenyl) carbazole, 9- (4-methoxyphenyl) carbazole, 9- (1-ethoxy-2-methyl-propyl) -9H. -Carbazole, 3-nitrocarbazole, 4-hydroxycarbazole, 3,6-dinitro-9H-carbazole, 3,6-diphenyl-9H-carbazole, 2-hydroxycarbazole, 3,6-diacetyl-9-ethylcarbazole and the like. Carbazole derivative, benzophenone, 4-phenylbenzophenone, 4,4'-bis (dimethoxy) benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, methyl 2-benzoylbenzoate Ester, 2- Benzophenone derivatives such as methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone and 2,4,6-trimethylbenzophenone, aromatic carbonyl compounds, [4- (4-methyl Phenylthio) phenyl] -phenylmethanone, xanthone, thioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 1- Examples thereof include thioxanthone derivatives such as chloro-4-propoxythioxanthone and coumarin derivatives.

  The cleavage type photoradical generator is a type of photoradical generator in which the compound is cleaved to generate a radical by irradiation with an active energy ray, and specific examples thereof include arylalkyl such as benzoin ether derivative and acetophenone derivative. Examples thereof include, but are not limited to, ketones, oxime ketones, acylphosphine oxides, S-phenyl thiobenzoates, titanocenes, and derivatives thereof having a high molecular weight. Commercially available cleavage type photoradical generators include 1- (4-dodecylbenzoyl) -1-hydroxy-1-methylethane, 1- (4-isopropylbenzoyl) -1-hydroxy-1-methylethane, 1-benzoyl. -1-hydroxy-1-methylethane, 1- [4- (2-hydroxyethoxy) -benzoyl] -1-hydroxy-1-methylethane, 1- [4- (acryloyloxyethoxy) -benzoyl] -1-hydroxy- 1-methylethane, diphenylketone, phenyl-1-hydroxy-cyclohexylketone, benzyldimethylketal, bis (cyclopentadienyl) -bis (2,6-difluoro-3-pyryl-phenyl) titanium, (η6-isopropylbenzene) -(Η5-Cyclopentadienyl) -iron (II) hexaf Luorophosphate, trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl) -phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2, 4-dipentoxyphenylphosphine oxide or bis (2,4,6-trimethylbenzoyl) phenyl-phosphine oxide, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 4- (methylthiobenzoyl) -1 -Methyl-1-morpholinoethane and the like, but not limited thereto.

  The photoradical generator (B), that is, the hydrogen abstraction type or cleavage type photoradical generator can be used alone or in combination of two or more, but the stability of the photoradical generator alone. Further, more preferable from the viewpoint of curability of the composition in the present invention is a combination of one or more cleavage type photoradical generators. Among the cleavage type photoradical generators, acylphosphine oxides are preferable, and more specifically, trimethylbenzoyldiphenylphosphine oxide (trade name "DAROCURE TPO"; manufactured by Ciba Japan), bis (2,6-dimethoxy-benzoyl). )-(2,4,4-Trimethyl-pentyl) -phosphine oxide (trade name "CGI 403"; manufactured by Ciba Japan) or bis (2,4,6-trimethylbenzoyl) -2,4-dipen Toxyphenylphosphine oxide (trade name "IRGACURE819"; manufactured by Ciba Japan) is preferable.

  The content of the (B) photoradical generator is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, with respect to the total amount of the active energy ray-curable adhesive. More preferably, 0.1-3 parts by mass is particularly preferable.

  When the active energy ray-curable adhesive according to the present invention is used as an electron beam-curable adhesive, the above-mentioned (B) photoradical generator can be optionally used as the adhesive. Further, a sensitizer represented by a carbonyl compound or the like which increases the curing speed and sensitivity by electron beam may be added.

  Examples of the sensitizer include anthracene, phenothiazene, perylene, thioxanthone, benzophenone thioxanthone and the like. Further, as the sensitizing dye, thiopyrylium salt dye, merocyanine dye, quinoline dye, styrylquinoline dye, ketocoumarin dye, thioxanthene dye, xanthene dye, oxonol dye, cyanine dye, rhodamine dye , Pyrylium salt dyes and the like.

  As specific anthracene compounds, dibutoxyanthracene, dipropoxyanthraquinone (Anthracure UVS-1331, 1221 manufactured by Kawasaki Kasei) and the like are effective.

  When the sensitizer is added, its content is preferably 0.01 to 20 parts by mass, and more preferably 0.01 to 10 parts by mass, based on the total amount of the active energy ray-curable adhesive. It is preferably 0.1 to 3 parts by mass, and particularly preferably.

  Further, various additives may be added to the active energy ray-curable adhesive as other optional components as long as the objects and effects of the present invention are not impaired. Such additives include polyamide, polyamideimide, polyurethane, polybutadiene, polychloroprene, polyether, polyester, styrene-butadiene block copolymer, petroleum resin, xylene resin, ketone resin, cellulose resin, fluorine-based oligomer, silicone-based oligomer. Polymers or oligomers such as polysulfide-based oligomers; polymerization inhibitors such as phenothiazine and 2,6-di-t-butyl-4-methylphenol; polymerization initiation aids; leveling agents; wettability improvers; surfactants; plasticizers Agents; ultraviolet absorbers, silane coupling agents, inorganic fillers, pigments, dyes and the like. However, in the active energy ray-curable adhesive, the content of the above-mentioned additive is preferably 0.005 to 20 parts by mass, and 0.01 to 10 parts by mass with respect to the total amount of the active energy ray-curable adhesive. More preferably, it is 0.1 to 5 parts by mass.

  As the photocationic polymerization type active energy ray-curable adhesive, for example, a composition containing a compound having an epoxy group and a photoacid generator can be used.

  The viscosity of the active energy ray-curable adhesive is preferably 10 to 350 cps (25 ° C.), more preferably 20 to 300 cps (25 ° C.), and further preferably 40 to 150 cps (25 ° C.). When the viscosity is 10 cps or less, the viscosity becomes too low, and the applied adhesive is applied to the back side of the film (single protective polarizing film), and it is difficult to design the thickness of the adhesive layer. Further, if the viscosity exceeds 300 cps, the viscosity becomes too high, and if the line speed is increased, the adhesive cannot be sufficiently coated or coating streaks are likely to occur, which is preferable in terms of productivity. Absent.

  The coating method of the active energy ray-curable adhesive on the second surface of the polarizer in the one-sided protective polarizing film is appropriately selected depending on the viscosity of the composition and the intended thickness. Examples of the coating method include a reverse coater, a gravure coater (direct, reverse or offset), a bar reverse coater, a roll coater, a die coater, a bar coater, a rod coater and the like. In addition, a method such as a dipping method can be appropriately used for coating.

  In addition, the application of the adhesive improves the adhesiveness between the second transparent protective film and the polarizer from the viewpoint of filling the stripes and irregularities on the surface of the polarizer to prevent bubbles from being trapped in the bonding surface. From this viewpoint, it is preferable that the thickness of the finally formed adhesive layer is 300 nm or more. On the other hand, it is considered that the thicker the adhesive layer is, the more it is possible to reduce the trapped air bubbles at the time of bonding, but it is not preferable in terms of water resistance if the adhesive layer is too thick. Therefore, the thickness of the adhesive layer is preferably 1.3 μm or less, more preferably 1.2 μm or less, and further preferably 1 μm or less. The thickness of the adhesive layer is preferably controlled to be 300 nm to 1 μm, more preferably 350 to 900 nm, and further preferably 400 to 800 nm.

<Step (2)>
After performing the step (1), the second transparent protective film is attached via the active energy ray-curable adhesive in the step (2). The bonding in the step (2) can be performed by a roll laminator or the like.

  Further, in the step (2), after applying the active energy ray-curable adhesive to the second surface of the polarizer in the one-sided protective polarizing film in the step (1), after 2 seconds or more, Is preferably applied. Depending on the type and viscosity of the active energy ray-curable adhesive, the adhesive was applied to the second surface of the polarizer in order to spread the adhesive on the second surface of the polarizer with many streaks and irregularities. It is preferable to attach the second transparent protective film after a short time. By setting the time after application of the adhesive to 2 seconds or more, the adhesive can be made to fit on the surface of the polarizer more than immediately after application, and trapped air bubbles when the second transparent protective film is attached It can be further reduced. The elapsed time is more preferably 4 seconds or longer, and further preferably 6 seconds or longer. If the elapsed time is too long, the coating liquid penetrates too much into the base material, and the adhesive single layer becomes thin so that the adhesive cannot be removed. Therefore, the elapsed time is preferably 30 seconds or less.

  As the second transparent protective film, the same materials as those exemplified in the first transparent protective film can be used, and a film having a similar thickness can be used. The second transparent protective film may have the same material and thickness as the first transparent protective film, or may have different material and thickness. The second transparent protective film can be appropriately selected and used.

<Step (3)>
Next, after performing the step (2), in step (3), the active energy ray-curable adhesive is irradiated with active energy rays to form an adhesive layer. Examples of active energy rays include ultraviolet rays and electron rays.

When a UV-curable adhesive is used, any appropriate conditions can be adopted as the UV irradiation conditions as long as the above-mentioned adhesive can be cured. The dose of ultraviolet rays is preferably from 100 to 500 mJ / cm ² in accumulated light quantity, and even more preferably 200 to 400 mJ / cm ^2.

  In the case of adopting an electron beam-curable adhesive, any appropriate condition can be adopted as the electron beam irradiation condition as long as the above-mentioned adhesive can be cured. For example, the electron beam irradiation has an acceleration voltage of preferably 5 kV to 300 kV, more preferably 10 kV to 250 kV. If the accelerating voltage is less than 5 kV, the electron beam may not reach the adhesive and may be insufficiently cured. If the accelerating voltage exceeds 300 kV, the penetrating force through the sample is too strong and the electron beam bounces off, resulting in a transparent protective film or It may damage the polarizer. The irradiation dose is 5 to 100 kGy, and more preferably 10 to 75 kGy.

  The electron beam irradiation is usually carried out in an inert gas, but if necessary, it may be carried out in the air or under the condition that a small amount of oxygen is introduced. Depending on the material of the transparent protective film, by appropriately introducing oxygen, it is possible to cause oxygen inhibition on the surface of the transparent protective film to which the electron beam first hits, which can prevent damage to the transparent protective film. The electron beam can be efficiently irradiated.

  The irradiation direction of the active energy ray in the step (3) can be irradiation from any appropriate direction, but the irradiation from the first transparent protective film side causes an excess of light because it is absorbed by the polarizer. Since irradiation is required, it is preferable to irradiate from the side of the second transparent protective film from the viewpoint of effective irradiation light.

  The method for producing a polarizing film of the present invention includes the steps (1) to (3), but may include steps other than the above steps. For example, in the step (1), a step of performing a dry treatment on the second surface of the polarizer before applying the active energy ray-curable adhesive to the second surface of the polarizer in the one-sided protective polarizing film. Can be provided. Specific dry treatments include corona treatment and plasma treatment. By performing the dry treatment, the surface modification treatment of the second surface of the polarizer is performed, which is preferable for improving the wettability and the adhesiveness of the adhesive.

  Further, in laminating the polarizer (on both the first surface and the second surface) and the transparent protective film, an easily adhesive layer can be provided between the transparent protective film and the adhesive layer. The easy-adhesion layer can be formed of various resins having a polyester skeleton, a polyether skeleton, a polycarbonate skeleton, a polyurethane skeleton, a silicone-based, a polyamide skeleton, a polyimide skeleton, a polyvinyl alcohol skeleton, or the like. These polymer resins may be used alone or in combination of two or more. Further, other additives may be added to form the easily adhesive layer. Specifically, a tackifier, a UV absorber, an antioxidant, a stabilizer such as a heat stabilizer, and the like may be used.

  The easy-adhesion layer is usually provided in advance on the transparent protective film, and the easy-adhesion layer side of the transparent protective film and the polarizer are bonded together by an adhesive layer. The easy-adhesion layer is formed by applying a material for forming the easy-adhesion layer onto the transparent protective film by a known technique and drying. The material for forming the easy-adhesion layer is usually prepared as a solution diluted to an appropriate concentration in consideration of the thickness after drying and the smoothness of coating. The thickness of the easily adhesive layer after drying is preferably 0.01 to 5 μm, more preferably 0.02 to 2 μm, and further preferably 0.05 to 1 μm. A plurality of easy-adhesion layers can be provided, but in this case as well, it is preferable that the total thickness of the easy-adhesion layers be within the above range.

  When the polarizing film of the present invention is produced in a continuous line, the line speed depends on the curing time of the adhesive, but is preferably 1 to 500 m / min, more preferably 5 to 300 m / min, further preferably 10 to 100 m / min. Is. If the line speed is too low, the productivity is poor, or the transparent protective film is damaged too much, and a polarizing film that can withstand a durability test or the like cannot be produced. If the line speed is too high, the curing of the adhesive may be insufficient and the desired adhesiveness may not be obtained.

  A polarizing film having the first transparent protective film and the second transparent protective film on both surfaces of the polarizer is obtained as described above, but a hard coat layer and an antireflection film are provided on the surface of the transparent protective film on which the polarizer is not adhered. Functional layers such as layers, anti-sticking layers, diffusion layers or anti-glare layers can be provided. The hard coat layer, the antireflection layer, the antisticking layer, the functional layer such as the diffusion layer and the antiglare layer can be provided on the transparent protective film itself, or separately, separately from the transparent protective film. You can also

  In practical use, the polarizing film of the present invention can be used as an optical film laminated with another optical layer. The optical layer is not particularly limited, but for example, for forming a liquid crystal display device such as a reflection plate, a semi-transmission plate, a retardation plate (including a wave plate such as 1/2 or 1/4), and a viewing angle compensation film. One or two or more optical layers that may be used can be used. In particular, a reflective polarizing film or a semi-transmissive polarizing film obtained by further laminating a reflective plate or a semi-transmissive reflective plate on the polarizing film of the present invention, an elliptical polarizing film or a circularly polarized light obtained by further laminating a retardation plate on the polarizing film. A wide viewing angle polarizing film obtained by further laminating a viewing angle compensation film on the film or the polarizing film, or a polarizing film obtained by further laminating a brightness improving film on the polarizing film is preferable.

  The optical film obtained by laminating the above optical layer on the polarizing film can be formed by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like. It is excellent in stability and assembling work, and has an advantage that the manufacturing process of a liquid crystal display device can be improved. Appropriate adhesion means such as an adhesive layer may be used for lamination. In adhering the above-mentioned polarizing film and other optical films, their optic axes can be set at an appropriate arrangement angle depending on the intended retardation characteristics and the like.

  An adhesive layer for adhering to another member such as a liquid crystal cell may be provided on the above-mentioned polarizing film or an optical film in which at least one layer of the polarizing film is laminated. The pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer is not particularly limited, but for example, an acrylic polymer, a silicone-based polymer, polyester, polyurethane, polyamide, polyether, or a fluorine-based or rubber-based polymer as a base polymer is appropriately selected. Can be used. In particular, an acrylic pressure-sensitive adhesive, which has excellent optical transparency, exhibits appropriate wettability, cohesiveness and adhesiveness, and has excellent weather resistance and heat resistance, can be preferably used.

  The pressure-sensitive adhesive layer may be provided on one side or both sides of the polarizing film or the optical film as a layer in which different compositions or types are laminated. When it is provided on both sides, an adhesive layer having different composition, type and thickness may be provided on the front and back of the polarizing film or the optical film. The thickness of the pressure-sensitive adhesive layer can be appropriately determined depending on the purpose of use, adhesive strength, etc., and is generally 1 to 500 μm, preferably 1 to 200 μm, and particularly preferably 1 to 100 μm.

  The exposed surface of the pressure-sensitive adhesive layer is temporarily covered with a separator for the purpose of preventing its contamination until it is put into practical use. As a result, it is possible to prevent contact with the adhesive layer in the usual handling state. As the separator, except for the above thickness conditions, for example, a plastic film, a rubber sheet, paper, cloth, a non-woven fabric, a net, a foam sheet or a metal foil, an appropriate thin sheet such as a laminate thereof, a silicone-based or Appropriate ones conventionally used, such as those coated with an appropriate release agent such as long-chain alkyl-based, fluorine-based or molybdenum sulfide, may be used.

  The polarizing film or optical film of the present invention can be preferably used for forming various devices such as liquid crystal display devices. The liquid crystal display device can be formed in a conventional manner. That is, a liquid crystal display device is generally formed by appropriately assembling a liquid crystal cell and a polarizing film or an optical film, and optionally a component such as an illumination system and incorporating a drive circuit. There is no particular limitation except that the polarizing film or the optical film according to the invention is used, and the conventional method can be applied. The liquid crystal cell may be of any type such as TN type, STN type, and π type.

  It is possible to form an appropriate liquid crystal display device such as a liquid crystal display device in which a polarizing film or an optical film is arranged on one side or both sides of a liquid crystal cell, or a device using a backlight or a reflector in an illumination system. In that case, the polarizing film or the optical film according to the present invention can be installed on one side or both sides of the liquid crystal cell. When polarizing films or optical films are provided on both sides, they may be the same or different. Furthermore, when forming a liquid crystal display device, for example, a diffusion plate, an anti-glare layer, an antireflection film, a protection plate, a prism array, a lens array sheet, a light diffusion plate, a backlight, and other appropriate components are provided at appropriate positions in a single layer or Two or more layers can be arranged.

  The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, all parts and% in each example are based on weight. A protective polarizing film was produced.

<Preparation of one-sided protective polarizing film (1)>
In order to manufacture a thin polarizing film, first, a laminated body in which a 9 μm-thick PVA layer is formed on an amorphous PET substrate is subjected to in-air auxiliary stretching at a stretching temperature of 130 ° C. to form a stretched laminated body, and then stretched. The laminated body is dyed to form a colored laminated body, and the colored laminated body is stretched integrally with the amorphous PET substrate so as to have a total stretching ratio of 5.94 times by stretching in a boric acid solution in water at a stretching temperature of 65 degrees. An optical film laminate including a 4 μm thick PVA layer was produced. The PVA molecules of the PVA layer formed on the amorphous PET substrate by such a two-stage stretching are highly oriented, and the iodine adsorbed by dyeing is highly oriented in one direction as a polyiodine ion complex. It was possible to produce an optical film laminate including a PVA layer having a thickness of 4 μm, which constitutes a highly functional polarizing film. Further, while applying a polyvinyl alcohol-based adhesive to the surface (first surface) of the polarizing film of the optical film laminate, a saponified 40 μm thick triacetyl cellulose film (first transparent protective film) was laminated. After that, the amorphous PET substrate was peeled off. Hereinafter, this is referred to as a thin piece protective polarizing film (1).

<Second transparent protective film>
A 60 μm-thick ZEONOR film (manufactured by Nippon Zeon Co., Ltd.) subjected to corona treatment was used.

(Adjustment of active energy ray curable adhesive)
The following components were mixed at a ratio of 40 parts of compound (a), 20 parts of compound (b), 40 parts of compound (c) and 3 parts of a photopolymerization initiator, and stirred at 50 ° C. for 1 hour to cure with active energy rays. A mold adhesive was obtained.
Radical polymerizable compound (a): HEAA (hydroxyethyl acrylamide), manufactured by Kojinsha;
Radical-polymerizable compound (b): Light acrylate BP-4EAL (EP adduct of bisphenol A diacrylate), manufactured by Kyoei Chemical Co., Ltd .;
Radical polymerizable compound (c): ACMO (acryloylmorpholine), manufactured by Kojinsha;
Photopolymerization initiator: IRGACURE819 (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide), manufactured by BASF.

<Measurement of viscosity of adhesive>
The viscosity of the adhesive was measured with a precision rotary viscometer.

Example 1
(Process 1)
The adhesive is applied to the second surface of the one-sided protective polarizing film (1) using a micro gravure coater (gravure roll: # 180, rotation speed 140% / line speed) to obtain the final thickness of the adhesive layer. Was 600 nm.

(Process 2)
Then, after applying the adhesive for 10 seconds, the second transparent protective film was pasted through the adhesive with a roll machine.

(Process 3)
Then, ultraviolet rays were radiated from the side of the laminated second transparent protective film to obtain a polarizing film having transparent protective films on both sides. The line speed was 20 m / min, and the irradiation amount of ultraviolet rays was 700 mJ / cm ² in terms of integrated light amount.

Examples 2-5 and Comparative Example 1
In Example 1, except that the coated surface of the adhesive, the thickness of the adhesive layer, the time after coating, the ratio of each compound of the adhesive, and the viscosity were changed as shown in Table 1. A polarizing film was produced in the same manner as in 1.

[Evaluation]
The following evaluation was performed about the polarizing film obtained by the Example and the comparative example. The results are shown in Table 1.

<Appearance evaluation>
The appearance of the obtained polarizing film was observed with an optical microscope, and bubbles having a maximum diameter of 5 μm to 200 μm were counted. The results are shown in Table 1.

Claims (7)

A method for producing a polarizing film, wherein the first and second transparent protective films are provided on the first and second surfaces of the polarizer.
An active energy ray-curable adhesive (provided that urethane is used) on the second surface of the polarizer in the one-sided protective polarizing film in which the first transparent protective film is provided on the first surface of the polarizer via the polyvinyl alcohol-based adhesive layer. A step (1) of applying an active energy ray-curable adhesive composition containing (meth) acrylate ,
A step (2) of bonding a second transparent protective film via the active energy ray-curable adhesive,
A polarizing film comprising: a step (3) of irradiating the active energy ray-curable adhesive with an active energy ray to form an adhesive layer having a thickness of 300 nm to 1.3 μm. Production method. The polarizer is a continuous web polarizing film made of a polyvinyl alcohol-based resin in which a dichroic material is oriented, and the one-sided protective polarizing film is a polyvinyl alcohol-based film formed on a thermoplastic resin substrate. A laminate including a resin layer is stretched in a two-stage stretching process consisting of auxiliary stretching in air and stretching in boric acid in water, and the polyvinyl alcohol adhesive layer is interposed on the surface of the polarizing film of the optical film laminate obtained. The method for producing a polarizing film according to claim 1, wherein the thermoplastic resin substrate is peeled off after the first transparent protective film is bonded to the first transparent protective film .   In the step (1), after applying the active energy ray-curable adhesive to the second surface of the polarizer in the one-sided protective polarizing film, two or more seconds have passed, and then the step (2) is performed. The method for producing a polarizing film according to claim 1 or 2, which is characterized in that.   The method for producing a polarizing film according to claim 1, wherein the active energy ray-curable adhesive has a viscosity of 10 to 350 cps (25 ° C.).   The method for producing a polarizing film according to any one of claims 1 to 4, wherein the active energy ray-curable adhesive contains a radically polymerizable compound.   The step (1) includes a step of performing a dry treatment on the second surface of the polarizer before applying the active energy ray-curable adhesive to the second surface of the polarizer of the one-sided protective polarizing film. The method for producing a polarizing film according to any one of claims 1 to 5, which is characterized in that. Irradiation with an active energy ray in said process (3) is performed from the 2nd transparent protective film side, The manufacturing method of the polarizing film in any one of Claims 1-6 characterized by the above-mentioned.