TW201231277A - Process for manufacture of polarizing laminate film, and process for manufacture of polarizing plate - Google Patents

Abstract

Provided is a process for manufacturing a polarizing laminate film having a small film thickness and high performance. A process for manufacturing a polarizing laminate film comprising a base film and a polarizer layer formed on one surface of the base film, which comprises a resin layer formation step, a stretching step and a dyeing step in this order, wherein the resin layer formation step comprises forming a resin layer containing a polyvinyl alcohol resin on one surface of the base film to produce a laminate film, the stretching step comprises carrying out the free-end uniaxial stretching of the laminate film, and the dyeing step comprises dyeing the resin layer in the laminate film with a dichroic dye to form the polarizer layer, and wherein the width (W1) of the laminate film that is not subjected to the free-end uniaxial stretching yet and the width (W2); of the laminate film that has been subjected to the free-end uniaxial stretching fulfill the relationship represented by formula (1).

Description

[Technical Field] The present invention relates to a method for producing a polarizing laminated film and a method for producing a polarizing plate. [Prior Art] The polarizing plate is widely used as a polarizing supply element in a liquid crystal display device and as a polarizing detecting element. As a polarizing plate, a protective film containing cellulose triacetate has been used in the past, and a polarizing film containing a polyethylene glycol resin has been used. However, in recent years, liquid crystal display devices have been used for notebook computers and mobile phones. The expansion of the mobile device and the expansion of a large-sized television set require thinner walls. In the polarizing plate, the polarizing film is sandwiched between two protective films. However, in order to reduce the thickness of the polarizing plate, it is proposed to reduce the protective film from two sheets to a crepe sheet (Patent Document 1) or to change the thickness of the protective film. Thin method. However, the polarizing film is produced by stretching and dyeing a film raw material sheet of a polyvinyl alcohol-based resin (usually about 75 μm thick), and the thickness of the film after stretching is usually about 30 μm. Further thinning has the problem that the film is easily broken when it is extended, and it is difficult. As another example of the method for producing a polarizing plate, a method of applying a solution containing a polyvinyl alcohol-based resin to a surface of a base film to form a resin layer, and then extending the laminated film including the base film and the resin layer is proposed. Then, the polarizing sheet layer ' is formed from the resin layer by dyeing to obtain a polarizing layer film having a polarizing sheet layer (for example, see Patent Document 2). A method in which the film is used as a polarizing plate directly after the film is used as a polarizing plate or a protective film is bonded to the film after peeling off the substrate is disclosed. This method has the advantage that a polyethylene oxide-based resin layer is formed by coating on a substrate, so that a polarizing sheet layer which is particularly thinner than a film raw material sheet using a polyethylene glycol-based resin can be obtained. 'Because the substrate is integrated with the polyethylene glycol base resin layer, there is less breakage during elongation. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A No. 2000-338329 (Patent Document 2) However, in the case of the patent document 2, the stretching ratio is 5 times or less and is relatively low, and the performance of the obtained polarizing laminate film and the polarizing plate may not be sufficient. An object of the present invention is to provide a method for producing a film and a high-performance polarizing laminate film and a method for producing the polarizing plate. [Technical means for solving the problem] An aspect of the present invention provides a method for producing a polarizing laminated film, which comprises a substrate film and a polarizing layer formed on a polarizing layer of one surface of the substrate film. The method for producing a film; the method for producing a polarizing plate includes the following steps: a resin layer forming step of forming a resin layer comprising a polyvinyl alcohol (polyvinyl alcohol) resin on one side of a substrate film to obtain a laminated film; An extending step of: performing a uniaxial stretching of the free end of the laminated film; and a dyeing step of dyeing the resin layer of the laminated film with a dichroic dye to form a polarizer layer; and in the extending step, The width W1 of the laminated film before the uniaxial stretching of the free end and the width W2 of the laminated film after the uniaxial stretching of the free end satisfy the following formula: (W1-W2) h-W1x 100^40 1) In the above extending step, preferably the free end uniaxial extension is carried out by transporting the laminated film between the two pairs of rolls having different circumferential speeds, and the distance L between the two sets of rolls satisfies the following Formula (2) Relations.

Wl - LS1.0 Formula (7) Further, in the above extension step, it is preferred that the ratio of the circumferential speeds of the two pairs of roller pairs exceeds 5 times. The base film used in the above production method preferably contains a polyolefin resin. In the resin layer forming step, the resin layer is preferably formed so as to have a thickness exceeding 3 and 30 μm or less. Further, the thickness of the polarizer layer of the polarizing laminated film is preferably from 1 to 5 pm. The thickness of the polarizer layer may be 4_0 to 5·5 μm or 4, 2 to 5.2 μm. Further, an aspect of the present invention provides a method for producing a polarizing plate, which comprises a polarizing plate, and a method for producing a polarizing plate bonded to a protective film on one side of a polarizing plate layer, and a method of manufacturing the polarizing plate In the order of the protective film bonding step, the polarizing laminated film is produced by the above-described manufacturing method, and the polarizing layer in the polarizing laminated film is opposite to the surface on the substrate film side. A protective film is bonded to the surface; and a substrate film peeling step of peeling the base film from the polarizing laminated film. [Effects of the Invention] 160675.doc 201231277 By the aspect of the production method of the present invention, a polarizing laminated film and a polarizing plate which are thin and have excellent optical properties can be obtained. [Embodiment] Hereinafter, preferred embodiments of the method for producing a polarizing laminated film of the present invention and a method for producing a polarizing plate will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments shown below. [Manufacturing method of polarizing laminated film] Fig. 1 is a flow chart showing an embodiment of a method for producing a polarizing laminated film of the present invention. The polarizing laminate film produced in the present embodiment comprises a base film and a polarizer layer formed on one surface of the base film. In the method for producing a polarizing laminated film of the present embodiment, the resin layer forming step (S10) is employed to form a resin layer containing a polyethylene glycol resin on one surface of the base film to obtain a laminated film; a step (S20) of performing a free end uniaxial stretching on the laminated film; and a dyeing step (S30) of dyeing the resin layer of the laminated film by a dichroic dye to form a polarizing layer 0. In the form, a laminate in which a resin layer containing a polyvinyl alcohol-based resin is formed on one surface of a base film is referred to as a "laminated film". The resin layer containing a polyvinyl alcohol-based resin is also referred to as a "polyvinyl alcohol-based resin layer". A polyvinyl alcohol-based resin layer having a function as a polarizer is referred to as a "polarized sheet layer". A laminated body having a polarizing plate layer on one surface of the base film is referred to as a "polarizing laminated film J. Further, a laminated body having a protective film on one surface of the polarizing film layer is referred to as a "polarizing plate". <Extension Step (S20)> 160675.doc 201231277 Here, the base film and the laminated film including the polyethylene glycol-based resin layer are subjected to free-end single-sleeve stretching. In the extending step (S20), the width W1 of the laminated film before the uniaxial stretching of the free end and the width W2 of the laminated film after the uniaxial stretching of the free end satisfy the following formula (1): (Wl-W2) +Wlxl00 2 40 relationship. Further, the width W1 means the width of the laminated film before stretching in the direction perpendicular to the extending direction. The width ψ2 refers to the width of the laminated 臈 after the extension in the direction perpendicular to the extending direction. The left side of the υ (W1-W2) is the difference between the width W1 of the laminated layer 前 before the uniaxial extension of the free end and the width W2 of the laminated film after the uniaxial extension of the free end, that is, the free end uniaxial The obtained shrinkage width (Hin) is a phenomenon in which W2 is smaller than W1 due to stretching. In the present embodiment, the ratio of the width of the laminate film to the width of the laminate film before stretching is expressed by the formula (1). The value obtained on the left side is called the "shrinkage ratio". When the ratio of the shrinkage is not satisfied; I is in the relationship of the above formula (1), that is, when the meter is not reached, the polyethylene resin layer is not sufficiently aligned. In some cases, the degree of polarization of the polarizer layer is not sufficiently high. Further, the shrinkage ratio is preferably 40 to 7〇%, more preferably 5〇 to 65%, and particularly preferably 52.6 to 6〇. In addition, the shrinkage ratio may be 52.6 to 56.8%, and may be 5U to the township. When the shrinkage ratio exceeds 鸠, cracking of the laminated film is liable to occur, so that the workability and handleability in the subsequent steps are lowered. The extension processing in the extension step (S20) is not limited to one stage extension, and may be more When the multi-stage extension is performed, the above-mentioned shrinkage ratio 160675.doc 201231277 is set as the shrinkage ratio of all the stages of the extension processing. = Stretching step (S20) t, free end uniaxial The stretching is preferably carried out by transferring the laminated crucible between the two pairs of rolls: that is, it is preferable to convey the laminated film from the pair of rolls having a slower peripheral speed toward the lighter speed of the circumferential speed. 2 is a schematic diagram showing a case where the laminated film is conveyed between two _ pairs in the extending step (S20) and the free end is uniaxially extended in the longitudinal direction. In the circle 2, in the direction of the arrow The group is lightly transporting the laminate (1) between the pair of rollers 2 of the month 2, and is located at the upstream of the transport direction " and the circumferential speed of the pair of rollers 2 is slower than the circumferential speed of the second group of pairs 3 which are located downstream of the transport direction. By the difference in circumferential speed, when the two sets of roller pairs 2, 3 are transported, the laminated film is stretched in the transport direction (the free end is uniaxially extended. The second set of roller pairs 2 includes two losses of the same peripheral speed) Pro ^, ^. Sandwich between two clips, 2b (4) The first telegraph pair 3 includes two clips, the lucky ones 3a, 3b having the same circumferential speed. The stacking stack is lost between the two cool rolls 3...b and is transported by rotation. The heating device 4 between the two and the 2'3 maintains the extended region in the heating device 4 at a specific extension temperature and twists the product (4) in the transfer. The laminated film before passing through the first group 2 is observed. That is, the width of the laminated film 1 before the uniaxial stretching of the free end is set to be W2. The width of the laminated film 1 after the uniaxial stretching of the laminated film 1 of the second group of rolls 3 is uniaxially extended. Let W1 and W2湓<2 L, 〇_., 2 satisfy the relationship of the above formula (1), adjust the peripheral speed of the pair of rollers 2, 3, the distance L between the two sets of roller pairs 2, 3, and the extension temperature, etc. . 160675.doc 201231277 It is preferable to make the distance L between the two pairs of roller pairs 2 and 3 satisfy the relationship of the following formula (2).

Wl-L^ 1.0 Equation (2) When the relationship of the formula (2) is satisfied, it is easy to extend in a manner that satisfies the relationship of the formula. More preferably, the value on the left side of the formula (2) is 0.5 or less. The value of the left side of the formula (2) may be 〇.〇7~〇·45, or 〇·〇7~〇.30, or 0.30~0.45. The circumferential speed of the second group of roller pairs 3 is preferably More than 5 times the circumferential speed of the second set of roller pairs 2. Further, in the present embodiment, when the free end uniaxial stretching is performed by transporting between the two pairs of the pair of circumferential speeds, the ratio of the peripheral speeds between the two sets of roller pairs is defined as the stretching ratio. The stretching ratio in the stretching step (S20) is preferably more than 5 times and 17 times or less. The difference between the circumferential speed of the second set of roller pairs 3 and the circumferential speed of the second set of roller pairs 2 is preferably in the range of 0.5 m/min to 14 〇 m/min, more preferably! The range of 〇 m/min is more preferably in the range of 3 〇 m/min to 79 m/min. Here, the peripheral speed of the second group of roller pairs 3 is preferably in the range of 〇6 m/min to 2 〇〇m/mini, more preferably in the range of 5.0 m/min to 8 〇 m/min. If the 6-axis is not reached, the productivity is not good, and when it exceeds the -, the processing will become difficult. Also in the first group of roller pairs 2 and 2 groups. Therefore, when the first group of roller pairs 2 and the second layer can suppress the conveyed laminated film 蜿, in the apparatus shown in FIG. 2, the pair of roller pairs such as guide rollers are further provided between the three pairs. When the distance L becomes longer, Jin Yan. The laminated film 1 is heated in the stretching step (S20). The heating method can be 160675.doc 201231277 for the heater heating method, Α ...... placed in the line heater, guillotine heater, panel heating Yisi 6 and placed in the waste abundance ^ X #^, below, and added by radiant heat ...,), the method of heating the coke itself, and the heating method (for example, heating in the extended area of the itch of the itch) . In the present invention, the area heating method is preferred from the viewpoint that the stretching temperature is 0 & = uniform. In this case, the two-roller fork can be placed in the temperature-adjusted extension area or outside the extension area. 々 # # ^ 1 疋 疋 为了 为了 为了 为了 为了 为了 为了 为了 为了 为了 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ In the case of the regional heating method, the so-called extension strictly selects the ambient temperature in the private area of the m X system. Moreover, in the heater heating method, when the furnace is patrolled and heated, the so-called extension vessel is in the heart of the furnace, and the method of adding the rail to the light itself is called the extension temperature. Surface temperature. In the stretching step (S20), the laminated film may be preheated as a preheating method, and any of the above-mentioned laminated films may be used in combination with μ, +, and butyl. The preheating can be carried out when the laminated film passes through the pair of rolls of the upstream j, passes through the pair on the upstream side, and passes through the pair of rolls on the upstream side. As the temperature for preheating, it is preferred to listen to a temperature lower than the extension temperature. In the case of passing the roller pair on the upstream side in a state of being preheated, if the preheating temperature is too high, there is a possibility that the upstream side is extended and the sufficient width cannot be generated. After the extension in the extension step (4), the laminate film can also be cured. The temperature of the thermosetting crucible is suitably determined, but is preferably in the range of (extension - 〇 ° C) ~ (extension temperature - 80 ° C), more preferably to the horse (extension temperature - 0 ° c) ~ (extension temperature - 50 °) C) The scope. I60675.doc • 10· 201231277 The free end uniaxial stretching process in the extending step (S20) of the present invention is preferably a longitudinal stretching process performed on the longitudinal direction of the laminated film as shown in FIG. 2 . The reason for this is that if it is a lateral extension, it is difficult to produce a shrinkage as in the above formula (1). According to the above production method, a polarizing laminate film having a polarizer layer having excellent polarizing performance on a substrate film can be obtained. Further, the polarizing film layer can be easily thinned by the above-described production method, and for example, the thickness of the polarizing plate layer can be made 1.5 μη to 15 μηη. As described below, the polarizing laminate film may also be used as an intermediate product for causing the polarizer layer to be transferred toward the protective film. Further, when the base film has a function as a heat retaining film, the polarizing laminated film can also be directly used as a polarizing plate. [Manufacturing Method of Polarizing Plate] Fig. 3 is a flow chart showing an embodiment of a method for producing a polarizing plate of the present invention. The polarizing plate produced in the present embodiment includes a polarizing plate layer and a protective film formed on one surface of the polarizing plate layer. In the method for producing a polarizing plate of the present embodiment, the polarizing laminated film is obtained by sequentially performing the following steps: a resin layer forming step (S10) of forming a resin layer containing a polyvinyl alcohol-based resin on one surface of the base film. Obtaining a laminated film; an extending step (S2〇) for uniaxially stretching the laminated film; and a dyeing step (S3〇) for dyeing the resin layer of the laminated film with a dichroic dye to form a polarizing layer . The method for producing a polarizing plate according to the present embodiment includes the following steps: a protective film bonding step (S40), which is a surface opposite to the surface of the polarizing film layer on the substrate film side in the polarizing laminated film. The upper protective film is adhered; and the substrate film peeling step (S50) is carried out from the polarizing laminated film peeling substrate 160675.doc 201231277 film. The resin layer forming step (S 1 〇), the stretching step (S20), and the dyeing step (S30) for obtaining a polarizing laminated film are the same as those for using the polarizing laminated film described with reference to Figs. A polarizing plate having a polarizing plate layer having excellent polarizing properties on the protective film can be obtained by the above-described production method. Moreover, the polarizing plate layer can be easily thinned by the above-described manufacturing method. For example, the thickness of the polarizing plate layer can be made 1 5 μηι to 15 μm. The polarizing plate can be used, for example, by bonding it to another optical film or a liquid crystal element via a pressure-sensitive adhesive. Hereinafter, each step of the resin layer forming step (s1〇), the dyeing step (S30), the protective film bonding step (S4〇), and the base film peeling step (S5〇) in FIGS. 1 and 3 will be described in detail. . Further, the extension step (S2〇) has been described in detail in the above. <Resin layer forming step (S10)> In the resin layer forming step (S10), a resin layer containing a polyethylene glycol-based resin as a main component is formed on one surface of the base film. (Base film) As the resin used for the base film, for example, a thermoplastic resin excellent in transparency, mechanical strength, thermal stability, and elongation can be used, and it can be based on the glass transition temperature Tg or the melting point of the substrate. A suitable resin is used. The base film is preferably used in a temperature range which is extendable to the elongation of the polyethylene-based resin layer which is laminated thereon. Specific examples of the thermoplastic resin include polyolefin resin. , polyester resin, cyclic polyolefin resin (norcene-based resin), (meth)acrylic resin, cellulose vinegar resin, polycarbonate resin, polyethylene 160675.doc -12· 201231277 alcohol Resin, vinyl acetate resin, polyarylate tree < Take this ethylene resin, polyether sulfone resin, polysulfone resin, polyamine resin, polyimide resin, and the like a mixture, a copolymer, etc. The base film may be a film containing only one type of the above-mentioned resin, and a film obtained by mixing two or more kinds of resins. The base film may be a single layer of ruthenium or a layer film. 1 as a hydrocarbon resin The poly(10) or polypropylene material is preferred, and the fat is preferably extended in a stable manner and at a high rate. Further, the ethylene/polypropylene condensate obtained by copolymerizing ethylene and propylene may also be used. Acrylate is copolymerized with other types of monomers. Examples of other monomers that can be used with other types of women include ethylene, α-futosan, and soot. Preferably, the carbon number is 4 and the number of bucks is 4. The above α-olefin is more preferably a carbon number of 4 to α-ene. As a carbon number of 4, a specific example of a <small smoke, for example, may be listed as -butene, 1- Pentene, bake dilute, 丨 _ ̄ ̄ ̄ ̄ ̄ ̄ 丨 辛 辛 辛 辛 丨 丨 丨 丨 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键 键Ethylene-based ring-containing material. The other monomer to be copolymerized with it can be a "copolymer" copolymer can be a random copolymer, can also be aged 'and a total of things. The ratio of the other monomer derived from the copolymer can be obtained by the method described in "Golden Eight Composition Early π Containing Zhuang Road... 妨J (1995, Ji Yiguowu Bookstore issued wq616 page) (=

Mfrared) was determined by spectrometry. , 'Good (IR is good as a propylene-based resin film constituting a propylene-based resin film, which can be compared with a homopolymer of propylene, a propylene-ethylene random copolymer, a small propylene, a copolymer, and a propylene- Vinyl-olefin random copolymer. 160675.doc 201231277 The propylene-based structure of the propylene-based resin film is essentially the same as the same row of ceramics. The propylene-based resin film of the olefinic resin is excellent, and it is excellent in mechanical strength in a high-temperature environment. 仏 is a good condensed vinegar-based resin, and a polycondensate of a mercapto alcohol having a vinegar bond. Even acid and polyacids, for example, there are "repulsive acid mainly used in the binary two of the four dicarboxylic acid, terephthalic acid, dibenzoic acid diterpene, naphthalene dicarboxylic acid dimetho_ _ corp. In addition, diol diol is mainly used as propylene glycol, butane diol, neopentyl glycol, cyclohexanol-methanol, etc. Specific examples of the resin include polyethylene terephthalate and poly Dibutyl terephthalate, polyethylene naphthalate, polyethylene naphthalate, poly Propylene phthalate, polycae propylene diacetate, polypair, hexane cyclohexane di ", polynaphthalene dicyclohexyl dicarboxylate, etc. These mixed resins or copolymers may also It is preferable to use a pentene-based resin as the cyclic polyolefin-based resin. The cyclic polyolefin-based resin is a general term for a resin obtained by polymerizing a cyclic olefin as a polymerization unit, and examples thereof include a Japanese patent. Kaipingbu 2 purchase No. 7 bulletin, Japanese special (four) Kaiping 3 catch 8 city pure, Japan special materials ... section A newspaper and other five loaded resin. As a specific example 'may be listed: ring open olefin open loop Copolymer of (co)polymer, cyclic dilute hydrocarbon, copolymer of cyclic dilute hydrocarbon with α-olefin such as acetamene or propylene (represented by random copolymer), and utilization of unsaturated carboxylic acid and A graft polymer obtained by modifying the derivative, a hydrogenated product thereof, etc. As a specific example of the cyclic rare hydrocarbon, a norbornene-based monomer is exemplified.

S •14· 201231277 As a % polyolefin resin, various products are commercially available. Specific examples are exemplified by T〇pas (registered trademark) (manufactured by Tic〇na Co., Ltd.), art〇ne ("main article trademark) (manufactured by JSR Co., Ltd.), and ZE〇N〇R (registered supplier titanium) ( Manufactured by Sakamoto Co., Ltd.), ΖΕ〇ΝΕχ (registered trademark) (manufactured by Nippon Co., Ltd.), and ApEL (registered trademark) (manufactured by Mitsui Chemicals, Inc.). As the (meth)acrylic resin, any suitable (meth)acrylic resin can be used. For example, poly(meth)acrylic acid vinegar such as polymethyl methacrylate, methacrylic acid methoxy(meth)acrylic acid copolymer, methyl methacrylate methyl vinegar-(meth)acrylic acid vinegar copolymer , methacrylate methacrylate _ acrylate-(meth) acrylic acid copolymer, (meth) methacrylate styrene copolymer (MS resin, etc.), alicyclic hydrocarbon group-containing polymer (for example) , methacrylic acid methacrylic acid cycloheximide copolymer, methyl methacrylate-(meth)acrylic acid-lowering ester copolymer, etc.). Preferably, poly(meth)acrylic acid C1_6 yard-based vinegar such as poly(meth)acrylic acid methyl vinegar is used. As the (meth)acrylic acid-based resin, a mercaptopropene-based resin containing methyl acetoacetate as a main component is more preferably used. The content of methyl methacrylate in the mercaptoacetic acid methyl vinegar resin is from 50 to 100% by weight, preferably from about 7 to about 1% by weight. Cellulose shirt resin is a vinegar of cellulose and fatty acid. Specific examples of the iron-based and diacetic acid fibers include, for example, cellulose triacetate, cellulose tripropionate, and cellulose dipropionate. Further, the copolymer or the moiety of the radical is modified by other types of substituents or the like. Among these, cellulose triacetate is particularly preferred. About triacetate 160675.doc •15- 201231277 Wessu has many products on the market and is also advantageous in terms of availability and cost. As an example of a commercial product of cellulose triacetate, for example,

Fujitac (registered trademark) TD80 (manufactured by Fujifilm Co., Ltd.),

Fujitac (registered trademark) Td8〇UF (manufactured by Fujifilm Co., Ltd.), Fujitac (registered trademark) TD8〇uz (manufactured by Fujifilm Co., Ltd.), Fujitac (registered trademark) TD4〇uz (manufactured by Fujifilm Co., Ltd.) KC8UX2M (manufactured by Konica Minolta Opto Co., Ltd.), KC4UY (manufactured by Konica Minolta Opto Co., Ltd.), and the like. The polycarbonate resin is an engineering plastic containing a polymer in which a monomer unit is bonded via a carbonate group, and has high impact resistance, heat resistance, and flame retardancy. Further, since the polycarbonate resin has high transparency, it can be preferably used for optical applications. For optical applications, a resin called modified polycarbonate, or a copolymerization polycondensate having improved wavelength dependence, which has been modified to reduce the photoelastic coefficient, has been commercially available. These are preferably used. As such a commercially available polycarbonate resin, for example, PanHte (registered trademark) (Teijin Chemical Co., Ltd.), Iupil〇n (registered trademark) (Mitsubishi Engineering Plastic Co., Ltd.), SD P〇LYCA (5) Main booklet trademark) (Sumit〇m〇D〇w Co., Ltd.), CAUBRE (registered trademark) (D〇w❹ (4) Money Co., Ltd.), etc. In addition to the above thermoplastic resin, any suitable additive may be added to the base film. As such an additive, for example, an ultraviolet absorbing agent, a chemicalizing agent, a lubricant, a plasticizer, a releasing agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic (four), a pigment, and Coloring (four). The content of the above thermoplastic resin in the substrate film is preferably 5 G to 1 () (% by weight), more preferably 160,675.doc 201231277 50 to 99% by weight, and still more preferably 60 to 98% by weight, and particularly preferably 7 〇~97% by weight. The reason for this is that when the content of the thermoplastic resin in the base film is less than 5% by weight, the high transparency of the thermoplastic resin originally appears to be insufficient. The thickness of the base film before stretching can be appropriately determined, and it is preferably 丨 5 〇〇, more preferably 1 to 300 Mm, and more preferably in terms of strength and handling. 5~2〇〇μηι, the best is 5~i5〇pm. The surface of the substrate film on the side where the polyethylene glycol-based resin layer is formed may be subjected to corona treatment, plasma treatment, flame treatment, or the like in advance. Thereby, the adhesion between the base film and the polyvinyl alcohol-based resin layer is improved. Further, in order to improve the adhesion, a thin layer β [undercoat layer] such as an undercoat layer may be formed on the surface of the base film on the side where the polyvinyl alcohol-based resin layer is formed, as a primer layer, to some extent. A material which exerts a strong adhesion to both the base film and the polyethylene resin contiguous resin layer is not particularly limited. For example, a thermoplastic resin excellent in transparency, heat resistance, and elongation can be used. Specifically, the acrylic resin-polyurethane resin may be mentioned, but it is not limited thereto. The resin constituting the undercoat layer can also be used in a state of being dissolved in a solvent. The solubility of the resin can also be used [, aromatic J such as benzene and xylene; ketones such as acetone f-ethyl, methyl iso-τ-ketone; vinegar such as ethyl acetate and isobutyl vinegar; A chlorinated hydrocarbon such as a gas, a trichloroethylene or a chloroform; a general organic solvent such as an alcohol such as ethanol, propanol, 2-propanol or 1-butanol. Stretching is ώt Α 疋 疋 疋 若 若 若 160 160 160 160 160 160 160 160 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 675 . When considering the influence on the environment, it is preferred to form an undercoat layer from a coating liquid using water as a solvent. Among them, a polyvinyl alcohol-based resin having a good adhesion can be preferably used. As the polyethylene (tetra) resin used as the undercoat layer, for example, a polyethylene glycol resin and derivatives thereof can be cited. Examples of the derivative of the polyethylene glycol resin include, in addition to the polyethylene sheet, the polyethylene shrink disk, and the like, a rare hydrocarbon such as ethylene or propylene, acrylic acid, butyl acid, or the like. Saturated acid, carboxylic acid, unsaturated carboxylic acid, acrylamide, etc. are modified to modify the polyethylene resin. Among the above polyvinyl alcohol-based resin materials, a polyvinyl alcohol resin is preferably used. In order to increase the strength of the undercoat layer, a crosslinking agent may be added to the above thermoplastic resin. As the crosslinking agent to be added to the resin, a known crosslinking agent such as an organic system or an inorganic system can be used. It suffices to select a suitable one for the thermoplastic resin to be used. For example, an epoxy-based, isocyanic acid-based or metal-based crosslinking agent can be selected. As the epoxy-based crosslinking agent, any of a one-liquid curing type crosslinking agent and a two-liquid curing type crosslinking agent can be used. Ethylene glycol diglycidyl scale, polyethylene glycol diglycidyl glycerol or glycerol, glycidol test, hexanediol diglycidyl ether, trimethyl methacrylate triglycidyl bond, two K is an epoxy such as glyceryl aniline or diglycidylamine.乍 is a cross-linking agent of isocyanic acid vinegar's can be mentioned: toluene diisocyanate vinegar, toluene diisocyanate vinegar, trimethoprimin-toluene diisocyanate vinegar adduct, three Isocyanate such as phenylmethyl triisophthalocyanine, methylene bis(4-phenylmethyl triazole 160675.doc 201231277 cyanate), isophorone diisocyanate, and phenol closure. ^ _ 肟 肟 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或. As a metal-based crosslinking agent, for example, a metal salt, a metal oxygen servant, a metal hydroxide, or an organic Μ χ χ 虱 ' ' ' ' 只要 只要 只要 只要 只要 只要 只要 只要 只要 只要For example, it can be exemplified by: salt, metal oxide, sodium, potassium, magnesium, calcium, aluminum, iron, bromine, titanium, dream, side, chain plus zinc, copper, hunger, chromium, tin, etc. A salt of a metal having a divalent or higher valence and an oxide or hydroxide thereof. The organometallic compound refers to a compound having at least one or less structure in the molecule: a structure in which an organic group is directly bonded to a metal atom, or a structure in which an organic group is bonded to a metal atom via an oxygen atom or a nitrogen atom. The term "organic group" means a functional group containing at least a carbon element, and may be, for example, an alkyl group, an alkoxy group, a brewing group or the like. Further, the bonding means not only a covalent bond but also a coordination bond using a coordination of a chelate compound or the like. Preferable examples of the metal organic compound include a titanium organic compound, a misorganic compound, an aluminum organic compound, and a ruthenium organic compound. These metal organic compounds may be used singly or in combination of two or more. Specific examples of the titanium organic compound include, for example, tetra-n-butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetrakis(2-ethylhexyl) titanate, and titanic acid Ortho-titanate such as methyl ester; titanium phthalate pyruvate, titanium tetraacetate, titanium, polyethyl phthalate, titanium octoxide, titanium lactate, three 160675.doc -19- 201231277 ethanolamine, B Such as acetylacetate, such as acetonitrile, etc.胄_ 'Poly(tetra)titanium stearin as a specific example of the above-mentioned mis-organic compound error and n-butanol supply %, for example, n-propanol can be cited as follows: ethyl acetonate, acid acetonate, monoethyl acetonide, double bis Bis(ethylacetamidineacetic acid) acetophenone pyruvate and the like. Specific examples of the above-mentioned aluminum-organic compound Griffin include, for example, an acetophenone acid chelate compound. As the material for feeding the organic compound, a compound having the above-described titanium organic compound and a ligand exemplified in the wrong organic compound can be exemplified. In addition to the above-mentioned low molecular weight crosslinking agent, the force J uses a hydroxyl group-derived crosslinking agent such as melamine t or a polyacrylamide epoxy resin. As a commercial product of the styrofoam epoxy resin, "Sumirez (registered trademark) such as 65 〇 (3 〇)" and "Sumirez (registered trademark) Resin 675" sold by Sumika Chemtex Co., Ltd. Product name). When a polyethylene-based resin is used as the thermoplastic resin, a polyamine epoxy resin, a methylated melamine, a diacid, a metal chelate crosslinking agent or the like is particularly preferable. The ratio of the thermoplastic resin to the crosslinking agent for forming the undercoat layer is from about 1 part by weight to about 1 part by weight based on the type of the resin and the type of the crosslinking agent. The range is suitably determined, and it is preferably selected from the range of about 0.1 to 50 parts by weight. The coating liquid for the undercoat layer preferably has a solid content concentration of about 1/2 to 25% by weight. It is preferably 〇.〇5~1 μιη. More preferably 〇"~〇4 μιη. If it is thinner than 〇.〇5 μιη, the adhesion between the substrate film and the polyvinyl alcohol layer is improved. 160675.doc •20 · 201231277 The effect is small. If it is thicker than 1 μm, the polarizing plate becomes thicker, so it is not preferable. When the undercoat layer is formed, the coating method to be used is not particularly limited, and a line can be appropriately selected and used from a known method. Bar coating method, reverse coating, gravure coating, etc., coating method, die coating method, kama coating method, lip coating method, spin coating method, screen (four) method, spray coating method, Dipping method, misting method, etc. (Resin layer) As a polyethylene glycol tree for resin layers, The saponification is carried out by using the heavy bar polyacetic acid sulfonate. As a polyacetate bake vinegar resin, in addition to the vinyl acetate vinegar homopolymer, namely, polyvinyl acetate vinegar, vinyl acetate can be exemplified. Copolymers of other monomers copolymerized, etc. As other monomers copolymerizable with vinyl acetate, for example, unsaturated carboxylic acids, olefins, squamous scales, unsaturated acid reflux, and women with money The range of saponification degree of the polyvinyl alcohol-based resin is preferably 80.0 mol%. 0 0 mol% is more preferably 90.0 mol. 〆〇~100 mol%, and then the best 94 〇莫耳. /] πη visit Gan • Moer ~ (10) Moer. /. Range. If the degree of 4 degrees does not reach the ear / 〇, there is the water resistance of the resin layer (polarized layer) after the dyeing step The problem that the damp heat is remarkably deteriorated. The degree of alcoholization of the alcohol refers to the value of the polyacetate tree which is the raw material of the polyethyl hexanthene group in terms of the unit ratio (% by mole). The method is determined by the method defined by the paraphrase. The degree specified in ...A994) is available. I60675.doc 201 231277 degree of saponification (mol% M by cardinality) + (higher saponification degree by base number + acetate group) means that the higher the proportion of the hydroxyl group, the lower the proportion of the acetate group which hinders crystallization. Further, the polyvinyl alcohol resin It can also be a partially modified modified polyvinyl alcohol. For example, it can be used to use flue-cured tobacco such as ethylene or propylene, unsaturated acid such as acrylic acid, methacrylic acid or butyric acid, and unsaturated (four) The base is brewed. The second (thickening amine) and the like are modified to the polyethylene (four) resin, etc. The proportion of the modified is preferably less than 30% by mole, more preferably less than _. When more than 3 moles are carried out When the modification is performed, the polyvinyl alcohol-based resin may become difficult to adsorb the monochromatic dye, and the polarizing performance may be lowered. The optimum polymerization degree of the preferred one is preferably 2000~ the polyvinyl alcohol-based resin. There is also no particular 100 to 10,000, more preferably 1500 to 8000, and further 5 〇〇 (^ the average degree of polymerization described herein is also a value obtained by the method specified by jis κ (1994). Examples of the polyvinyl alcohol-based resin having such characteristics include PVA124 (saponification degree: 98.G to 99.0 mol/〇) made by Kuraray Co., Ltd. (Phase degree: 98.0 to 99.0 Mohr). %), PVA624 (saponification degree: 95.0 to 96.0 mol%) and pvA617 (internationality: 94 5 to 95 5 mol%) 'For example, the degree of chemical conversion manufactured by Nippon Synthetic Chemical Co., Ltd.: 97.0 to 98.8 mol %), AH_22 (saponification degree: 97 5~% 5 moles / 〇), NH-18 (internationalization degree: 98 〇~99 〇 耳 %) ' and N 3 〇〇 (interesting degree · 98.0~ 99.0 mol%); for example, JC-33 of JAPAn VAM & p〇VAL Co., Ltd. (saponification degree: 99.0 mol% or more), JM_33 (saponification degree: 93.5 to 95.5 m./°), JM-26 (Saponification degree: 95.5 to 97.5 MoI I60675.doc • 22-201231277%), JP-45 (saponification degree: 86.5 to 89.5 mol%), jF_17 (saponification degree: 98.0 to 99·〇······· -17LC saponification degree: 98.0 to 99.0 mol%), and JF_20 (saponification degree: 98.0 to 99.0 mol%), and the like can be preferably used to form the polyvinyl alcohol-based resin film of the present embodiment. In the above polyvinyl alcohol-based resin, an additive such as a plasticizer or a surfactant may be added as needed. As the plasticizer, a polyhydric alcohol, a condensate thereof, or the like can be used, and examples thereof include glycerin, diglycerin, triglycerin, ethylene glycol propylene glycol, and polyethylene glycol. The amount of the additive to be added is not particularly limited, but is preferably 20% by weight or less in the polyvinyl alcohol-based resin. The thickness of the resin layer is preferably more than 3 μηι and is 3 〇 μηη or less, more preferably 5 〜 20 μ ΐΏ. When it is 3 μm or less, the dyeability is remarkably deteriorated after stretching, and if it exceeds 30 μm, the thickness of the polarizing laminate film or the polarizing plate becomes thick, which is not preferable. The resin layer in the present embodiment is preferably coated on the surface of one side of the base film by a solution of a polyethylene resin obtained by dissolving a powder of a polyvinyl alcohol resin in a good solvent, and a solvent. Formed by evaporation. By forming the resin layer in the above manner, it can be formed thin. As a method of applying a polyvinyl alcohol-based resin solution to a base film, it is suitably selected from known methods, and is applied by a bar coating method, a reverse coating method, a gravure coating method, a die coating method, or a die coating method. The drying temperature of the solution of the Kama coating method, the lip coating method, the spin coating method, the screen coating method, the spray coating method, the dipping method, and the (4) coating 1 is, for example, 50 to·. C, preferably _耽. The drying time is, for example, 2 to 20 minutes. Further, the resin layer in the present embodiment may be attached to the base by a raw material sheet film containing a polyethylene glycol I60675.doc • 23 - 201231277 resin. ~Example of the surface on the surface <Staining step (S30)> Here, the resin layer coloring pigment of the laminated film using a dichroic dye, for example, can be used (4) or _ ^ as can be used · · Red BR, Red LR "r from organic dyes, such as _, LR red ruler, pink LB' red pigment BL, blush GS, sky blue LG, 搂婼主社严红Β (four) ''Blue BR, Blue 2R, Navy Blue, Green LG , purple LB, purple B, Li H, Li r field pots π phase black and black GSP, yellow 3G, yellow R, orange lr, orange red sink, red KGL, Congo red, bright purple Β, super blue g, super red , Super dial GL, direct sky blue, direct light orange S, mouth black, etc. Cough and other dichroic substances may be used alone or in combination of two or more. The dyeing step is, for example, by immersing the stretched laminated film as a whole. It is carried out in an aqueous solution (dyeing solution) containing a dichroic dye. As the dyeing solution, a solution obtained by dissolving the dichroic dye in a solvent can be used. As a solvent for the dyeing solution, water is usually used, but further Adding is compatible with water! · Raw organic * agent. The concentration of dichroic dye is preferably Ha wt%, more preferably 0.02~7 %, especially preferably 25 to 5 wt%. When the moth is used as a dichroic dye, the dyeing efficiency can be further improved. The car father adds the telluride to the dyeing solution. Examples of the compound include: catalyzed unloading, mothening, 峨 纳 纳, 破 〃 〃 碘 碘 碘 碘 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 。 。 。 。 。 。 。 In the solution, the addition ratio of the ruthenium compounds is preferably 0.01 to 20% by weight. Among the ruthenium compounds, it is preferable to add bismuth to the cardiolyzed solution. In the case of adding potassium iodide, iodine and potassium iodide. The ratio of 160675.doc

-24 - 201231277, better in the encirclement. The weight ratio is preferably in the range of 1:5 to 1:1 1: in the range of 1:6 to 1:80, and particularly preferably in the range of 1:7 to 1:70, usually in the clock. Further, the dyeing is more preferably in the range of 15 seconds to 15 minutes in the layering film in the dyeing solution, more preferably 2 seconds to 6 minutes, and the temperature of the solution is preferably in the range of 1 〇. 6〇t>c is within the range of 20 to 40 °C. <Crosslinking step> The cross-linking treatment can be carried out after the dyeing step. The crosslinking treatment is carried out, for example, by immersing the laminated film in a solution (crosslinking solution) containing a crosslinking agent. As the crosslinking agent, a previously known substance can be used. For example, a compound such as a butterfly acid or a butterfly, and oxalic acid or glutaric acid may be mentioned. These may be used alone or in combination of two or more. As the crosslinking solution, a solution obtained by dissolving a crosslinking agent in a solvent can be used. As the solvent, for example, water may be used, and further, an organic solvent compatible with water may be contained. The concentration of the crosslinking agent in the crosslinking solution is not limited to this. Preferably, it is in the range of (four)% by weight, and more preferably (4) the breaking compound may be added to the crosslinking solution. By adding a Weiwu, the polarization characteristics in the surface of the resin layer can be more uniform. Examples of the moth compound include moth-removing, hardening, sodium iodide, sputum, sputum, lead, copper iodide, cesium iodide, (4), antimony telluride, and titanium iodide. The content of the iodide is 0.05 to 15% by weight, more preferably 5 to 8 % by weight. The impregnation time of the laminate film in the crosslinking solution is usually preferably from Η second to (9) minutes', more preferably from 30 seconds to 15 minutes. The temperature of the cross-linking solution is preferably in the range of from 10 to 80 ° C in the range of I60675.doc -25 - 201231277. <Cleaning step> After the crosslinking step, it is preferred to carry out the washing step. The water cleaning treatment can be carried out. The water washing treatment can usually be carried out by dipping the product into pure water such as ion-exchanged water or distilled water, and the film is usually 3 to 50 ° C, preferably 4 t 2 (the van wash temperature is 2 to 300 seconds). Preferably, it is 3 seconds to (four) seconds. ^ The time is usually used as a washing step, and the washing step (4) of the telluride solution can be combined and washed. As the washing liquid, it is also possible to use methanol and ethanol as appropriate. a liquid alcohol such as isopropyl alcohol, butanol or propanol. <drying step> After the washing step, a drying step may also be carried out. As the drying step, any appropriate method may be employed (for example, natural 'drying, drum Drying by air, heating and drying. For example, the drying temperature at the time of heat drying is 2 〇 to 95 ° C, and the drying time is usually about 17 minutes. After the above steps, the polyvinyl alcohol-based resin layer functions as a polarizing sheet layer, thereby A polarizing laminated film having a polarizing plate layer formed on the surface of the base film. (Polarizing sheet layer) The polarizing plate layer specifically means that the dichroic dye is adsorbed and aligned on the uniaxially stretched polyethylene resin layer. Founder. The thickness of the light sheet layer (the thickness of the stretched polyethylene resin film) is preferably 1.5 μm. By setting the thickness of the polarizer layer to 15 μm or less, a thin polarizing laminate can be formed. Protective film bonding step (S40) > 160675.doc • 26· 201231277 The protective film is disposed on the surface opposite to the surface on the substrate film side of the polarizing layer in the polarizing laminated film. The bonding method of the protective film is not particularly limited. For example, an adhesive layer or an adhesive layer is formed on the bonding surface of the polarizer layer and/or the protective film, and the two are bonded via an adhesive layer or an adhesive layer. The material suitable as the adhesive layer and the adhesive layer will be described later. (Protective film) The protective film may be only a protective film having no optical function, or may be an optical function such as a retardation film or a brightness enhancement film. The protective film is not particularly limited, and examples thereof include a cyclic polyolefin resin film, a cellulose acetate resin film containing a resin such as cellulose triacetate or diacetyl cellulose, and a polycondensation film. Ethylene terephthalate, polycai A polyester resin film, a polycarbonate resin film, an acrylic resin film, a polypropylene resin film, and the like of a resin such as acid ethylene diacetate or polybutylene terephthalate are used in the field. As a cyclic polyolefin-based resin, a commercially available product such as T〇pas (registered trademark) (manufactured by Ticona Co., Ltd.) and art〇ne (registered trademark KJSR Co., Ltd.) can be preferably used. ZE〇N〇R (registered trademark of Nippon Co., Ltd.), ΖΕ〇ΝΕχ (registered trademark X曰本ΖΕΟΝ股份有限公司), ApEL (registered trademark) (Mitsui Chemicals Co., Ltd. is a limited A division). When a film is formed by forming a film of the cyclic polyolefin resin, a known method such as a solvent casting method, a melt extrusion method, or the like can be suitably used. In addition, S-SINA (registered trademark) (manufactured by Sekisui Chemical Co., Ltd.), SCA40 (manufactured by Sekisui Chemical Co., Ltd.), ZEONOR (registered trademark) membrane (manufactured by 0pts Co., Ltd.), etc., 160675.doc -27- 201231277 A commercially available product of a film made of a cyclic polyolefin resin which has been formed into a film has been obtained in advance. The % polyolefin resin film may also be uniaxially stretched or biaxially stretched. By extending, an arbitrary phase difference value can be imparted to the cyclic polyolefin resin film. The stretching is usually carried out continuously while rolling up the film roll, and in the heating furnace, the film is advanced in the direction forward of the roll, in the direction perpendicular to the advancing direction, or in both directions. The temperature of the heating furnace is usually in the range from the vicinity of the glass transition temperature of the cyclic polyolefin resin to the glass transition temperature of +1 〇 (rc). The stretching ratio is usually 丨丨6 times in each direction, preferably The cyclic polyolefin resin film generally has a poor surface activity. Therefore, it is preferred to subject the surface of the cyclic polyolefin resin film to the surface of the polarizer (4) with plasma treatment, corona treatment, and ultraviolet rays. Surface treatment such as irradiation treatment, fiame treatment, and the like. Among them, electropolymerization treatment and corona treatment which are relatively easy to perform are preferred. As the cellulose acetate resin film, a suitable city can be preferably used. For sale, for example, Fujhac (registered trademark) TD8〇 (made by Fujifilm Co., Ltd.), Fujhac (registered trademark) TD8〇UF (made by Fujifilm Co., Ltd.), Fujitac (registered trademark) TD8〇uz (Fuji film limited stock) Manufactured by the company), Fujitac (registered trademark) TD4〇uz (manufactured by Fujifilm Co., Ltd.), KC8UX2M (manufactured by K〇nica Minolta 〇pt〇 Co., Ltd.), KC4UY (K〇nica Min) Lta 〇pt〇 Co., Ltd. manufactures a liquid crystal layer to improve the viewing angle characteristics, and also stretches the resin film. In order to impart a phase difference on the surface of the cellulose acetate resin film Adhesion to polarizing film, usually for acetic acid\60675.doc

S • 28· 201231277 The cellulose resin film is subjected to a saponification treatment. As the saponification treatment, a method of impregnation in an alkaline aqueous solution such as sodium hydroxide or potassium hydroxide can be employed. An optical layer such as a hard coat layer, an antiglare layer, or an antireflection layer may be formed on the surface of the protective film as described above. The method of forming the optical layers on the surface of the protective film is not particularly limited, and a known method can be used. The thickness of the protective film is preferably as thin as possible, and is preferably 90 or less, more preferably 5 Å or less. On the other hand, if it is too thin, the strength is lowered, and the workability is poor, so it is preferably 5 μη or more. (Adhesive Layer) The (4) agent constituting the adhesive layer usually contains an acrylic resin, a styrene resin, a polyoxymethylene resin or the like as a base polymer, and an isocyanate compound or an epoxy compound is added thereto. A composition obtained by a crosslinking agent such as an aziridine compound. Further, fine particles may be blended in the adhesive to form an adhesive layer exhibiting light scattering properties. ▲ When the adhesive layer is formed, it is preferred to apply the adhesive to a thin layer and/or a protective film in such a manner that the workability of the adhesive layer is not deteriorated. The thickness of the adhesive layer is preferably -: 3 to 25 (four). If it is 3 to 25 Å, the adhesive layer has a good processing and it is easy to suppress the dimensional change of the polarizing film. If the adhesive layer is not working, then the adhesion is lowered. If (4) is not m·more than 4G_, it is easy to cause the adhesive to protrude on the polarizer layer or to form the adhesive layer. There is no particular limitation. The solution may also be on the polarizer layer or the solution of the component which is mainly composed of the polymer, and the coating on the dry film may be formed by the above-mentioned foundation drying to form the adhesive layer 160675.doc -29-201231277 Plate or other type of film fits. It is also possible to form an adhesive layer on the separator and then attach it to the polarizer layer or the protective film surface for lamination. Further, when an adhesive layer is formed on the polarizer layer or the protective film, a polarizing treatment (e.g., corona treatment, etc.) may be performed on the polarizer layer or the protective film surface or on one or both sides of the adhesive layer as needed. (Adhesive layer) The adhesive agent constituting the adhesive layer ′ is, for example, a polyvinyl alcohol-based eucalyptus water; a gluten-based liquid, and a water-based adhesive using an aqueous two-liquid urethane lactic acid-based emulsifier. Among them, a polyvinyl alcohol-based resin aqueous solution can be preferably used. In the polyvinyl alcohol-based resin used as the adhesive, in addition to the vinyl alcohol homopolymer obtained by saponifying the polyvinyl acetate homopolymer, that is, polyvinyl acetate, there are vinyl acetate and other copolymerizable copolymers thereof. A vinyl alcohol-based copolymer obtained by subjecting a copolymer of a monomer to a saponification treatment, and a modified polyvinyl alcohol-based polymer obtained by partially modifying a hydroxyl group. A polyfurfural, a water-soluble epoxy compound, a melamine-based compound, an oxidative compound, a zinc compound or the like may be added as an additive to the aqueous binder. In the case where such a water-based adhesive is used, the adhesive layer obtained therefrom is usually much thinner than 1 μm, and the adhesive layer is not actually observed even when the cross section is observed by an optical microscope. There is no particular method for bonding a film using a water-based adhesive. The water-based adhesive may be uniformly applied or applied to the surface of the polarizer layer or the protective film. The other film may be laminated on the coated surface and then bonded by light or the like, followed by addition and drying. Usually, the adhesive is applied at a temperature of 15 40 C after its preparation, and the bonding temperature is usually in the range of 15 to 3 〇 c > 160675.doc 201231277 When a water-based adhesive is used, the water-based adhesive is dried in order to remove the water contained in the water-based adhesive after bonding the film. The temperature of the drying oven is preferably 30. 〇90. (: If it is less than 3 (rc, it tends to be. If it is 90 〇C or more), there is a polarizer which has an optical property such that the surface is easily peeled off due to heat. The drying time can be set to 丨〇~i. After drying, the adhesive may be cured at room temperature or a temperature slightly higher than room temperature, for example, at a temperature of about 2 〇 to 45 ° C, for about 2 to 6 hours. In general, the temperature at the time of aging is set to be lower than the temperature at the time of drying. Further, a photocurable adhesive can be used as the non-aqueous adhesive. Examples of the photocurable adhesive include photohardening. A mixture of an epoxy resin and a photocationic polymerization initiator, etc. As a method of film bonding by a photocurable adhesive, a conventionally known method can be used, and for example, a casting method, Meyer bar, and the like can be cited. Coating method, gravure coating method, gamma coating method, knife forming method, die coating method, dipping method, spray method, etc. By these methods, an adhesive is applied to the film. Face, and make two films coincide. The so-called casting method (fl〇w expanding meth Od) means that the two films as the object to be coated are moved in a substantially vertical direction, a substantially horizontal direction, or an oblique direction therebetween, and the adhesive is flowed down to the surface thereof and diffused and coated. After applying the adhesive to the surface of the polarizer layer or the protective film, the polarizing laminated film and the protective film are sandwiched by a nip roll or the like to bond the film, thereby bringing the two together. A method of uniformly spreading the laminated body 160675-doc • 31 - 201231277 by pressurization with a roller or the like can be preferably used. When the Η衿 π is used for the clearing, metal or rubber can be used as the material of the roller. , γ ', can preferably be used to pass the laminate between the roller and the roller, press it to expand the basin. In this case, the: the same material, can also be different The thickness of the adhesive layer before bonding or bonding after the bonding is preferably 5 or less and 0 or 0 1 μmη or more. In order to improve the adhesion, it is also possible to obliquely limit the J to the polarized light. The film and the bonding film are suitable for the plasma treatment, Ray I + Surface treatment such as spoon treatment, ultraviolet irradiation treatment, flame (fl:me) treatment, saponification treatment, etc. As the saponification treatment, a method of treating the alkaline aqueous solution such as hydrazine hydroxide #3 or oxyhydroxide can be mentioned. 0 When the photocurable tree (4) is used as an adhesive, the photocurable adhesive is cured by irradiating the active energy line after the laminated film. The light source of the active energy ray is not particularly limited, and is preferably 4 An active energy line having a light-emitting distribution in a wavelength band below 〇〇nm, specifically, a low-pressure mercury lamp medium-pressure mercury lamp, a pressure mercury lamp, an ultra-high pressure mercury lamp, a chemical lamp, a black light lamp, a microwave-excited mercury lamp, a metal letter can be preferably used. The light irradiation intensity of the photocurable adhesive is appropriately determined depending on the composition of the photocurable adhesive, and is not particularly limited, and is preferably an irradiation intensity in a wavelength region effective for activation of the polymerization initiator. For 〇丨~ (9) mW/cm. When the irradiation intensity is 〇. 1 mW/cm2 or more, the reaction time does not become too long. When the irradiation intensity is 6,000 mW/cm2 or less, there is less possibility that yellowing of the epoxy resin or deterioration of the polarizing film due to heat generated by the light source fs and heat generated by curing of the photocurable adhesive agent is small. For light 160675.doc • 32· 201231277 The light irradiation time of the curable adhesive is applied according to the cured photocurable adhesive ‘are not specifically limited. It is preferable to set the light irradiation time so that the integrated light amount expressed as the product of the irradiation intensity and the irradiation time is 1 〇 to 1 〇〇〇〇 mJ/cin. When the cumulative light amount to the photocurable adhesive is 10 mj/cm2 or more, a sufficient amount of the active material derived from the polymerization initiator can be generated to make the hardening reaction more sure. When the cumulative light amount is 10000 mj/cm2 or less, the irradiation time does not become too long, and good productivity can be maintained. Further, the thickness of the adhesive layer after the irradiation of the active energy ray is usually about 0.001 to 5 μm, preferably 001 μη or more and 2 μη or less, more preferably 〇1 μπι or more and 1 or less. When the polarizing sheet layer and the photocurable adhesive on the protective film are cured by irradiation with an active energy ray, it is preferred that the polarizing plate such as transmittance, hue, and transparency of the film is subjected to all the steps. The function is hardened without falling. <Substrate film peeling step (S50)> In the method for producing a polarizing plate of the present embodiment, as shown in Fig. 3, after the protective film is bonded to the polarizing film layer, the protective film bonding step (S40) is performed. The target substrate film peeling step (S5〇). In the substrate film peeling step (S5〇), the substrate film is peeled off from the polarizing laminate film. The peeling method of the base film is not particularly limited, and the same method as the peeling step of the peeling film which is carried out on a usual polarizing plate with an adhesive can be employed. After the protective film bonding step (s4〇), it may be directly peeled off immediately, or may be wound into a roll shape, and a peeling step may be separately provided for peeling. Through the above steps, a polarizing plate having a protective film on one side of the polarizing layer is manufactured. I60675.doc -33· 201231277 (Other optical layers) The above polarizing plate can be used as a polarizing plate in which other optical layers are laminated in actual use. Further, the protective film may have the function of the optical layers. Examples of the other optical layer include a reflective polarizing film that transmits a certain polarized light and reflects polarized light having a property opposite thereto, and a film having an anti-glare function having a concave-convex shape on the surface thereof. A film with a surface reflection function, a reflective film having a reflective function on the surface, a semi-transmissive reflective film having both a reflection function and a transmission function, and a viewing angle compensation film. A commercially available product of a reflective polarizing film that transmits a polarized light having a property of transmitting a polarized light and reflecting the opposite property, for example, DBEF (available from 3M Company, available from Sumitomo 3M Co., Ltd.), APF (manufactured by 3M Company, available from Sumitomo 3M Co., Ltd.). The viewing angle compensation film includes an optical compensation film in which a liquid crystal compound is applied to a surface of a substrate and is aligned, and a retardation film containing a polycarbonate resin includes a phase difference of a cyclic polyolefin resin. membrane. A commercially available product of an optical compensation film which is obtained by applying a liquid crystal compound to the surface of a substrate and aligning the surface of the substrate is exemplified by WV film (manufactured by Fujifilm Co., Ltd.) and NH film (Nippon Oil Co., Ltd.) Manufactured):: 尺尺膜 (manufactured by Nippon Oil Co., Ltd.). In addition, as a commercial item corresponding to a retardation film containing a cyclic polyolefin resin, ART〇NE (registered trademark) film (manufactured by JSR Co., Ltd.) and S-SINA (registered trademark) (Shuishui Chemical Industry) Manufactured by a company limited by shares, ZEONOR (registered trademark) film (manufactured by 〇ptes Co., Ltd.). [Examples]

The present invention will be more specifically described below, but the present invention is not limited to the embodiments. [Example 1] (Base film) As the substrate 骐, a homopolypropylene (ΡΡ) film having a thickness of 丨10 μπΐ2 and not stretched was used. (Undercoat layer forming step) Polyvinyl alcohol powder (manufactured by Sakamoto Synthetic Chemical Co., Ltd., having an average degree of polymerization of 1,100, a degree of saponification of 99 5 mol%, trade name: Ζ-200) was dissolved in 95 〇c. In the hot water, an aqueous solution having a concentration of 3% by weight was prepared. In the obtained aqueous solution, 5 parts by weight of a crosslinking agent (manufactured by Sumika Chemtex Co., Ltd., trade name: Sumirez (registered trademark) Resin 65〇) was mixed with 6 parts by weight of the polyvinyl alcohol powder. The obtained mixed aqueous solution was applied onto a substrate film subjected to corona treatment at 80. (: Under drying for 10 minutes to form an undercoat layer having a thickness of 02 μm. (Resin layer forming step) Polyvinyl alcohol powder (manufactured by Kuraray Co., Ltd.) has an average degree of polymerization of 2,400 and a degree of saponification of 98.0 to ". Mol %) was dissolved in hot water of 95 ° C to prepare a polyvinyl alcohol aqueous solution having a concentration of 8 wt %. The obtained aqueous solution was applied onto the above undercoat layer, and dried for 20 minutes to prepare a base. a laminated film of three layers of a material film, an undercoat layer, and a resin layer. The thickness of the resin layer is 1 〇μΐγ|. (Extension step, dyeing step) Using the stretching device shown in Fig. 2, the width is 380 mm (Wl) The above-mentioned 160675.doc •35· 201231277 laminated film is subjected to free-end uniaxial stretching. The extension temperature is set to i5yc, the circumferential speed of the first group of pair 2 is set to 1 m/miη, and the second group is paired with 3 The peripheral speed is set to 5 · 8 m / min and extends to 5 · 8 times in the longitudinal direction. At this time, the distance L between the two pairs of rollers 2 ' 3 is 1.28 m, and the width of the extended film is 164 mm (W2) The contraction ratio of the embodiment 1 is 568. The value of the left side (W1/L) of the formula (2) becomes 〇.3〇. The results are shown in Table i. Thereafter, the stretched laminated film was immersed in a 60 ° C warm bath for 6 sec seconds, and then immersed in a mixed aqueous solution of iodine and potassium iodide at 30 ° C for 2 sec. (Staining step). Use 1 (TC pure water' to wash away the excess iodine solution from the laminated film after the dyeing step. Then 'layer the film in a 76eC mixture of boric acid and potassium iodide _ immersion for 400 seconds (crosslinking step) Thereafter, the laminated film was washed with 1 (r pure water for 4 seconds) and finally dried at 300 ° for 300 seconds to obtain a polarizing laminated film including three layers of a base film, an undercoat layer, and a polarizer layer. In this case, the thickness of the polarizer layer is 4.2 μm. (Protective film bonding step, substrate film peeling step) Polyvinyl alcohol is applied to the surface of the polarizing laminated film opposite to the surface on the substrate film side. After the adhesive was applied, a protective film (manufactured by K〇nica Co., Ltd., film thickness: 40 μm, TAC) was bonded to obtain a polarizing plate comprising four layers of a base film, an undercoat layer, a polarizer layer, and a protective film. The base film is peeled off from the obtained polarizing plate. The base film is easily peeled off, and an undercoat layer is obtained. Polarizing plate of three layers of a light sheet layer and a protective film (Measurement of optical characteristics) A primer obtained by peeling a base film by a spectrophotometer with an integrating sphere (manufactured by Sakamoto Seiki Co., Ltd. 'V71 00) Layer, polarized light 160675.doc

S .36 · 201231277 The optical properties of the polarizer of the three layers of the film and the protective film were measured. The MD transmittance and the td transmittance were determined in the range of 380 nm to 780 nm, and the monomer transmittance and the degree of polarization at each wavelength were calculated from the equations (3) and (4). Further, the visibility correction was performed by a 2 degree field of view (C light source) of JIS Z 8701, and the visibility corrected single transmittance (Ty) and the visibility corrected polarization (Py) were obtained. In addition, the "MD transmittance" refers to the transmittance when the transmission axis of the polarizing plate sample is parallel to the direction of the polarized light emitted from the Glan-Thompson prism. In the equations (3) and (4), the "Md transmittance" is expressed as "MD". In addition, the "TD transmittance" refers to the transmittance when the transmission axis of the polarizing plate sample is orthogonal to the direction of the polarization emitted from the Glan-Thompson, and in the formulas (3) and (4), The "TD Transmittance" table is not "TD". Monomer transmittance (%) = (MD + TD) / 2 Equation (3) Polarization degree (%) = {(MD - TD) / (MD + TD)} 丨 / 2 χ 100 Equation (4) The polarizing plate of Example 1. The 'T' is 41_80/. , Py is 99.99%. The results are shown in Table 1. [Example 2] A laminate film comprising the base film, the undercoat layer, and the two layers of the eucalyptus layer of Example 2 was produced in the same manner as in Example 1. In the second embodiment, the laminated film having a width of 4 mm (Wl) was subjected to free end uniaxial stretching using an extension device not shown in Fig. 2. The extension temperature was set to 15 〇. That is, the circumferential speed of the first group of roller pairs 2 was set to 1 m/min. The circumferential speed of the second group of roller pairs 3 was set to 5.8 m/min, which was extended to 58 times in the longitudinal direction. At this time, the distance between the two sets of roller pairs 2, 3, 160675.doc • 37- 201231277 is 0.85 m, and the width of the extended film is 18 mm (w2). The shrinkage ratio of Example 2 was 52.6%, and the value of the left side of the formula (2) (W1/L) was 0.45. The results are shown in Table 1. Using the stretched laminated film, the polarizing laminated film of Example 2 was produced by the same method as in Example 其, and then three layers including an undercoat layer, a polarizer layer, and a protective film were produced. Polarized plate. The thickness of the polarizer layer of Example 2 was 4.0 μm. The optical characteristics of the polarizing plate of Example 2 were measured in the same manner as in Example ’. The result was Ty of 4 1.5% and Py of 99.99%. The results are shown in Table 1. [Example 3] In the same manner as in Example 1, a layered crucible of Example 3 comprising a base film, an undercoat layer and a layer of a layer of a tree layer was produced. In Example 3, the laminate film having a width of 4 mm (wl) was freely uniaxially stretched using the stretching device shown in Fig. 2. The extension temperature was set to 15 〇t > c, the circumferential speed of the i-th set of roller pairs 2 was set to 1 m/min, and the circumferential speed of the second set of roller pairs 3 was set to 5 8 m/min, extending in the longitudinal direction. Up to 5 8 times. At this time, the distance L between the two pairs of roller pairs 2, 3 was 6.0 m, and the width of the extended film was 16 〇 mm (W2). The contraction ratio of the third embodiment is 6 〇 〇%, and the value on the left side of the equation (wi/l) becomes 0·〇7. The results are shown in Table 1. Using the stretched laminated film, the polarizing laminated film of Example 3 was produced in the same manner as in Example 1, and thereafter, a polarizing plate comprising two layers of an undercoat layer and a polarizer layer protective film was produced. The thickness of the polarizer layer of Example 3 was 4·5 μm. The optical polarizer of the polarizing plate of Example 3 was measured in the same manner as in Example ’. The result was 42.0% of Ty and Py of 99.99%. Will knot 160675.doc

S -38· 201231277 The results are shown in Table 1. [Example 4] Example 4 differs from Example 3 in the following points: the kind of the polyvinyl alcohol powder used in the resin layer forming step, the degree of the resin layer before the stretching step, the temperature of the mixed aqueous solution in the dyeing step, and the dip Crash time. Except for these differences, the polarizing film of the example was produced in the same manner as in Example 3, and the polarizing Μ @ thickness of the polarizing plate of Example 4 was also different from that of Example 3. The thickness of the polarizer layer of Example 4 was 5.2 μηη. In the resin layer forming step of Example 4, polyvinyl alcohol powder (manufactured by JAPAN VAM & P〇VAl Co., Ltd., having an average degree of polymerization of 2,600 and a degree of saponification of 95.5 to 97.5 mol%) was used. In the dyeing step of Example 4, the laminated film was at 25. (: immersed in a mixed aqueous solution of iodine and potassium iodide for 6 sec. The shrinkage ratio of Example 4 was 60.0%, and the value of the left side of the formula (2) (wi/l) was 0.07. The same as Example i. The optical characteristics of the polarizing plate of Example 4 were measured, and as a result, Ty was 41.5%, and Py was 99.99%. The results are not shown in Table 1. [Example 5] Example 5 was the following and Example 3 The difference is: the type of the polyvinyl alcohol powder used in the resin layer forming step, the thickness of the resin layer before the stretching step, the temperature of the mixed aqueous solution in the dyeing step, the impregnation time, and the impregnation time in the crosslinking step. The polarizing laminate film of Example 5 and the polarizing plate were produced in the same manner as in Example 3 except for the difference. Example 5 160675.doc •39·201231277 The thickness of the polarizer layer in the polarizing plate was also implemented. The thickness of the polarizer layer of Example 5 was 5 5 μηι. In the resin layer forming step of Example 5, polyvinyl alcohol powder (manufactured by Nippon Synthetic Chemical Co., Ltd., average degree of polymerization was 33 〇〇) was used. , the degree of saponification is 93.5~95.5 m . /) In the staining procedure of Example 5, the film is laminated to a 25 <) of the mixed aqueous solution of iodine and potassium iodide dipped C is the second collapse. In the crosslinking step of Example 5, the laminated film was immersed in a mixed aqueous solution of boric acid and potassium iodide in 76 tons for 50 seconds. The shrinkage ratio of the example 5 is 6 〇 〇%, and the value of the left side of the formula (2) is 0.07. The optical characteristics of the polarizing plate of Example 5 were measured in the same manner as in the case of the actual example, and the result was Ty44 8%, "99 99%. The results are shown in Table 1. [Comparative Example 1] 1 The same method was used to produce a laminated film of Comparative Example i including a base film, an undercoat layer, and a layer of a tree S layer. In Comparative Example i, the stretching device shown in Fig. 2 was used, and the width was 380 mm (Wl). The laminated film is subjected to uniaxial stretching at the free end. The extension temperature is set to g15 〇 < t, the peripheral speed of the i-th set of roller pairs 2 is set to 1 m/min, and the second set of roll pairs 3 is set to 5 8 m/min, extending in the longitudinal direction to 58 times. At this time, the distance L between the two pairs of rollers 2' 3 is 310 mm, and the width of the extended film is 264 mm (W2). The ratio was 30.5%, and the value (W1/L) on the left side of the formula (2) was 1.23. The results are shown in Table i. Comparative Example 1 was produced by the same method as in Example 使用 using the stretched laminated film. Polarized laminated film, followed by preparation of undercoat layer, polarizer 160675.doc

-40· 201231277 Layer, protective film, three layers of polarizing plates. The thickness of the polarizer layer of Comparative Example 1 was 2 · 5 μηι. The optical characteristics of the polarizing plate of Comparative Example 1 were measured in the same manner as in Example 1. As a result, Ty was 41.6%, and Py was 99.97%. The results are shown in Table 1. [Table 1] PVA saponification degree (mole%) Roller distance L (four) Film width W1 (mni) before stretching Film width W2 (mm) after stretching Length ratio (%) W1/L Monomer transmittance Ty (%) Polarization Py (%) Example 1 98.0-99.0 1.28 380 164 56.8 0.30 41.8 99.99 Example 2 98.0-99.0 0.85 380 180 52.6 0.45 41.5 99.99 Example 3 98.0-99.0 6.0 400 160 60.0 0.07 42.0 99.99 Example 4 95.5 ~97.5 6.0 400 160 60.0 0.07 41.5 99.99 Example 5 93.5 to 95.5 6.0 400 160 60.0 0.07 40.8 99.99 Comparative Example 1 98.0-99.0 0.31 380 264 30.5 1.23 41.6 99.97 [Industrial Applicability] By the manufacturing method of the present invention Since the obtained polarizing laminated film and polarizing plate are thin and have excellent optical characteristics, they are suitable for mobile devices such as notebook personal computers and mobile phones, and liquid crystal display devices for large televisions. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing an embodiment of a method for producing a polarizing laminated film of the present invention. Fig. 2 is a schematic view showing an embodiment of an extension step in the method of the present invention. Fig. 3 is a flow chart showing an embodiment of a method for producing a polarizing plate of the present invention. [Main component symbol description] 160675.doc •41 - 201231277 1 Laminated film 2 Group 1 roller pair 2a, 2b Inflame roller 3 Group 2 roller pair 3a, 3b Clamping roller 4 Heating device 160675.doc -42-

Claims (1)

201231277 VII. Patent application scope: 1. A method for producing a polarizing laminated film, comprising: a base film; and a method for producing a polarizing laminated film formed on a polarizing layer of one surface of the base film; the polarizing plate The manufacturing method includes the following steps: a resin layer forming step of forming a resin layer containing a polyvinyl alcohol-based resin on one surface of the base film to obtain a laminated film; and an extending step of performing the free end of the laminated film a uniaxial stretching; and a dyeing step of dyeing the resin layer of the laminated film by a dichroic dye to form a polarizer layer; and in the extending step, performing the laminated film before the free end uniaxial stretching The width wi and the width W2 of the laminated film after the uniaxial stretching of the free end satisfy the relationship of the following formula (1): (W1-W2)h-W1 X 100^40 Formula (1). 2. The method for producing a polarizing laminated film according to claim 1, wherein in the extending step, the free end uniaxial stretching is performed by transferring the laminated film between two sets of roller pairs having different circumferential speeds, and the above The distance L between the two sets of roller pairs satisfies the relationship of the following formula (2): Wl - L ^ 1.0 Equation (2). 3. The manufacturing method of the polarizing laminated film of claim 1, wherein in the extending step, the ratio of the peripheral speeds of the two groups (four) exceeds 5 times. 4. The method for producing a polarizing laminate film according to claim 1, wherein the base film comprises a polyolefin resin. 5. The method for producing a polarizing laminated inclined arm film according to claim 1, wherein the resin layer is formed in the above-mentioned tree 160675.doc 201231277 曰 layer forming step to have a thickness exceeding 3 μm and being 30 μη or less. 6. The method of producing a polarizing laminate film according to claim 1, wherein the thickness of the polarizing layer is 1.5 μm to 15 μχ. A method of producing a polarizing plate, comprising: a polarizing plate layer; and a method of manufacturing a polarizing plate attached to a protective film on one side of the polarizing plate layer; the manufacturing method of the polarizing plate sequentially comprises the following steps: a film-bonding step of producing a polarizing laminate film by the production method according to any one of claims 1 to 4, wherein the polarizer layer and the substrate film side of the polarizing laminate film are The protective film is bonded to the surface on the opposite side; and the base film peeling step is performed by peeling off the base film from the polarizing laminated film. 160675.doc