JP2016170438A - Polarizing laminate film and laminate film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polarizing laminate film having a polarizer layer on a substrate film and having high durability against tear when handled in a rework process or the like.SOLUTION: The polarizing laminate film includes a polarizer layer 30 on at least one surface of a substrate film 20, in which the substrate film 20 has a layered structure of two or more resin layers comprising resins having different phase transition temperatures from each other, and the layered structure includes layers in an order of A/B/A or B/A/B, where A represents a resin layer A composed of a resin showing the highest phase transition temperature and B represents a resin layer showing the lowest phase transition temperature. The resin layer A is an oriented state in any direction within the plane, while the resin layer B is substantially non-orientation state within the plane. The resin layers A and B are made of linear polyolefin resins having different melting points from each other.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a polarizing laminated film in which a polarizer layer is laminated on a base film and a laminated film suitable as a production intermediate thereof.

  A polarizing plate is widely used as a polarized light supplying element and a polarized light detecting element in a liquid crystal display device. As such a polarizing plate, a polarizing film made of a polyvinyl alcohol resin and having a protective film made of triacetylcellulose bonded on one or both sides has been used. In recent years, notebook personal computers for liquid crystal display devices have been used. With the development of mobile devices such as mobile phones and mobile phones, as well as the development of large televisions, there is a demand for thinner and lighter polarizing plates.

  For example, in Patent Documents 1 to 4, as a method for producing a thin polarizing plate, a resin layer made of a polyvinyl alcohol-based resin is formed on one surface of a base film made of a single resin layer, and then stretched. A method of using the stretched film obtained in this manner for the production of a polarizing plate is disclosed.

JP 2000-338329 A JP 2009-93074 A JP 2009-98653 A JP 2003-43257 A

  In general, a polarizing plate is incorporated in a liquid crystal display device or the like by forming a pressure-sensitive adhesive layer on one side to form a polarizing plate with a pressure-sensitive adhesive layer, and bonding the liquid crystal cell via the pressure-sensitive adhesive layer. In the bonding process of the polarizing plate to such a liquid crystal cell, when there is some inconvenience in the bonding state of the bonded polarizing plate, the liquid crystal cell is collected and used for the second bonding process. In addition, a so-called rework process may be performed in which the polarizing plate is peeled off from the liquid crystal cell together with the pressure-sensitive adhesive layer.

  However, the conventional polarizing plate produced from the stretched film as described above has a problem that when the polarizing plate is peeled from the liquid crystal cell in the rework process, the polarizing plate is torn in the stretching direction of the stretched film and cannot be easily peeled off. there were. Moreover, since it is very easy to tear in the extending | stretching direction, there also existed a problem that handling was difficult not only in the said rework process.

  Accordingly, the present invention is a polarizing laminated film that is provided with a polarizer layer on a substrate film and can be used as a polarizing plate itself, and has high resistance to tearing during handling such as the reworking process (resistance to resistance). An object of the present invention is to provide a polarizing laminated film having excellent tearability and a laminated film suitable as a production intermediate thereof.

  The present invention provides a polarizing laminated film comprising a base film and a polarizer layer laminated on at least one surface of the base film. In the polarizing laminated film of the present invention, the base film has a laminated structure of two or more resin layers composed of resins having different phase transition temperatures, and the highest phase transition of the two or more resin layers. When A is a resin layer composed of a resin exhibiting a temperature and B is a resin layer composed of a resin exhibiting the lowest phase transition temperature, these are represented by A / B / A or B / A / B Include in order. In the polarizing laminate film of the present invention, the resin layer A is oriented in any direction within the plane, and the resin layer B is substantially non-oriented in the plane.

  Here, the phase transition temperature means the glass transition temperature Tg when the resin constituting the resin layer is an amorphous resin, and means the melting point Tm when the resin is a crystalline resin.

  The difference between the phase transition temperature of the resin constituting the resin layer A and the phase transition temperature of the resin constituting the resin layer B is preferably 10 ° C. or higher. For example, the resin layers A and B can be made of a chain polyolefin resin having different melting points.

  The polarizer layer is preferably one in which a dichroic dye is adsorbed and oriented on a polyvinyl alcohol-based resin layer, and the thickness thereof is preferably 10 μm or less. In one preferable embodiment, the absorption axis of the polarizer layer and the orientation axis of the resin layer A are parallel.

  The polarizing laminated film of the present invention can further include a transparent protective layer laminated on at least one polarizer layer.

  Moreover, this invention provides a laminated film provided with a base film and the stretched polyvinyl alcohol-type resin layer laminated | stacked on the at least one surface of this base film. In the laminated film of the present invention, the base film has a laminated structure of two or more resin layers composed of resins having different phase transition temperatures, and has the highest phase transition temperature of the two or more resin layers. When the resin layer composed of the resin shown is A and the resin layer composed of the resin showing the lowest phase transition temperature is B, these are in the order of A / B / A or B / A / B Including. In the laminated film of the present invention, the resin layer A is oriented in any direction in the plane, and the resin layer B is substantially non-oriented in the plane. The phase transition temperature here has the same meaning as described above.

  In the laminated film of the present invention, the difference between the phase transition temperature of the resin constituting the resin layer A and the phase transition temperature of the resin constituting the resin layer B is preferably 10 ° C. or higher. For example, the resin layers A and B can be made of a chain polyolefin resin having different melting points. The thickness of the polyvinyl alcohol-based resin layer is preferably 10 μm or less. In one preferred embodiment, the orientation axis of the polyvinyl alcohol-based resin layer and the orientation axis of the resin layer A are parallel.

  ADVANTAGE OF THE INVENTION According to this invention, while being thin, the polarizing laminated film excellent in the tear resistance at the time of handling, such as a rework process, is provided. Since the polarizing laminated film of the present invention has good polarizing performance, it can be used as a polarizing plate itself, or can be used as a production intermediate for a polarizing plate having a transparent protective layer. According to the polarizing laminate film of the present invention, a thin and highly durable image display device such as a polarizing plate or a liquid crystal display device can be produced with good yield and stability. The liquid crystal display device using the polarizing laminated film of the present invention exhibits a high contrast ratio.

  Moreover, according to this invention, while being thin, the laminated | multilayer film excellent in tear resistance are provided. The laminated film of the present invention is extremely suitable as an intermediate for producing the above polarizing laminated film because it is difficult to tear in each step of performing treatment for imparting polarization performance thereto. According to the laminated film of the present invention, a thin polarizing laminated film having excellent tear resistance can be produced with good yield and stability.

It is a schematic sectional drawing which shows a preferable example of the light-polarizing laminated film which concerns on this invention. It is a schematic sectional drawing which shows another preferable example of the light-polarizing laminated film which concerns on this invention. It is a schematic diagram which shows the sample produced in order to measure the orientation state of the resin layer which comprises a base film. It is a schematic diagram which shows a mode that the orientation state of the resin layer which comprises a base film is measured using the sample shown by FIG. It is a schematic sectional drawing which shows another preferable example of the light-polarizing laminated film which concerns on this invention. It is a schematic sectional drawing which shows another preferable example of the light-polarizing laminated film which concerns on this invention. It is a schematic sectional drawing which shows a preferable example of the laminated | multilayer film concerning this invention. It is a schematic sectional drawing which shows another preferable example of the laminated | multilayer film based on this invention. It is a polarizing microscope photograph when the sample of Example 3 is arranged in an orientation in which the length direction (stretching direction) forms an angle of 45 ° with respect to the transmission axis of the polarizer. It is a photograph which shows the rework property evaluation test result of the light-polarizing laminated film of Example 3. It is a photograph which shows the rework property evaluation test result of the light-polarizing laminated film of the comparative example 3.

<Polarizing laminated film>
The polarizing laminated film of the present invention includes a polarizer layer laminated on at least one surface of a base film, and the base film is composed of two or more kinds of resins having different phase transition temperatures. It is composed of a laminated structure of layers. A resin layer composed of a resin showing the highest phase transition temperature among two or more resin layers is A (hereinafter also referred to as resin layer A), and a resin layer composed of a resin showing the lowest phase transition temperature is B. When referred to as (hereinafter also referred to as resin layer B), the base film includes these resin layers in the order of A / B / A or B / A / B.

  In the polarizing laminated film of the present invention, the resin layer A composed of a resin having the highest phase transition temperature among two or more types of resin layers having different phase transition temperatures is oriented in any direction within the plane of the resin layer. In this state, the resin layer B composed of the resin exhibiting the lowest phase transition temperature is in a substantially non-oriented state in the resin layer plane.

  The preferable example of the light-polarizing laminated film which concerns on this invention is shown with a schematic sectional drawing in FIG.1 and FIG.2. The polarizing laminated films 10 and 10 ′ shown in FIG. 1 and FIG. 2 are both base film 20, 20 ′ and polarizer layers 30, 30 laminated on one surface of the base film 20, 20 ′. It consists of 'and. The base film 20 of the polarizing laminated film 10 shown in FIG. 1 includes a resin layer A composed of a resin exhibiting the highest phase transition temperature, and a resin layer B composed of a resin exhibiting the lowest phase transition temperature. More specifically, it has a laminated structure in which three resin layers are laminated in the order of resin layer A / resin layer B / resin layer A. The polarizer layer 30 is laminated on the resin layer A.

  On the other hand, the base film 20 ′ of the polarizing laminated film 10 ′ shown in FIG. 2 has a structure in which three resin layers are laminated in the order of resin layer B / resin layer A / resin layer B. The polarizer layer 30 ′ is laminated on the resin layer B.

  Here, the “phase transition temperature” means the glass transition temperature Tg when the resin constituting the resin layer is an amorphous resin, and means the melting point (crystalline melting point) Tm when the resin is a crystalline resin. Both are measured in accordance with JIS K7121.

  Further, “the resin layer is in a state of being oriented in any direction within the resin layer surface” and “it is in a substantially non-oriented state within the resin layer surface” are defined as follows.

  First, as shown in FIG. 3, after peeling the base film from the polarizing laminated film, it is cooled to −90 ° C., and the cooled base film is cut twice using a cryomicrotome, A base film piece having a width of 3 μm (length is about 1 to 2 mm, thickness is the thickness of the base film) is cut out and used as a sample (FIG. 3A). FIG. 3B is an enlarged perspective view showing the sample. At this time, as shown in FIG. 4, the sample is cut out from the base film so that the orientation direction of the resin layer A constituting the base film is parallel to the length direction of the sample. Note that FIG. 3 and FIG. 4 to be described later show, as an example, a case where the base film is composed of three resin layers of resin layer A / resin layer B / resin layer A as shown in FIG. ing.

  The orientation direction of the resin layer A constituting the base film is, for example, when a “laminated film” according to the present invention is produced by stretching an “unstretched film” described later, and a polarizing laminated film is produced using this. Is the stretching direction of the unstretched film.

  When the orientation direction of the resin layer A constituting the base film is unknown, a commercially available phase difference measuring instrument (for example, “KOBRA-WPR” manufactured by Oji Scientific Instruments Co., Ltd., Otsuka Electronics Co., Ltd.) The orientation direction is confirmed using “RETS” manufactured by Co., Ltd., or the orientation direction is confirmed as follows.

  That is, first, there is an in-plane phase difference between a polarizer and an analyzer of a polarizing microscope arranged so that the transmission axes are orthogonal to each other, and the slow axis direction (orientation direction) is known. A phase difference film is arranged such that its plane is parallel to the planes of the polarizer and the analyzer. At this time, the retardation film is arranged such that the orientation direction thereof forms an azimuth angle of 45 ° (or 135 °) with respect to the transmission axis of the polarizer. In this state, when the light is irradiated from the direction perpendicular to the retardation film surface using a light source and the brightness of the transmitted image to the analyzer side is observed with a polarizing microscope, the retardation film is It is observed brighter than when placed at other azimuth angles.

  Next, the base film whose orientation direction is unknown is disposed between the polarizer of the polarizing microscope and the retardation film, and the base film is rotated around an axis parallel to the optical axis of the polarizing microscope. When the brightness of the transmitted image to the analyzer side is observed with a polarizing microscope while rotating the base film, the orientation of the base film is parallel to the orientation direction of the base film and the orientation direction of the retardation film. As a result of superimposing the phase difference and the phase difference of the phase difference film, it is observed brighter than when the base film is not interposed. Therefore, in this case, the orientation direction of the resin layer A constituting the base film is a direction parallel to the orientation direction of the retardation film (while the orientation direction of the base film and the orientation direction of the retardation film are orthogonal to each other). In some cases, the observation is darker than when the base film is not interposed. Therefore, the orientation direction of the resin layer A may be confirmed from this observation result).

  Next, as shown in FIG. 4, between the polarizer and analyzer of the polarizing microscope arranged so that the transmission axes are orthogonal to each other, the two resin layer laminated sections facing each other in the sample are respectively a polarizer, Place the sample parallel to the polarizer and the analyzer so that it faces the analyzer (at this time, the side of the sample having a width of 3 μm is parallel to the optical axis direction of the polarizing microscope (light traveling direction)) Light is irradiated using a light source from the direction perpendicular to the resin layer lamination cross section of the sample, and the brightness of the transmitted image of each resin layer to the analyzer side under the crossed Nicols is measured with a polarizing microscope. Observe at. This observation is performed on the analyzer side from a direction perpendicular to the resin layer lamination cross section of the sample (a direction parallel to the optical axis of the polarization microscope).

  In the above state, the sample is rotated about the axis parallel to the optical axis of the polarizing microscope through the center of the sample, so that the transmission axis of the polarizer (that is, the polarization direction of the polarized light incident on the sample) ) When the azimuth in the length direction of the sample is changed (when the azimuth in the initial state before rotation is 0 °, at least until the azimuth is 180 °), the azimuth increases by 45 °. Each time, when the transmitted image is observed brightest and when it is observed darkest, the resin layer is defined as “orientated in any direction within the resin layer surface”. Is done. Such repeated bright and dark transmission images under crossed Nicols are such that the resin layer is oriented in the plane (in the plane defined by the length direction and width direction of the sample), and is orthogonal to the orientation direction. This is due to a difference in refractive index between the direction and the direction.

  For example, when the resin layer A of the sample is oriented in the length direction (uniaxial orientation), when the sample is rotated, the orientation axis (alignment direction) and the transmission axis of the polarizer (polarization direction of polarized light) Is at the azimuth of 45 ° and 135 °, the transmitted image is observed brightest, and when it is at the angles of 0 °, 90 °, and 180 °, the transmitted image is observed at the darkest.

  On the other hand, even if the azimuth angle of the sample in the length direction with respect to the transmission axis of the polarizer is changed, no change is observed in the brightness of the transmitted image, and when it is recognized that the dark state is maintained, The resin layer is defined as “substantially non-oriented in the plane of the resin layer”.

  FIG. 4 shows that when a sample in which the resin layer A is oriented in the length direction is arranged in an orientation in which the length direction forms an azimuth angle of 45 ° with respect to the transmission axis of the polarizer, the resin layer A This shows a state where the brightly observed non-oriented resin layer B is darkened.

  Since the polarizing laminated film of the present invention includes the resin layer A in an oriented state and the resin layer B that is not substantially oriented as the resin layer constituting the base film, the polarizing property includes a rework process and the like. Excellent tear resistance when handling laminated films. That is, since the resin layer B that is not substantially oriented and therefore exhibits high tear resistance in any direction is included, the resin layer A and the polarizer layer that are relatively easy to tear in the orientation direction are included. However, the resin layer B gives tear resistance to the entire polarizing laminate film, and the entire polarizing laminate film has excellent tear resistance in all directions including the orientation directions of the resin layer A and the polarizer layer. Showing gender. Therefore, the polarizing laminated film of the present invention is excellent in durability.

  In contrast, a conventional polarizing plate using a stretched film obtained by stretching a film having a polyvinyl alcohol-based resin layer on a base film composed of a single resin layer has a stretched base film. Since it is oriented in the direction, there is a problem that it is easy to tear in the stretching direction.

  More specifically, the stretching of a film having a polyvinyl alcohol-based resin layer on a base film is fluid if the base film is a single resin layer as in the prior art, and the stretching temperature is too low. Is too low to easily break the base film, and if it is too high, the base film will be in an excessively molten state and cannot be stretched. Therefore, the phase transition temperature of the resin constituting the base film (resin layer) (amorphous) Usually, it is carried out at a temperature in the vicinity of the glass transition temperature Tg in the case of a crystalline resin, and the melting point Tm in the case of a crystalline resin. However, when the stretching treatment is performed in the vicinity of the phase transition temperature, the base film is also oriented in the stretching direction together with the polyvinyl alcohol-based resin layer. Therefore, the base film in the stretching direction, and thus the stretched film, and a polarizing plate using the same It becomes easy to tear.

  In the polarizing laminated film of the present invention, the base film is formed by laminating resin layers A and B such as resin layer A / resin layer B / resin layer A or resin layer B / resin layer A / resin layer B. Since they are arranged symmetrically with respect to the direction, curling of the film is effectively suppressed, and there is an advantage that handling is easy.

  The polarizing laminated film of the present invention is not limited to the examples shown in FIGS. 1 and 2, and may include a polarizer layer on both sides of the base film in consideration of curling suppression of the film, for example. . Moreover, the other resin layer arrange | positioned between the resin layer A and the resin layer B and / or the base film surface may be included. If the example of another resin layer is given, it will comprise base film itself, has a phase transition temperature lower than a phase transition temperature of resin which constitutes resin layer A, and higher than a phase transition temperature of resin which constitutes resin layer B One or more other resin layers (resin layer C); an adhesive layer responsible for adhesion between the polarizer layer and the substrate film; to improve the adhesion between the polarizer layer and the substrate film Intervening layers (also referred to as easy-adhesion layers, primer layers, etc.). When the base film includes the resin layer C, from the viewpoint of suppressing curling of the film, the three or more types of resin layers constituting the base film are arranged so as to have a symmetric structure with respect to the stacking direction as described above. Is preferred.

  Further, as shown in FIGS. 5 and 6, the polarizing laminated film of the present invention can further include a transparent protective layer 40, 40 ′ laminated on the polarizer layer 30, 30 ′. The polarizing laminated film 25 shown in FIG. 5 is an example in which the transparent protective layer 40 is laminated on the polarizer layer 30 of the polarizing laminated film 10 of FIG. 1, and the polarizing laminated film 25 ′ shown in FIG. This is an example in which a transparent protective layer 40 ′ is laminated on the polarizer layer 30 ′ of the polarizing laminate film 10 ′. When providing a polarizer layer on both surfaces of a base film, a transparent protective layer may be laminated | stacked on one polarizer layer, and may be laminated | stacked on both polarizer layers.

  The transparent protective layer can be, for example, a transparent protective film made of an appropriate thermoplastic resin, and has a hard coat layer, an antiglare layer, and an antireflection coating on the surface of the transparent protective film opposite to the polarizer layer. An optical layer such as a layer may be formed.

Hereinafter, the polarizing laminate film of the present invention will be described in more detail.
(Base film)
As described above, the base film constituting the polarizing laminated film of the present invention has a laminated structure of three or more resin layers including at least two types of resin layers A and B exhibiting different phase transition temperatures. The resin layer A is a resin layer composed of a resin exhibiting the highest phase transition temperature among two or more types of resin layers constituting the base film, and is oriented in any direction within the resin layer surface. . The resin layer B is a resin layer composed of a resin exhibiting the lowest phase transition temperature among two or more kinds of resin layers, and is in a substantially non-oriented state in the resin layer plane.

  Each of the three or more resin layers constituting the base film may be made of an amorphous resin or may be made of a crystalline resin. That is, only a resin layer made of an amorphous resin may be combined, or only a resin layer made of a crystalline resin may be combined, or a resin layer made of an amorphous resin and a resin layer made of a crystalline resin And may be combined.

  The orientation state of the resin layer constituting the base film as described above can also be achieved by laminating a resin layer having a predetermined orientation state in advance, but formation of a polarizer layer (giving polarization performance) Since it is possible to simultaneously perform the stretching treatment required for the coating and the provision of the predetermined orientation state of the resin layer constituting the base film, the stretching treatment and the dichroic dye are formed on the base film having the predetermined resin layer configuration. It is preferable to give the orientation state of the resin layer by stretching an “unstretched film” in which a resin layer (such as a polyvinyl alcohol-based resin layer) that becomes a polarizer layer by adsorption orientation is laminated. That is, the polarizing laminated film of the present invention can be obtained by subjecting a stretched film obtained by stretching the unstretched film to a dichroic dye adsorption orientation treatment. As the stretched film, a “laminated film” according to the present invention described later can be suitably used. The stretching is usually uniaxial stretching. In this case, the absorption axis of the polarizer layer and the orientation axis (orientation direction) of the resin layer A are parallel (both are parallel to the stretching direction).

  The orientation state of the resin layer in the case where the polarizing laminate film of the present invention is formed from the stretched film will be described more specifically. The stretch temperature of the unstretched film is the phase transition temperature indicated by the resin constituting the resin layer A. If it is set in the vicinity, the layers other than the layer to be the resin layer A (particularly the layer to be the resin layer B) are in a molten state at the time of stretching, and thus do not cause orientation (or hardly occur). As a result, the resin layer A is imparted with resistance to tearing in the stretching direction as a whole of the polarizing laminated film, even though the resin layer A is oriented by stretching.

  In addition, since the layer that becomes the resin layer A maintains a relatively rigid state at the time of stretching, it serves as a support for holding the layer that becomes the resin layer B that is in a molten state at the time of stretching, and also at the time of stretching. The material film can retain its shape. In this regard, when the example of FIG. 1 is compared with the example of FIG. 2, the resin layer B is interposed between the two resin layers A in the example of FIG. Although it can be said that the film retainability of the layer to be used and the handleability and heat resistance of the film at the time of stretching are excellent, in the example of FIG. 2 as well, appropriate selection of the stretching temperature and the type of resin constituting the resin layer Thus, the stretching process can be performed satisfactorily.

  Thus, in the case of the stretched film obtained by stretching the unstretched film, the polarizing laminated film of the present invention is given resistance to tearing in the stretching direction by the resin layer B that is not substantially oriented by stretching. Has been. In such a case, the orientation axis of the resin layer A is parallel to the absorption axis of the polarizer layer. However, in the present invention, the orientation axis direction of the resin layer A is not limited to this, and it is only necessary to have the orientation axis in any direction within the resin layer surface.

  The greater the difference between the phase transition temperature indicated by the resin constituting the resin layer A and the phase transition temperature indicated by the resin constituting the resin layer B, the greater the unstretched film near the phase transition temperature indicated by the resin constituting the resin layer A. When the film is stretched, the layer that becomes the resin layer B tends to be in a molten state, so that the orientation expression in the resin layer B is further suppressed, and the tear resistance in the stretching direction of the polarizing laminated film can be further improved. . From such a viewpoint, the difference between the phase transition temperature exhibited by the resin constituting the resin layer A and the phase transition temperature exhibited by the resin constituting the resin layer B is preferably 10 ° C. or higher, and is 20 ° C. or higher. Preferably there is. On the other hand, if the difference is extremely large, the handleability of the unstretched film and the heat resistance of the unstretched film at the time of stretching (for example, the layer that becomes the resin layer B is in a molten state with extremely high fluidity). Therefore, the difference is preferably 100 ° C. or less.

  The phase transition temperature of each resin constituting each resin layer of the base film (the glass transition temperature Tg in the case of an amorphous resin, the melting point Tm in the case of a crystalline resin) is the handleability of the base film. In view of the above, it is preferably 25 ° C. or higher, more preferably 40 ° C. or higher. Moreover, from the viewpoint of heat resistance of the unstretched film during stretching, the phase transition temperature of each resin is preferably 60 ° C. or higher, more preferably 80 ° C. or higher.

  On the other hand, the phase transition temperature of each resin is preferably 250 ° C. or lower, and more preferably 200 ° C. or lower. In order to stretch the unstretched film, it is necessary to raise the temperature to the vicinity of the highest phase transition temperature. When there is a resin layer having a phase transition temperature exceeding 250 ° C., when the temperature is raised to the vicinity of the temperature. This is because there is a concern that thermal degradation may occur in a resin layer (such as a polyvinyl alcohol-based resin layer) that becomes a polarizer layer due to the adsorption orientation of the dichroic dye. As for the type of resin (phase transition temperature) constituting each resin layer, the difference between the highest phase transition temperature (phase transition temperature of resin layer A) and the lowest phase transition temperature (phase transition temperature of resin layer B) is the above. It is preferable that the range is selected.

  The resins constituting the plurality of resin layers of the base film are preferably selected so as to satisfy the relationship of the phase transition temperatures described above. Further, these resins are preferably thermoplastic resins excellent in transparency, mechanical strength, thermal stability, stretchability, and the like. Specific examples of thermoplastic resins include cellulose ester resins such as cellulose triacetate; polyester resins; polyethersulfone resins; polysulfone resins; polycarbonate resins; polyamide resins; polyimide resins; And polyolefin resins such as cyclic resins and cyclic polyolefin resins (such as norbornene resins); (meth) acrylic resins; polyarylate resins; polystyrene resins; polyvinyl alcohol resins; and mixtures thereof. In particular, because of excellent smoothness for applying a polyvinyl alcohol-based resin and excellent stretchability of an unstretched film in which a polyvinyl alcohol-based resin layer is laminated, the base film is a cellulose ester resin, a chain It is preferable to include a resin layer composed of at least one selected from the group consisting of polyolefin resins, cyclic polyolefin resins, and (meth) acrylic resins.

  The cellulose ester resin is an ester of cellulose and a fatty acid. Specific examples of the cellulose ester resin include cellulose triacetate, cellulose diacetate, cellulose tripropionate, and cellulose dipropionate. Among these, cellulose triacetate is particularly preferable. Many products of cellulose triacetate are commercially available, which is advantageous in terms of availability and cost. Examples of commercially available cellulose triacetate are “Fujitac TD80” (manufactured by Fuji Film Co., Ltd.), “Fujitac TD80UF” (manufactured by Fuji Film Co., Ltd.), “Fujitac TD80UZ” (Fuji Film ( Co., Ltd.), “Fujitac TD40UZ” (Fuji Film Co., Ltd.), “KC8UX2M” (Konica Minolta Opto Co., Ltd.), “KC4UY” (Konica Minolta Opto Co., Ltd.), and the like.

  The polyester resin is a resin containing an ester bond in the main chain, and a typical example thereof is polyethylene terephthalate (PET) which is a copolymer of terephthalic acid and ethylene glycol. Polyethylene terephthalate is a crystalline resin, but the one in a state before crystallization treatment is more easily subjected to treatment such as stretching. If necessary, it can be crystallized during stretching or by heat treatment after stretching. In addition, a copolymerized polyester whose crystallinity is lowered (or made amorphous) by further copolymerizing another monomer with a polyethylene terephthalate skeleton is also preferably used. Examples of such resins include, for example, those obtained by copolymerization of cyclohexanedimethanol, isophthalic acid, and the like. These resins are also excellent in stretchability and can be suitably used. In the case of such resins, the glass transition temperature Tg can be considered as an index if it is amorphous before stretching, and the melting point Tm can be considered as an index if it has already been crystallized before stretching. Those that are amorphous before stretching are more preferred because they are excellent in stretchability.

  Further, as polyester resins other than polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polycyclohexane dimethyl terephthalate (PCT), polycyclohexane dimethyl naphthalate (PCN), polytrimethylene terephthalate (PTT), polytrimethylene naphthalate (PTN) and the like can be suitably used.

  Examples of the chain polyolefin-based resin include homopolymers such as polyethylene resin and polypropylene resin, and copolymers composed of two or more chain olefins.

  Cyclic polyolefin resin is a general term for resins that are polymerized using cyclic olefin as a polymerization unit, and is described in, for example, JP-A-1-240517, JP-A-3-14882, JP-A-3-122137, and the like. Resin. Specific examples of cyclic polyolefin resins include, for example, ring-opening (co) polymers of cyclic olefins, addition polymers of cyclic olefins, copolymers of cyclic olefins and chain olefins such as ethylene and propylene (typical) Random copolymers), graft polymers obtained by modifying them with unsaturated carboxylic acids or their derivatives, and hydrides thereof. Among these, norbornene resins using norbornene monomers such as norbornene and polycyclic norbornene monomers as cyclic olefins are preferably used.

  Various products are commercially available as cyclic polyolefin resins. Examples of commercial products of cyclic polyolefin resins are trade names, “Topas” (manufactured by TOPAS ADVANCED POLYMERS GmbH, available from Polyplastics Co., Ltd.), “Arton” (manufactured by JSR Corporation). “ZEONOR” (manufactured by Nippon Zeon Co., Ltd.), “ZEONEX” (manufactured by Nippon Zeon Co., Ltd.), “Apel” (manufactured by Mitsui Chemicals, Inc.), and the like.

  Any appropriate (meth) acrylic resin can be adopted as the (meth) acrylic resin. For example, poly (meth) acrylic acid ester such as polymethyl methacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester -(Meth) acrylic acid copolymer, (meth) acrylic acid methyl-styrene copolymer (MS resin, etc.), polymer having an alicyclic hydrocarbon group (for example, methyl methacrylate-cyclohexyl methacrylate copolymer) And methyl methacrylate- (meth) acrylate norbornyl copolymer). Preferably, poly (meth) acrylic acid alkyl having 1 to 6 carbon atoms in the alkyl moiety, such as poly (meth) acrylic acid methyl, and more preferably, methyl methacrylate as the main component (50 to 100 weight). %, Preferably 70 to 100% by weight).

  Among the thermoplastic resins described above, since the extensibility is excellent and the adjustment of the phase transition temperature is easy, the plurality of resin layers of the base film are preferably made of a chain polyolefin resin, Polypropylene resin (polypropylene resin that is a homopolymer of propylene, copolymer mainly composed of propylene, etc.), polyethylene resin (polyethylene resin that is a homopolymer of ethylene, copolymer mainly composed of ethylene, etc.) Etc.).

  The chain polyolefin resin is often crystalline, and the polypropylene resin, which is a propylene homopolymer, has a melting point Tm in the range of about 150 to 180 ° C. In the case of a polyethylene resin which is a homopolymer of ethylene, the melting point Tm can vary depending on its density and the like, but the melting point Tm is generally in the range of 100 to 140 ° C. Further, for example, a polypropylene resin obtained by copolymerizing propylene with another monomer such as ethylene can obtain a melting point lower than the melting point of a propylene homopolymer. Thus, the phase transition temperature of the resin can be controlled by adjusting the type of the main monomer, the presence or absence of the copolymer component, the type and content of the copolymer component, and the like.

  Examples of other types of monomers copolymerizable with propylene include ethylene and α-olefin. As the α-olefin, an α-olefin having 4 or more carbon atoms is preferably used, and more preferably an α-olefin having 4 to 10 carbon atoms. Specific examples of the α-olefin having 4 to 10 carbon atoms include linear monoolefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene; Branched monoolefins such as 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene; vinylcyclohexane and the like. The copolymer of propylene and other monomers copolymerizable therewith may be a random copolymer or a block copolymer. In addition, the content rate of the structural unit derived from the said other monomer in a copolymer is infrared (IR) according to the method described on page 616 of "Polymer Analysis Handbook" (1995, published by Kinokuniya). ) It can be obtained by performing a spectrum measurement.

  Among these, as the polypropylene resin, a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-1-butene random copolymer, and a propylene-ethylene-1-butene random copolymer are preferable. Used.

  The stereoregularity of the polypropylene resin is preferably substantially isotactic or syndiotactic. The base film containing a resin layer made of a polypropylene resin having substantially isotactic or syndiotactic stereoregularity is relatively easy to handle and has excellent mechanical strength in a high temperature environment. ing.

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

  In addition, the base film in an unstretched film may be previously stretched in a direction perpendicular to the stretching direction in the stretching process in the film plane. Stretching in a direction perpendicular to the stretching direction in the film plane means, for example, transverse stretching in the case of longitudinal stretching in which stretching of an unstretched film is performed in the film transport direction (longitudinal direction of the unstretched film), that is, in the longitudinal direction. Stretching (stretching in the film width direction) is meant.

  The thickness of the base film in the unstretched film (before stretching) is not particularly limited, but is preferably 1 to 500 μm, more preferably 1 to 300 μm, and further preferably 5 to 200 μm from the viewpoint of workability such as strength and handleability. 5 to 150 μm is most preferable.

  The thickness of the base film in a polarizing laminated film and the laminated film mentioned later is 1-300 micrometers normally, Preferably it is 1-100 micrometers. When the polarizing laminated film and the laminated film are produced through stretching of an unstretched film, when the thickness of the unstretched film is in the above range, the thickness of the polarizing laminated film and the laminated film is usually 1 to 300 μm. Within range.

  There are no particular restrictions on the thickness of the unstretched film, the polarizing laminated film, and the thickness of each resin layer constituting the laminated film, but in order to impart sufficient tear resistance, the polarizing laminated film and the laminated film substantially The thickness of the resin layer B that is not oriented is preferably 2 μm or more, and more preferably 5 μm or more. In the example shown in FIGS. 1 and 2, it is preferable that the two outer layers of the base film have the same thickness so that the resin layer structure of the base film is symmetrical.

  The base film according to the present invention including a plurality of resin layers can be easily produced as an unstretched film by, for example, a coextrusion molding method using a multilayer extrusion molding machine. Alternatively, a base film can be obtained by laminating a plurality of resin layers that have been in a predetermined orientation state in advance.

(Polarizer layer)
The polarizer layer may be any layer having polarization performance, but is typically a dichroic dye adsorbed and oriented on a stretched polyvinyl alcohol resin layer. The stretching is usually uniaxial stretching. A polarizer layer is laminated | stacked on the single side | surface or both surfaces of a base film.

  As a polyvinyl alcohol-type resin which forms a polarizer layer, polyvinyl alcohol resin and its derivative (s) are mentioned, for example. Derivatives of polyvinyl alcohol resin include polyvinyl formal, polyvinyl acetal, etc., olefins such as ethylene and propylene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and alkyl esters of unsaturated carboxylic acids. And those modified with acrylamide or the like. Among these, it is preferable to use a polyvinyl alcohol resin.

  100-10000 are preferable and, as for the average degree of polymerization of polyvinyl alcohol-type resin, 1000-10000 are more preferable. If the average degree of polymerization is less than 100, it is difficult to obtain preferable polarization characteristics. If it exceeds 10,000, the solubility in water deteriorates and it becomes difficult to form a polyvinyl alcohol resin layer. The average saponification degree of the polyvinyl alcohol resin is preferably 80 to 100 mol%, more preferably 94 mol% or more. When the average saponification degree is less than 80 mol%, it is difficult to obtain preferable polarization characteristics.

  If necessary, additives such as a plasticizer and a surfactant may be added to the polyvinyl alcohol resin. As the plasticizer, a polyol or a condensate thereof can be used, and examples thereof include glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, and polyethylene glycol. The amount of the additive is not particularly limited, but is preferably 20% by weight or less in the polyvinyl alcohol resin.

  The thickness of the polyvinyl alcohol-based resin layer in the polarizer layer and the laminated film described later is preferably 10 μm or less from the viewpoint of thinning, and the dyeability to the laminated film, and the polarizing laminated film and the laminated film are thinned. From this viewpoint, it is more preferably 1 to 10 μm, and further preferably 2 to 8 μm. In addition, it is preferable that the thickness of the polyvinyl alcohol-type resin layer in an unstretched film is 3-30 micrometers, and it is more preferable that it is 5-20 micrometers.

  As will be described later, the formation of the polyvinyl alcohol-based resin layer in the unstretched film can be carried out by coating and drying the polyvinyl alcohol-based resin solution directly on one side of the base film. In order to improve the adhesion between the system resin layer and the base film, a primer layer (easy adhesion layer) may be formed on the base film surface. The polyvinyl alcohol-based resin layer can also be formed by sticking a film made of a polyvinyl alcohol-based resin on the base film, but in this case, an adhesive is used for sticking between the films. it can.

(Transparent resin layer)
The transparent resin layer is a layer that is optionally provided on at least one of the polarizer layers (see FIGS. 5 and 6). For example, the transparent resin layer can be a transparent protective film made of an appropriate thermoplastic resin, and can be transparent. 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 opposite to the polarizer layer.

  The polarizing laminated film having a transparent protective layer can be used as a polarizing plate, similarly to the polarizing laminated film not having a transparent protective layer, and a polarizing plate having a transparent protective layer is prepared by peeling the substrate film. It is also useful as a production intermediate.

  Examples of the transparent protective film include polyolefin resins such as chain polyolefin resins (polypropylene resin films, etc.) and cyclic polyolefin resins (norbornene resins, etc.); cellulose esters composed of resins such as cellulose triacetate and cellulose diacetate. Examples thereof include polyester resin films; polyester resin films made of resins such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polycarbonate resin films; acrylic resin films.

  As the cyclic polyolefin-based resin, appropriate commercial products, for example, “Topas” (manufactured by TOPAS ADVANCED POLYMERS GmbH, available from Polyplastics Co., Ltd.), “Arton” (JSR Corp.) ZEONOR (manufactured by Nippon Zeon Co., Ltd.), "ZEONEX" (manufactured by Nippon Zeon Co., Ltd.), "Appel" (manufactured by Mitsui Chemicals, Inc.), etc. Can do. When such a cyclic polyolefin resin is formed into a film, a known method such as a solvent casting method or a melt extrusion method is appropriately used. In addition, film names such as “ESCINA” (manufactured by Sekisui Chemical Co., Ltd.), “SCA40” (manufactured by Sekisui Chemical Co., Ltd.), “ZEONOR FILM” (manufactured by Nippon Zeon Co., Ltd.), etc. You may use the commercial item of the film made from the made cyclic polyolefin resin.

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

  Since the cyclic polyolefin resin film is generally inferior in surface activity, surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame (flame) treatment, saponification treatment, etc. is applied to the surface attached to the polarizer layer. It is preferred to do so. Among these, plasma treatment and corona treatment that can be performed relatively easily are preferable.

  As the cellulose ester-based resin film, appropriate commercial products, for example, “Fujitac TD80” (manufactured by FUJIFILM Corporation), “FUJITAC TD80UF” (manufactured by FUJIFILM Corporation), “Fujitac TD80UZ” "Fuji Film KK", "Fujitac TD40UZ" (Fuji Film KK), "KC8UX2M" (Konica Minolta Opto), "KC4UY" (Konica Minolta Opt) It can be used suitably.

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

  The transparent protective film is preferably thin, but if it is too thin, the strength is lowered and the processability is poor. On the other hand, when it is too thick, problems such as a decrease in transparency and a longer curing time after lamination occur. Therefore, the thickness of the transparent protective film is preferably 80 μm or less, more preferably 5 to 60 μm. Further, from the viewpoint of thinning the polarizing laminated film and the polarizing plate, the total thickness of the polarizer layer and the transparent protective film is preferably 100 μm or less, more preferably 90 μm or less, and further preferably 80 μm or less. .

  Bonding of the polarizer layer of the polarizing laminate film and the transparent protective film can be performed using an adhesive or a pressure-sensitive adhesive.

<Laminated film>
The laminated film of the present invention includes a stretched polyvinyl alcohol-based resin layer laminated on at least one surface of a base film, and the base film is composed of two resins having different phase transition temperatures. It is comprised from the laminated structure of the above resin layer. The base film is composed of a resin exhibiting the highest phase transition temperature among the two or more types of resin layers, and is oriented in any direction within the resin layer surface, and the lowest phase transition temperature. A resin layer B that is made of a resin having a substantially non-oriented state in the resin layer surface is included in the order of A / B / A or B / A / B. The definitions of “phase transition temperature”, “in a state of being oriented in any direction in the resin layer surface”, and “in a substantially non-oriented state in the resin layer surface” are the same as described above.

  That is, in the laminated film of the present invention, the layer laminated on at least one surface of the base film is a stretched polyvinyl alcohol-based resin layer that becomes a polarizer layer by adsorption orientation of the dichroic dye. , Having the same configuration as the polarizing laminated film. Therefore, the laminated film of the present invention is extremely effective as a production intermediate for obtaining the polarizing laminated film of the present invention by using the polyvinyl alcohol resin layer as a polarizer layer by adsorption orientation of the dichroic dye.

  The preferable example of the laminated | multilayer film based on this invention is shown with a schematic sectional drawing in FIG. 7 and FIG. The laminated films 15 and 15 ′ shown in FIGS. 7 and 8 are both base film 20, 20 ′ and a stretched polyvinyl alcohol-based resin layer laminated on one surface of the base film 20, 20 ′. 35, 35 '. The base film 20 of the laminated film 15 shown in FIG. 7 has a laminated structure in which three resin layers are laminated in the order of resin layer A / resin layer B / resin layer A. The polyvinyl alcohol-based resin layer 35 is laminated on the resin layer A.

  On the other hand, the base film 20 ′ of the laminated film 15 ′ shown in FIG. 8 has a structure in which three resin layers are laminated in the order of resin layer B / resin layer A / resin layer B. The polyvinyl alcohol resin layer 35 ′ is laminated on the resin layer B.

  The laminated film of the present invention, like the polarizing laminated film, has excellent tear resistance in all directions due to the substantially non-oriented resin layer B. The polarizing laminated film obtained as above also has excellent tear resistance.

  Further, according to the laminated film of the present invention, the polarizing laminated film can be produced stably and with good yield because it is difficult to tear even in the dyeing step of the dichroic dye when producing the polarizing laminated film. . On the other hand, when manufacturing a polarizing plate using a conventional stretched film obtained by stretching a film having a polyvinyl alcohol-based resin layer on a base film composed of a single resin layer, Since the entire material film is oriented in the stretching direction, especially when the stretch ratio of the stretched film to be used is high, when the polyvinyl alcohol-based resin layer is dyed, the film is rolled up with a roll such as a nip roll. There was a problem that it was difficult to obtain a desired polarizing plate because it was torn in the stretching direction.

  Further, in the laminated film of the present invention, the substrate film is a resin such as resin layer A / resin layer B / resin layer A or resin layer B / resin layer A / resin layer B, similar to the polarizing laminate film. Since the layers A and B are arranged symmetrically with respect to the stacking direction, curling of the film is effectively suppressed, and there is an advantage that handling is easy.

  The laminated film of the present invention is not limited to the examples shown in FIGS. 7 and 8, and may include, for example, polyvinyl alcohol resin layers on both surfaces of the base film in consideration of curling suppression of the film. . Moreover, the other resin layer arrange | positioned between the resin layer A and the resin layer B and / or the base film surface may be included. If the example of another resin layer is given, it will comprise base film itself, has a phase transition temperature lower than a phase transition temperature of resin which constitutes resin layer A, and higher than a phase transition temperature of resin which constitutes resin layer B One or more other resin layers (resin layer C); an adhesive layer responsible for adhesion between the polyvinyl alcohol-based resin layer and the substrate film; adhesion between the polyvinyl alcohol-based resin layer and the substrate film An intervening layer (also referred to as an easy-adhesion layer, a primer layer, or the like). When a base film contains the resin layer C, it is preferable to arrange | position 3 or more types of resin layers which comprise a base film so that it may become a symmetrical structure regarding a lamination direction from a viewpoint of suppressing the curl of a film.

  The laminated film of the present invention is the above except that the layer laminated on at least one surface of the base film is a stretched polyvinyl alcohol-based resin layer that becomes a polarizer layer by adsorption orientation of the dichroic dye. It has the same configuration as the polarizing laminated film. Therefore, details of the base film and the polyvinyl alcohol-based resin layer are basically cited from the description of the polarizing laminated film (however, in the laminated film, the dichroic dye is adsorbed and oriented in the polyvinyl alcohol-based resin layer). It has not been).

  The laminated film can be obtained by laminating a stretched polyvinyl alcohol-based resin layer (film) on a base film obtained by laminating a resin layer in a predetermined orientation in advance. It can also obtain by extending | stretching the "unstretched film" which laminated | stacked the polyvinyl alcohol-type resin layer on the base film which has a layer structure. The stretching is usually uniaxial stretching. In this case, the orientation axis of the polyvinyl alcohol-based resin layer and the orientation axis of the resin layer A are parallel (both are parallel to the stretching direction). However, in the present invention, the orientation axis direction of the resin layer A is not limited to this, and it is only necessary to have the orientation axis in any direction within the resin layer surface, which is different from the orientation axis of the polyvinyl alcohol-based resin layer. Also good.

  The laminated film obtained by such stretching is given resistance to tearing in the stretching direction by the resin layer B that is not substantially oriented by stretching.

<Polarizing laminated film and method for producing laminated film>
As described above, the polarizing laminated film and laminated film of the present invention are prepared in advance so as to have a predetermined configuration (the resin layer and the polarizer layer constituting the base film, or the stretched polyvinyl alcohol system). It can also be manufactured by laminating a resin layer), but can also be produced through a process of stretching an unstretched film in which a polyvinyl alcohol-based resin layer is laminated on a base film having a predetermined resin layer configuration. it can. That is, the laminated film of the present invention has the following steps:
(A) a step of forming an unstretched film by forming a polyvinyl alcohol-based resin layer on at least one surface of a base film having a predetermined resin layer configuration;
(B) a step of stretching an unstretched film;
The polarizing laminated film of the present invention can be produced by the following steps following the steps (a) and (b):
(C) a step of dyeing a polyvinyl alcohol-based resin layer of the obtained laminated film with a dichroic dye to obtain a dyed film;
(D) a step of immersing the polyvinyl alcohol resin layer of the dyed film in a solution containing a crosslinking agent to form a polarizer layer, and obtaining a crosslinked film;
(E) a step of drying the crosslinked film;
It can manufacture by the method containing.

Hereinafter, each step will be described.
[Step (a)]
The “base film having a predetermined resin layer configuration” used in step (a) refers to a layer (resin layer A ′) to be the resin layer A and a layer (resin layer B ′) to be the resin layer B, A ′. It is a film having a laminated structure of three or more resin layers including / B ′ / A ′ or B ′ / A ′ / B ′ in this order. Although this base film is basically an unstretched film, as described above, it is previously stretched in a direction perpendicular to the stretching direction in the stretching step (step (b)) in the film plane. Also good.

  The polyvinyl alcohol resin layer is preferably applied to at least one surface of the base film with a polyvinyl alcohol resin solution obtained by dissolving polyvinyl alcohol resin powder in a good solvent, and the solvent is evaporated by drying. Formed by. According to such a method, since it becomes possible to form a polyvinyl alcohol-type resin layer thinly, it is advantageous to thickness reduction of a light-polarizing laminated film. As a method for coating a polyvinyl alcohol resin solution on a base film, a wire bar coating method, a roll coating method such as reverse coating or gravure coating, a spin coating method, a screen coating method, a fountain coating method, a dipping method, or a spray method. It can select suitably from well-known methods, such as. A drying temperature is 50-200 degreeC, for example, Preferably it is 60-150 degreeC. The drying time is, for example, 5 to 30 minutes.

  Before forming the polyvinyl alcohol-based resin layer, a primer layer (adhesive layer) is formed in advance on the surface of the base film on the side where the polyvinyl alcohol-based resin layer is formed in order to improve adhesion. It may be left. The primer layer can be formed, for example, by applying a solution containing a polyvinyl alcohol-based resin and a crosslinking agent in the same manner as described above and drying. Moreover, you may perform surface treatments, such as a corona treatment, a plasma treatment, and a flame treatment, on the said surface.

  In addition, as above-mentioned, a polyvinyl alcohol-type resin layer can also be formed by sticking the film which consists of polyvinyl alcohol-type resins on the at least one surface of a base film.

[Step (b)]
A process (b) is a process of extending | stretching an unstretched film provided with a base film and a polyvinyl alcohol-type resin layer. The stretching is usually uniaxial stretching. The stretch ratio of the unstretched film can be appropriately selected according to the desired polarization characteristics, but is preferably more than 3 times and less than 17 times, more preferably more than 5 times the original length of the unstretched film. 8 times or less. When the draw ratio is 3 or less, the polyvinyl alcohol-based resin layer is not sufficiently oriented, and as a result, the polarization degree of the polarizing laminated film is not sufficiently increased. On the other hand, if the draw ratio exceeds 17 times, the unstretched film is likely to break during stretching, and at the same time, the thickness of the unstretched film becomes unnecessarily thin, and the workability and handleability in subsequent steps may be reduced. . In the present invention, since the base film composed of a plurality of resin layers as described above is used, the laminated film according to the present invention obtained by stretching is in the stretching direction even when the stretching ratio is more than 5 times. High resistance to tearing. Therefore, it is possible to provide a polarizing laminate film and a polarizing plate that exhibit high polarization characteristics and high durability.

  The stretching process is not limited to stretching in one stage, and can be performed in multiple stages. In this case, it is preferable to perform the stretching treatment so as to obtain a stretching ratio of more than 3 times in total for all stages of the stretching treatment.

  The stretching method is not particularly limited, and various stretching methods such as a longitudinal stretching method, a lateral stretching method, an overfeed lateral stretching method, a simultaneous biaxial stretching method, and an oblique stretching method can be applied. Examples of the stretching method include an inter-roll stretching method, a compression stretching method, and a stretching method using a tenter.

  As the stretching treatment, either a wet stretching method or a dry stretching method can be adopted. However, it is preferable to use the dry stretching method because the temperature at which the unstretched film is stretched can be selected from a wide range.

  The stretching temperature is at least the lowest phase except for the resin layer (that is, the resin layer A ′ that becomes the resin layer A) composed of the resin having the highest phase transition temperature among the plurality of resin layers of the base film. Resin that constitutes the resin layer A at a temperature equal to or higher than the temperature at which the resin layer composed of the resin exhibiting the transition temperature (that is, the resin layer B ′ that becomes the resin layer B) is in a molten state (so as not to melt away) Is preferably set in the vicinity of the phase transition temperature (= the phase transition temperature of the resin constituting the resin layer A ′), specifically, (the phase transition temperature of the resin constituting the resin layer A−30 ° C.). The range of ~ (the phase transition temperature of the resin constituting the resin layer A + 30 ° C) is preferable. When the stretching temperature is lower than (the phase transition temperature of the resin constituting the resin layer A−30 ° C.), it becomes difficult to stretch at a high magnification. If the stretching temperature exceeds (the phase transition temperature of the resin constituting the resin layer A + 30 ° C.), the fluidity of the base film tends to be too high to make stretching difficult.

  The temperature adjustment of the stretching process is usually based on the temperature adjustment of the heating furnace, but the temperature of the heating furnace and the actual temperature of the film do not always match, and the resin has a distribution in molecular weight, etc., and does not necessarily reach the phase transition temperature. Since it does not immediately melt away at the time, the stretching may be carried out at a temperature set higher than the phase transition temperature. That is, a temperature lower than the temperature at which the film substantially melts may be selected depending on the situation.

[Step (c)]
Step (c) is a step in which the polyvinyl alcohol resin layer of the laminated film obtained by stretching is dyed with a dichroic dye and adsorbed and oriented. Examples of the dichroic dye include iodine and organic dyes. Examples of organic dyes include Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Spura Blue G, Spura Blue GL, Spura Orange GL, Direct Sky Blue, Direct First Orange S, First Black, etc. can be used. These dichroic substances may be used alone or in combination of two or more.

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

  When iodine is used as the dichroic dye, it is preferable to further add iodide to the dyeing solution containing iodine because the dyeing efficiency can be further improved. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and iodide. Examples include titanium. The iodide concentration in the dyeing solution is preferably 0.01 to 10% by weight. Of the iodides, it is preferable to add potassium iodide. When potassium iodide is added, the ratio of iodine to potassium iodide is preferably in the range of 1: 5 to 1: 100, more preferably in the range of 1: 6 to 1:80, by weight. A range of 1: 7 to 1:70 is particularly preferable.

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

  Although the dyeing process can be performed before or simultaneously with the stretching process, the unstretched film is subjected to the stretching process so that the dichroic dye adsorbed on the polyvinyl alcohol-based resin layer can be well oriented. It is preferable to carry out after this. At this time, it may be dyed in advance stretched at a target draw ratio, or stretched again to reach the target stretch ratio while dyeing a stretch previously drawn at a lower ratio than the target stretch ratio. Also good.

[Step (d)]
Step (d) is a step in which a polyvinyl alcohol resin layer of a dyed film obtained by dyeing with a dichroic dye is subjected to a crosslinking treatment to obtain a crosslinked film having the polyvinyl alcohol resin layer as a polarizer layer. It is. The crosslinking step can be performed, for example, by immersing the dyed film in a solution containing a crosslinking agent (crosslinking solution). Conventionally known substances can be used as the crosslinking agent. Examples thereof include boron compounds such as boric acid and borax, glyoxal, and glutaraldehyde. These may be used alone or in combination of two or more.

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

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

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

  In addition, a bridge | crosslinking process can also be performed simultaneously with a dyeing process by mix | blending a crosslinking agent in a dyeing solution. Moreover, you may perform a bridge | crosslinking process and an extending process simultaneously. At this time, the one stretched in advance at the target draw ratio may be cross-linked, or the one stretched in advance at a lower ratio than the target draw ratio is re-stretched so as to reach the target draw ratio. Also good.

[Step (e)]
The obtained crosslinked film is usually dried after washing. Washing can be performed by immersing the crosslinked film in pure water such as ion exchange water or distilled water. The water washing temperature is usually in the range of 3 to 50 ° C, preferably 4 to 20 ° C. The immersion time is usually 2 to 300 seconds, preferably 5 to 240 seconds. The washing may be a combination of a washing treatment with an iodide solution and a water washing treatment, and a solution in which a liquid alcohol such as methanol, ethanol, isopropyl alcohol, butanol, propanol or the like is appropriately blended may be used.

  Any appropriate method (for example, natural drying, air drying, heat drying) can be adopted as the drying method. For example, the drying temperature in the case of heat drying is usually 20 to 95 ° C., and the drying time is usually about 1 to 15 minutes.

<Polarizing plate>
Although the said polarizing laminated film itself can be used as a polarizing plate, after making it into the state which laminated | stacked the transparent protective layer, peeling a base film from a polarizer layer and making it a polarizing plate which has a transparent protective layer. it can. By using the polarizing laminated film, a polarizing plate having a transparent protective layer having a thin and high durability and a good polarizing performance can be efficiently produced with a high yield. The liquid crystal display device using the polarizing plate according to the present invention exhibits a high contrast ratio.

  The polarizing plate having a transparent protective layer can be produced by a method including the following steps using the polarizing laminated film of the present invention.

(A) The process of bonding a transparent protective layer to the surface on the opposite side to the base film side in the polarizer layer of a light-polarizing laminated film,
(B) A step of peeling and removing the base film.

  Referring to the drawings, for example, after the transparent protective layer 40 is bonded onto the polarizer layer 30 of the polarizing laminated film 10 shown in FIG. 1 to obtain the polarizing laminated film 25 shown in FIG. By peeling off, a polarizing plate composed of “transparent protective layer / polarizer layer” can be obtained. From a polarizing laminated film in which a polarizer layer and a transparent resin layer are laminated on both surfaces of a base film, peeling at two polarizer layer-base film interfaces results in a “transparent protective layer / polarizer layer”. Two polarizing plates made of can be obtained.

  As the transparent protective layer used in the step (A), the above-mentioned transparent protective film (on the surface opposite to the polarizer layer of the transparent protective film, optical such as a hard coat layer, an antiglare layer, an antireflection layer, etc.) Including those in which layers are formed).

  Bonding of the polarizer layer of the polarizing laminate film and the transparent protective film can be performed using an adhesive or a pressure-sensitive adhesive. Examples of the adhesive include aqueous adhesives such as an aqueous polyvinyl alcohol resin solution and an aqueous two-component urethane emulsion adhesive. When using a cellulose ester resin hydrophilized by saponification or the like as the transparent protective film, a polyvinyl alcohol resin aqueous solution is suitably used as the adhesive. Polyvinyl alcohol resins used as adhesives include vinyl alcohol homopolymers obtained by saponifying polyvinyl acetate, which is a homopolymer of vinyl acetate, as well as other single quantities copolymerizable with vinyl acetate. And vinyl alcohol copolymers obtained by saponifying the copolymer with the polymer, and modified polyvinyl alcohol polymers obtained by partially modifying the hydroxyl groups. A polyhydric aldehyde, a water-soluble epoxy compound, a melamine compound, a zirconia compound, a zinc compound, or the like may be added as an additive to the water-based adhesive. When an aqueous adhesive is used, the adhesive layer obtained therefrom is usually 1 μm or less.

  The method of bonding the polarizer layer and the transparent protective film using the water-based adhesive is not particularly limited. For example, casting method, Mayer bar coating method, gravure coating method, comma coater method, doctor plate method Apply the adhesive uniformly to the surface of the polarizer layer and / or transparent protective film by die coating, dip coating, spraying, etc., and then apply the other film on the coated surface and paste using a roll. And a drying method. The casting method is a method in which a polarizer layer or a transparent protective film, which is an object to be coated, is moved in a generally vertical direction, generally in a horizontal direction, or in an oblique direction between the two while flowing down an adhesive on the surface and spread. It is a method to make it. Usually, an aqueous adhesive is apply | coated at the temperature of 15-40 degreeC after the preparation, and the bonding temperature is the range of 15-30 degreeC normally.

  After the adhesive is applied, the polarizer layer and the transparent protective film are overlapped, and the films are bonded by nip rolls. Bonding using a nip roll is, for example, a method in which an adhesive is applied and then pressurized with a roll or the like and spreads uniformly. After applying an adhesive, it is passed between the rolls and pressed and spread out. A method etc. can be adopted. In the former case, it is possible to use metal or rubber as the material of the roll. In the latter case, the plurality of rolls may be made of the same material or different materials.

  When using an aqueous adhesive, after laminating the polarizer layer and the transparent protective film, the laminated film is dried to remove water contained in the aqueous adhesive. The drying temperature is preferably 30 to 90 ° C. If it is lower than 30 ° C., the polarizer layer and the transparent protective film tend to be peeled off. Moreover, there exists a possibility that polarization performance may deteriorate with heat that it is 90 degreeC or more. The drying time can be 10 to 1000 seconds, and particularly from the viewpoint of productivity, it is preferably 60 to 750 seconds, more preferably 150 to 600 seconds.

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

  Moreover, a photocurable adhesive can also be used as an adhesive at the time of bonding a polarizer layer and a transparent protective film. Examples of the photocurable adhesive include a mixture of a photocurable epoxy resin and a photocationic polymerization initiator.

  When using a photocurable adhesive, after bonding a polarizer layer and a transparent protective film like the above, a photocurable adhesive is hardened by irradiating an active energy ray. The light source of the active energy ray is not particularly limited, but an active energy ray having a light emission distribution at a wavelength of 400 nm or less is preferable. A microwave excitation mercury lamp, a metal halide lamp and the like are preferably used.

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

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

  In addition, in bonding of a polarizer layer and a transparent protective film, in order to improve adhesiveness to the adhesive surface of a polarizer layer and / or a transparent protective film, plasma treatment, corona treatment, ultraviolet irradiation treatment, frame ( A surface treatment such as a flame treatment or a saponification treatment may be applied as necessary. Examples of the saponification treatment include a method of immersing in an aqueous alkali solution such as sodium hydroxide or potassium hydroxide.

  On the other hand, the adhesive used for bonding the polarizer layer and the transparent protective film is usually based on an acrylic resin, a styrene resin, a silicone resin, etc., and an isocyanate compound, an epoxy compound, an aziridine compound. It consists of a composition to which a crosslinking agent such as Furthermore, it can also be set as the adhesive layer which contains microparticles | fine-particles and shows light-scattering property.

  The thickness of the pressure-sensitive adhesive layer is preferably 1 to 40 μm, but is preferably formed as thin as possible without impairing workability and durability, and more preferably 3 to 25 μm. When it is 3 to 25 μm, it has good processability and is suitable for suppressing the dimensional change of the polarizer layer. When the thickness of the pressure-sensitive adhesive layer is less than 1 μm, the adhesiveness is lowered, and when it exceeds 40 μm, problems such as the pressure-sensitive adhesive protruding easily occur.

  The method of bonding the polarizer layer and the transparent protective film with the adhesive is not particularly limited, and a solution (adhesive) containing each component including the above-mentioned base polymer on the polarizer layer surface or the transparent protective film surface. After the adhesive composition) is applied and dried to form an adhesive layer, the polarizer layer and the transparent protective film may be bonded together, or after the adhesive layer is formed on the separator (release film), You may transfer to a polarizer layer surface or a transparent protective film surface, and may bond a polarizer layer and a transparent protective film together.

  In addition, when bonding a polarizer layer and a transparent protective film through an adhesive layer, in order to improve adhesiveness, the bonding surface of a polarizer layer and / or a transparent protective film, or an adhesive layer One or both surfaces may be subjected to surface treatment such as corona treatment as necessary.

  The said process (B) is a process of peeling and removing a base film from a polarizer layer. The method of peeling a base film is not specifically limited, It can peel by the method similar to the peeling process of the separator (release film) performed with a normal polarizing plate with an adhesive. After laminating the transparent protective layer, the base film may be peeled off as it is, or after laminating the transparent protective layer, the base film is peeled off while being unwound in a subsequent process. May be.

  The polarizing plate manufactured as described above may be laminated with another optical layer in practical use. Moreover, the transparent protective layer may have the function of these optical layers. As other optical layers, in addition to the hard coat layer, the antiglare layer, and the antireflection layer described above, (1) a reflective polarizing film that transmits a certain kind of polarized light and reflects polarized light that shows the opposite property. (2) a film with an antiglare function having a concavo-convex shape on the surface; (3) a film with a surface antireflection function; (4) a reflective film having a reflection function on the surface; (5) a half having both a reflection function and a transmission function; Transflective film; (6) Viewing angle compensation film. These (1) to (6) films can also be applied to a polarizing laminate film used as a polarizing plate.

  For example, “DBEF” (available from 3M, Sumitomo 3M Co., Ltd.) can be used as a commercial product equivalent to a reflective polarizing film that transmits certain types of polarized light and reflects polarized light that exhibits the opposite properties. ), “APF” (manufactured by 3M, available from Sumitomo 3M Limited). Examples of the viewing angle compensation film include an optical compensation film in which a liquid crystal compound is applied to the substrate surface and oriented, a retardation film made of a polycarbonate resin, and a retardation film made of a cyclic polyolefin resin. Commercially available products corresponding to an optical compensation film coated with a liquid crystal compound on the substrate surface are "WV film" (manufactured by FUJIFILM Corporation), "NH film" (Shin Nippon Oil Co., Ltd.) And “NR Film” (manufactured by Nippon Oil Corporation). Commercial products corresponding to retardation films made of cyclic polyolefin resin include “Arton Film” (manufactured by JSR Corporation), “Essina” (manufactured by Sekisui Chemical Co., Ltd.), “Zeonor Film” (Japan) ZEON Co., Ltd.).

<Liquid crystal display device>
The above-mentioned polarizing laminated film or polarizing plate can be suitably applied to an image display device such as a liquid crystal display device. When applied to a liquid crystal display device, the liquid crystal display device comprises the above-mentioned polarizing laminated film or polarizing plate laminated on one side (which may be either the viewing side or the back side) or both sides of the liquid crystal cell. including. As the liquid crystal cell, those of various known drive methods can be used. This liquid crystal display device may have a conventionally known configuration except that it includes the above-described polarizing laminated film or polarizing plate. The liquid crystal display device provided with the polarizing laminate film or polarizing plate of the present invention is reduced in thickness and exhibits a high contrast ratio due to the excellent polarizing performance of the polarizing laminate film or polarizing plate.

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

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

(2) Formation of primer layer Polyvinyl alcohol powder (“Z-200” manufactured by Nippon Synthetic Chemical Industry Co., Ltd., average polymerization degree 1100, average saponification degree 99.5 mol%) was dissolved in 95 ° C. hot water, A polyvinyl alcohol aqueous solution having a concentration of 3% by weight was prepared. The resulting aqueous solution was mixed with 5 parts by weight of a crosslinking agent (“SUMIREZ RESIN 650” manufactured by Sumitomo Chemical Co., Ltd.) with respect to 6 parts by weight of polyvinyl alcohol powder. The obtained mixed aqueous solution was coated on the corona-treated surface of the base film subjected to the corona treatment using a micro gravure coater, and dried at 80 ° C. for 10 minutes to form a primer layer having a thickness of 0.5 μm. Formed.

(3) Formation of polyvinyl alcohol resin layer Polyvinyl alcohol powder (“PVA124” manufactured by Kuraray Co., Ltd., average polymerization degree 2400, average saponification degree 98.0-99.0 mol%) is dissolved in hot water at 95 ° C. An aqueous polyvinyl alcohol solution having a concentration of 8% by weight was prepared. The obtained aqueous solution was coated on the primer layer using a lip coater, and dried under conditions of 80 ° C. for 2 minutes, 70 ° C. for 2 minutes, and then 60 ° C. for 4 minutes, whereby a base film An unstretched film having a three-layer structure consisting of / primer layer / polyvinyl alcohol-based resin layer was produced. The thickness of the polyvinyl alcohol-based resin layer was 11.2 μm.

(4) Production of Laminated Film The unstretched film was stretched 5.8 times at a stretching temperature of 160 ° C. to obtain a laminated film. The thickness of the obtained laminated film was 55.5 μm, and the thickness of the polyvinyl alcohol-based resin layer was 5.2 μm. In the obtained laminated film, no curling of the film was observed.

<Example 2>
On both sides of a resin layer made of linear low density polyethylene ("FV401" manufactured by Sumitomo Chemical Co., Ltd., melting point Tm = 119 ° C), which is a homopolymer of ethylene, homopolypropylene (Sumitomo Chemical Co., Ltd.) A laminated film was prepared in the same manner as in Example 1 except that a base film having a three-layer structure in which a resin layer made of “Sumitomo Noblen FLX80E4”, melting point Tm = 163 ° C.) was used was used. The total thickness of the obtained laminated film was 90 μm, and the thickness ratio (FLX80E4 / FV401 / FLX80E4) of each layer was 3/4/3. In the obtained laminated film, no curling of the film was observed.

<Comparative Example 1>
An unstretched film having a thickness of 105 μm was obtained in the same manner as in Example 1 except that a single-layer substrate film made of homopolypropylene (“Sumitomo Noblen FLX80E4” manufactured by Sumitomo Chemical Co., Ltd., melting point Tm = 163 ° C.) was used. Produced. Next, free end longitudinal uniaxial stretching was performed under the same conditions as in Example 1 to obtain a laminated film having a thickness of 50.1 μm. The thickness of the polyvinyl alcohol-based resin layer in the laminated film was 5.5 μm.

<Comparative example 2>
Except for using a single-layer substrate film made of a propylene / ethylene random copolymer (Sumitomo Chemical Co., Ltd. “Sumitomo Nobrene W151”, melting point Tm = 138 ° C.) containing about 5% by weight of ethylene units, In the same manner as in Example 1, an unstretched film having a thickness of 105 μm was produced. Next, free end longitudinal uniaxial stretching was performed under the same conditions as in Example 1 to obtain a laminated film having a thickness of 50.5 μm. The thickness of the polyvinyl alcohol-based resin layer in the laminated film was 5.5 μm.

(Preparation of polarizing laminated film)
<Example 3>
Using the laminated film obtained in Example 1, a polarizing laminated film was produced by the following procedure. First, the laminated film is immersed in a 60 ° C. hot bath for 60 seconds, and then immersed in a dyeing solution at 30 ° C., which is an aqueous solution containing iodine at 30 ° C. and potassium iodide, for about 150 seconds to dye the polyvinyl alcohol resin layer. Then, the excess iodine solution was washed away with pure water at 10 ° C. Next, it was immersed for 600 seconds in the 76 degreeC bridge | crosslinking solution which is the aqueous solution containing a boric acid and potassium iodide. Thereafter, the film was washed with pure water at 10 ° C. for 4 seconds, and finally dried at 50 ° C. for 300 seconds to obtain a polarizing laminated film. In the obtained polarizing laminated film, no curling of the film was observed.

<Example 4, Comparative Examples 3-4>
A polarizing laminated film was produced in the same manner as in Example 3 except that the laminated film of Example 2, Comparative Example 1 or Comparative Example 2 was used instead of the laminated film of Example 1 (Example 4 respectively). Comparative Example 3 and Comparative Example 4). In any of the obtained polarizing laminated films, no curling of the film was observed.

  In Examples 3 and 4, in each step until the polarizing laminated film was produced, there was no problem such as tearing of the laminated film, and the polarizing laminated film could be produced stably. On the other hand, in Comparative Examples 3 and 4, tearing occurred partially in the stretching direction in the line until the polarizing laminated film was obtained. For Comparative Examples 3 and 4, the following evaluation was performed using a portion where no tear occurred.

[Evaluation of polarizing laminated film]
(1) Measurement of orientation state of resin layer constituting base film After peeling the base film from the polarizing laminate film prepared above, the base film was cooled to -90 ° C, and the cooled base film was subjected to cryomicrotome. The base film with a width of 3 μm (length is about 1 to 2 mm, thickness is the thickness of the base film) is cut twice so that the length direction is parallel to the stretching direction of the polarizing laminated film A piece (sample) was cut out (see FIG. 3). Subsequently, the orientation state of the resin layer which comprises a base film was confirmed using this sample according to the measuring method mentioned above.

  As a result, for the two resin layers (“FLX80E4”) outside the base film in the polarizing laminated film produced in Examples 3 and 4, the sample was rotated once to make the sample length relative to the transmission axis of the polarizer. When the azimuth angle in the vertical direction (stretching direction) is changed, every time the azimuth angle increases by 45 °, the transmitted image is observed brightest and the darkest image is alternately repeated. It was confirmed that the film was oriented in the stretching direction (length direction of the sample). On the other hand, in any of Examples 3 and 4, for the resin layer at the center of the base film (Example 3: “W151”, Example 4: “FV401”), the length of the sample with respect to the transmission axis of the polarizer Even if the azimuth angle of the direction was changed, no change was observed in the brightness of the transmitted image, and it was confirmed that a completely dark state was maintained, and it was found that the image was substantially non-oriented.

  FIG. 9 is a polarization micrograph when the sample of Example 3 is arranged in such an orientation that its length direction (stretching direction) forms an angle of 45 ° with respect to the transmission axis of the polarizer. As shown in FIG. 9, the two resin layers (“FLX80E4”) outside the base film are observed brightly, while the central resin layer (“W151”) is observed in black.

  On the other hand, in the base film (both made of a single resin layer) in the polarizing laminated film produced in Comparative Examples 3 and 4, the sample length direction (stretching direction) relative to the transmission axis of the polarizer When the azimuth angle was changed, every time the azimuth angle increased by 45 °, it was confirmed that the transmitted image was observed the brightest and the darkest observed alternately. It was found that the entire base film was oriented in the stretching direction. The above results are summarized in Table 1.

(2) Measurement of tear strength The tear strength of the polarizing laminated film produced above was measured by the following method. First, a cut was made in parallel with the stretching direction using a cutter from the center of the short side end of the polarizing laminated film (the center in the film width direction). Next, using a universal tensile testing machine ("Autograph AG-I" manufactured by Shimadzu Corporation), the polarizing laminated film is torn from the base point of the cut, and the tear strength at that time is measured using the same device. It was measured. The film tearing speed was 300 mm / min. This measurement gives the tear strength at each tear distance (distance of the film torn from the base point of the cut). Until the angle stabilizes, the tear strength often increases. Therefore, in this measurement, this portion was excluded, and an average value of the tear strength in a region where the tear strength was stable was obtained, and this was taken as the tear strength. The results are shown in Table 1.

(3) Evaluation of reworkability The polarizing laminate film produced above is cut into a size of 100 mm x 60 mm, a sheet-like adhesive having a thickness of 25 µm is bonded to the outer surface of the polarizer layer, and the adhesive is interposed therebetween. The polarizing laminated film was bonded to the surface of a commercially available liquid crystal cell (one obtained by disassembling and taking out PSP-3000 sold by Sony Corporation). Then, after performing the crimping | compression-bonding process for 20 minutes at 50 degreeC and 5 atmospheres, it left still at room temperature for 2 days.

  In addition, the said sheet-like adhesive was formed from the adhesive composition which added the urethane acrylate oligomer and the isocyanate type crosslinking agent to the butyl acrylate / acrylic acid copolymer, and the storage elastic modulus is 0 in 23 degreeC. It was 0.19 MPa at .41 MPa and 80 ° C.

  When a test for peeling the polarizing laminated film from the liquid crystal cell by hand was performed and the reworkability was evaluated, it was confirmed that the polarizing laminated films of Examples 3 and 4 could be peeled well without tearing. On the other hand, the polarizing laminated films of Comparative Examples 3 and 4 were torn in the stretching direction during the peeling (breakage occurred), and it was difficult to rework. The above results are summarized in Table 1.

  FIG. 10 is a photograph showing a reworkability evaluation test result of the polarizing laminated film of Example 3, and it can be seen that the polarizing laminated film is peeled well without breaking. FIG. 11 is a photograph showing the reworkability evaluation test result of the polarizing laminated film of Comparative Example 3. A portion that is split in the stretching direction in the middle of peeling is not peeled off from the liquid crystal cell but remains in a band shape on the liquid crystal cell.

  As described above, the polarizing laminated films and laminated films of Examples 1 to 4 are composed of the resin layer in which the base film is oriented and the non-oriented resin layer, and thus Comparative Example 1 Compared to ˜4, it was confirmed to have higher resistance to tearing in the stretching direction.

[Preparation of polarizing plate]
<Example 5>
A laminated film was obtained in the same manner as in Example 1 except that a primer layer was formed on both surfaces of the base film, and a polyvinyl alcohol-based resin layer was formed on each of the both primer layers. Next, a polarizing laminate film was produced in the same manner as in Example 3.

  Polyvinyl alcohol powder (“KL-318” manufactured by Kuraray Co., Ltd., average polymerization degree 1800) was dissolved in hot water at 95 ° C. to prepare a polyvinyl alcohol aqueous solution having a concentration of 3% by weight. The resulting aqueous solution was mixed with 1 part by weight of a crosslinking agent (“SUMIREZ RESIN 650” manufactured by Sumitomo Chemical Co., Ltd.) with respect to 2 parts by weight of polyvinyl alcohol powder to obtain an adhesive solution.

  Next, after applying the adhesive solution on the polyvinyl alcohol resin layer of each of the polarizing laminated films obtained above, a transparent protective film made of triacetyl cellulose (TAC) (manufactured by Konica Minolta Opto Co., Ltd.) "KC4UY") and a transparent protective film comprising 9 layers of transparent protective film / adhesive layer / polarizer layer / primer layer / substrate film / primer layer / polarizer layer / adhesive layer / transparent protective film A polarizing laminated film was obtained. From the obtained polarizing laminated film with a transparent protective film, the base film was removed by peeling at the interface between the two primer layers and the base film, and the transparent protective film / adhesive layer / polarizer layer / primer layer 4 Two polarizing plates composed of layers were produced. The base film could be easily peeled off.

  10, 10 ′, 25, 25 ′ Polarized laminated film, 15, 15 ′ laminated film, 20, 20 ′ base film, 30, 30 ′ polarizer layer, 35, 35 ′ stretched polyvinyl alcohol resin layer, 40, 40 'Transparent protective layer.

Claims (10)

A polarizing laminated film comprising a base film and a polarizer layer laminated on at least one surface of the base film,
The base film has a different phase transition temperature (where the phase transition temperature means a glass transition temperature when the resin constituting the resin layer is an amorphous resin, and is a crystalline resin) Consists of a laminated structure of two or more resin layers composed of a resin exhibiting a melting point),
Of the two or more types of resin layers, the base film has a resin layer composed of a resin exhibiting the highest phase transition temperature and A represents a resin layer composed of a resin exhibiting the lowest phase transition temperature. Sometimes these include A / B / A or B / A / B in this order,
The resin layer A is oriented in any direction in the plane, and the resin layer B is substantially non-oriented in the plane,
A polarizing laminated film in which the resin layers A and B are made of a chain polyolefin resin having different melting points.   The polarizing laminated film according to claim 1, wherein the difference between the melting point of the resin constituting the resin layer A and the melting point of the resin constituting the resin layer B is 10 ° C. or more.   The polarizing laminate film according to claim 1, wherein the polarizer layer is a polyvinyl alcohol resin layer in which a dichroic dye is adsorbed and oriented.   The polarizing laminated film according to claim 1, wherein the polarizer layer has a thickness of 10 μm or less.   The polarizing laminated film according to claim 1, wherein the absorption axis of the polarizer layer and the orientation axis of the resin layer A are parallel.   The polarizing laminated film according to claim 1, further comprising a transparent protective layer laminated on at least one polarizer layer. A laminated film comprising a base film and a stretched polyvinyl alcohol-based resin layer laminated on at least one surface of the base film,
The base film has a different phase transition temperature (where the phase transition temperature means a glass transition temperature when the resin constituting the resin layer is an amorphous resin, and is a crystalline resin) Consists of a laminated structure of two or more resin layers composed of a resin exhibiting a melting point),
Of the two or more types of resin layers, the base film has a resin layer composed of a resin exhibiting the highest phase transition temperature and A represents a resin layer composed of a resin exhibiting the lowest phase transition temperature. Sometimes these include A / B / A or B / A / B in this order,
The resin layer A is oriented in any direction in the plane, and the resin layer B is substantially non-oriented in the plane,
A laminated film in which the resin layers A and B are made of a chain polyolefin resin having different melting points.   The laminated film according to claim 7, wherein the difference between the melting point of the resin constituting the resin layer A and the melting point of the resin constituting the resin layer B is 10 ° C. or more.   The laminated film according to claim 7 or 8, wherein the polyvinyl alcohol-based resin layer has a thickness of 10 µm or less.   The laminated film according to any one of claims 7 to 9, wherein an orientation axis of the polyvinyl alcohol-based resin layer and an orientation axis of the resin layer A are parallel.