WO2016042964A1

WO2016042964A1 - Method for manufacturing polarizing layered film, and protective-film-equipped stretched film

Info

Publication number: WO2016042964A1
Application number: PCT/JP2015/073186
Authority: WO
Inventors: 薫川▲崎▼
Original assignee: 住友化学株式会社
Priority date: 2014-09-18
Filing date: 2015-08-19
Publication date: 2016-03-24
Also published as: TW201615383A; KR20170056578A; CN106687834B; KR102417465B1; JP2016061959A; CN106687834A; JP6543447B2

Abstract

　A stretched film (1) wherein an affixing step (S30) for affixing a protective film (2) to the surface of a polyvinyl alcohol resin layer on the reverse side thereof from a substrate film and obtaining a protective-film-equipped stretched film (3), a winding step (S40) for winding the protective-film-equipped stretched film (3), a peeling step (S50) for unwinding the protective-film-equipped stretched film (3) and peeling the protective film (2) from the stretched film (1), and a dyeing step (S60) for dyeing the stretched film (1) and obtaining a polarizing layered film are included in this order, and in the winding step (S40), the protective-film-equipped stretched film (3) is configured so that the positions of both ends of the polyvinyl alcohol resin layer in the width direction thereof and the positions of both ends of the protective film (2) in the width direction thereof do not coincide.

Description

Method for producing polarizing laminated film and stretched film with protective film

The present invention relates to a method for producing a polarizing laminated film and a stretched film with a protective film.

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

As a method for producing such a thin polarizing plate, a solution containing a polyvinyl alcohol-based resin is applied to the surface of a base film to provide a resin layer, and then stretched and then dyed to have a polarizer layer. It is known that a polarizing laminate film is prepared and used as a polarizing plate as it is, or a protective film is bonded to the polarizer layer and then a substrate film is peeled off and used as a polarizing plate. (See, for example, International Publication Nos. 2013/114532, 2011-2816, and 2012-73570).

International Publication No. 2013/114532 JP 2011-2816 A JP 2012-73570 A

In the case of obtaining a laminated film having a base film and a polarizer layer by stretching and then dyeing after providing a polyvinyl alcohol-based resin layer on the surface of the base film as in the above-described conventional technology, Since the line speed in stretching and the line speed in dyeing are often different, generally, a method of winding the stretched laminated film into a roll and then unwinding the laminated film and dyeing it is employed. Further, when the stretching equipment and the dyeing equipment are in different places, it is necessary to adopt a method of winding up after drawing as described above, transferring the roll to the dyeing equipment, and then unwinding it and flowing it to the dyeing line. In addition, when winding a laminated | multilayer film once in roll shape, in order to protect a polyvinyl alcohol-type resin layer, it is preferable to wind up, after bonding a protective film on the surface of a polyvinyl alcohol-type resin layer.

However, when a protective film is bonded to the surface of the polyvinyl alcohol-based resin layer, it may interfere with the polyvinyl alcohol-based resin layer when peeling it, causing a problem that the polyvinyl alcohol-based resin layer is peeled off from the base film. there were. In particular, after the protective film is bonded to the surface of the polyvinyl alcohol-based resin layer, when the end portion in the width direction of the entire film is cut off to align the ends, the polyvinyl alcohol-based resin layer is more than the base film. However, there is a problem that the polyvinyl alcohol-based resin layer is easily peeled off from the base film when the protective film is peeled off.

In any of the above-mentioned prior art documents, there is no disclosure of pasting a protective film on the surface of the polyvinyl alcohol-based resin layer after the stretching step, and then winding the laminated film into a roll shape. The problem that occurs when the film is peeled off is a problem that the present inventors have found for the first time.

In the present invention, a polyvinyl alcohol-based resin layer is provided on the surface of a base film to form a laminated film, and after stretching, a protective film is pasted on the surface of the polyvinyl alcohol-based resin layer, wound, and then unwound A production method for obtaining a polarizing laminate film by dyeing after the protective film is peeled off, and a production method capable of suppressing the peeling of the polyvinyl alcohol-based resin layer from the base film when the protective film is peeled off The purpose is to provide. It is another object of the present invention to provide a stretched film with a protective film in which the polyvinyl alcohol-based resin layer is hardly peeled off from the base film even when the protective film is peeled off.

The present invention includes the following.
[1] A resin layer forming step of forming a polyvinyl alcohol-based resin layer on a base film to obtain a laminated film, a stretching step of drawing the laminated film to obtain a stretched film, and the stretched film, wherein the polyvinyl alcohol Bonding step of obtaining a stretched film with a protective film by pasting a protective film on the surface of the resin layer opposite to the base film, a winding step for winding the stretched film with the protective film, and the protection Unwinding the stretched film with a film, and including a peeling step for peeling the protective film from the stretched film, and a dyeing step for dyeing the stretched film to obtain a polarizing laminated film in this order,
In the winding step, the stretched film with a protective film is a polarizing laminated film in which the positions of both end portions in the width direction of the polyvinyl alcohol-based resin layer and both end portions in the width direction of the protect film are not coincident. Method.

[2] In the winding process, in the stretched film with a protective film, the positional deviation between the end portion in the width direction of the polyvinyl alcohol-based resin layer and the end portion in the width direction of the protect film is 1 mm or more. The manufacturing method of the light-polarizing laminated film as described in [1].

[3] In the stretched film with a protective film after the bonding step, both end portions in the width direction of the protect film are located on the inner side than both end portions in the width direction of the polyvinyl alcohol-based resin layer, [1] or The manufacturing method of the light-polarizing laminated film as described in [2].

[4] Before the pasting step, including a protect film end removing step of cutting and removing the end in the width direction of the protect film, and in the pasting step, the width of the protect film is the polyvinyl alcohol. The manufacturing method of the polarizing laminated film as described in [3] narrower than the width | variety of a resin layer.

[5] The method for producing a polarizing laminated film according to [4], further including a stretched film edge removing step of cutting and removing the edge in the width direction of the stretched film before the bonding step.

[6] In the stretched film with a protective film after the bonding step, both end portions in the width direction of the protect film are positioned outside both end portions in the width direction of the polyvinyl alcohol-based resin layer, [1] or The manufacturing method of the light-polarizing laminated film as described in [2].

[7] A stretched film end removing step of cutting and removing the end in the width direction of the stretched film before the pasting step, and in the pasting step, the width of the protective film is the polyvinyl alcohol. The manufacturing method of the polarizing laminated film as described in [6] wider than the width | variety of a resin layer.

[8] A base film, a stretched polyvinyl alcohol resin layer provided on the base film, and a protective film provided on the surface of the polyvinyl alcohol resin layer opposite to the base film A stretched film with a long protective film comprising:
A stretched film with a protective film, wherein the positions of both end portions in the width direction of the polyvinyl alcohol-based resin layer are not aligned with the positions of both end portions in the width direction of the protect film.

[9] The stretched film with a protective film according to [8], wherein a shift between an end of the polyvinyl alcohol resin layer and an end of the protective film in the width direction is 1 mm or more.

According to the production method of the present invention, after providing a polyvinyl alcohol resin layer on the surface of the base film, stretching, winding the protective film after bonding, unwinding the protective film after unwinding, and stretching the film In producing a polarizing laminated film by dyeing or the like, peeling of the polyvinyl alcohol-based resin layer from the base film when peeling the protective film can be suppressed.

It is a flowchart which shows the manufacturing method of the light-polarizing laminated film of this invention. It is a top perspective view showing an example of the pasting process of the present invention (before (a) pasting process, after (b) pasting process). It is a top perspective view showing an example of the pasting process of the present invention (before (a) pasting process, after (b) pasting process). It is a top perspective view showing an example of the pasting process of the present invention (before (a) pasting process, after (b) pasting process). It is a top perspective view showing typically some processes of the manufacturing method of a 1st embodiment. It is an upper surface perspective view showing typically a part of process of the manufacturing method of a 2nd embodiment. It is a top perspective view showing typically some processes of the manufacturing method of a 3rd embodiment.

FIG. 1 is a flowchart showing a method for producing a polarizing laminate film of the present invention. The production method of the present invention includes a resin layer forming step (S10) in which a polyvinyl alcohol-based resin layer is formed on a base film to obtain a laminated film, and a stretching step (S20) in which the laminated film is drawn to obtain a stretched film. In the stretched film, a bonding step (S30) for obtaining a stretched film with a protective film by laminating a protective film on the surface opposite to the base film of the polyvinyl alcohol-based resin layer, and winding the stretched film with a protective film The winding process (S40) to take, the peeling process (S50) which unwinds the stretched film with a protective film and peels the protective film from the stretched film, and the dyeing process (S60) to dye the stretched film are included in this order. . Through the above steps, the polyvinyl alcohol-based resin layer becomes a polarizer layer, and a polarizing laminated film is produced.

In the winding step (S40) of the present invention, in the stretched film with a protective film, the positions of both end portions in the width direction of the polyvinyl alcohol-based resin layer and both end portions in the width direction of the protect film do not match. In order to carry out this, in the bonding step (S30), the both ends of the polyvinyl alcohol-based resin layer in the width direction are bonded so that the positions of the both ends in the width direction of the protective film do not coincide with each other. After the combining step (S30) and before the winding step (S40), both ends of the stretched film with a protective film are cut, that is, both ends in the width direction of the polyvinyl alcohol-based resin layer and the width of the protective film. Both ends in the direction are cut at the same time so that the process of aligning both ends is not performed.

In the production method of the present invention, with respect to the stretched film with a protective film in the winding step (S40), the positions of both ends in the width direction of the polyvinyl alcohol-based resin layer and both ends in the width direction of the protective film are not coincident. Thus, interference between the protective film and the end portion of the polyvinyl alcohol-based resin layer can be suppressed, and when the protective film is peeled from the stretched film in the peeling step (S50), the polyvinyl alcohol-based resin layer is the base material. It can prevent peeling from the film. Note that when both ends of the stretched film with a protective film are cut off to align the ends of the polyvinyl alcohol-based resin layer and the protective film, both ends are not only aligned but the ends of both are crushed. There is a problem that the polyvinyl alcohol-based resin layer is more easily peeled off from the base film in the peeling step (S50) starting from this part. Such a problem does not occur.

The production method of the present invention protects the surface of the polyvinyl alcohol-based resin layer by having a bonding step (S30) for bonding the protective film to the stretched film before the winding step (S40), and also protects the surface of the polyvinyl alcohol resin layer. Thus, the slipperiness of the outermost surface of the film to be wound can be improved and the stretched film can be stably wound into a roll. If the surface of the polyvinyl alcohol-based resin layer is wound up without being protected by a protective film, the back surface of the base film is transferred to the surface of the polyvinyl alcohol-based resin layer and the quality is deteriorated, and the surface of the polyvinyl alcohol-based resin layer is slipped. Since the property is very bad, it is difficult to stably wind up the film and lengthen the film.

2 to 4 are top perspective views schematically illustrating the bonding step (S30) of the present invention. 2 to 4, (a) shows the stretched film 1 before the bonding step (S30), and (b) shows the stretched film 3 with a protective film after the bonding step (S30). In addition, after the bonding step (S30) and before the winding step (S40), when a protective film end portion removing step (S70) or a stretched film end portion removing step (S80) described later is performed, The stretched film 3 with a protect film shown in each of FIGS. 2 to 4 is after the protect film end portion removing step (S70) or the stretched film end portion removing step (S80) and before the winding step (S40). Shows the state.

In the bonding step (S30), the protective film 2 is bonded to the stretched film 1, and the stretched film 3 with a protective film is formed. 2 to 4 exemplify the stretched film 1 in which both ends of the base film according to the present invention and the polyvinyl alcohol-based resin layer are coincident with each other. It may be used.

In the stretched film 3 with a protect film illustrated in FIG. 2B, both

end portions

2 a and 2 b in the width direction of the protect film 2 are positioned at both end portions in the width direction of the stretched film 1 (positions at both end portions of the polyvinyl alcohol-based resin layer). 1a and 1b). In the stretched film 3 with a protective film illustrated in FIG. 2B, the protective film 2 does not touch both ends of the polyvinyl alcohol-based resin layer, so that the protective film 2 is peeled from the stretched film 1 in the peeling step (S50). In that case, the force in the peeling direction is less likely to be applied to the end of the polyvinyl alcohol-based resin layer, and the polyvinyl alcohol-based resin layer can be more effectively prevented from peeling from the base film.

In the stretched film 3 with a protect film illustrated in FIG. 3B, both

end portions

2a and 2b in the width direction of the protect film 2 are positioned at both end portions in the width direction of the stretched film 1 (positions of both end portions of the polyvinyl alcohol-based resin layer). (Coincides with) 1a and 1b. In the stretched film 3 with a protect film illustrated in FIG. 4B, one end 2 a in the width direction of the protect film 2 is the end in the width direction of the stretched film 1 (the position of the end of the polyvinyl alcohol-based resin layer). The other end 2b in the width direction of the protective film is the end in the width direction of the stretched film 1 (matches the position of the end of the polyvinyl alcohol-based resin layer) 1b. Located inside.

In the stretched film 3 with a protect film shown in FIGS. 2B, 3B, and 4B, one end in the width direction of the protect film 2 and one end in the width direction of the stretched film 1 are used. The positional deviation W from the portion (one end in the width direction of the polyvinyl alcohol-based resin layer) is preferably 1 mm or more, more preferably 1 mm or more and less than 7 mm, and further 2 mm or more and 5 mm or less. Preferably there is. By setting the positional deviation W to 1 mm or more, interference between the protective film 2 and the end portions of the polyvinyl alcohol-based resin layer can be more reliably suppressed. Further, by setting the positional deviation W to be less than 7 mm, the end portions where the protective film 2 and the stretched film 1 are not laminated are bent and difficult to carry, or the stretched films of the portions not covered by the protective film 2 It is possible to avoid the occurrence of problems such as sticking and peeling off.

In the present invention, in addition to the above-described steps, a protective film end removing step (S70) for cutting and removing the end portion so that the width of the protective film becomes a predetermined width may be provided. There may be provided a stretched film edge removing step (S80) in which the edge is cut and removed so that the width of the film becomes a predetermined width. By such a process, after the bonding process (S30) and before the peeling process (S50), both ends of the stretched film with a protective film are cut and removed, that is, in the width direction of the polyvinyl alcohol-based resin layer. Since the widths of the protective film and the stretched film constituting the stretched film with the protective film can be arbitrarily adjusted without carrying out the process of cutting and removing at the same time both ends and the widthwise ends of the protective film, It is possible to prevent the end portion from being folded or winding failure in the step (S40).

The protective film edge removal step (S70) and the stretched film edge removal step (S80) may be performed before the bonding step (S30) or after the bonding step (S30). When the protective film edge removing step (S70) is performed prior to the bonding step (S30), this step is a step that does not affect other steps for producing a stretched film, and the timing thereof is particularly limited. No, before the resin layer forming step (S10), after the resin layer forming step (S10) and before the stretching step (S20), after the stretching step (S20) and bonding step (S30). Before or simultaneously with any step. When the protective film edge removal step (S70) and the stretched film edge removal step (S80) are performed after the bonding step (S30), winding is performed in order to prevent end folding or winding failure. It is preferable to carry out before the step (S40). In addition, when performing after a bonding process (S30), it is made to perform the process which cut | disconnects an edge part only about the film (protect film or stretched film) in which the edge part of the width direction is located outside. When the protective film edge removal step (S70) or the stretched film edge removal step (S80) is performed after the bonding step (S30), the positional shift W after cutting the edge of the protection film or stretched film is It is preferable to be within the above numerical range, and the positional shift W immediately after the bonding step (S30) may not be within the above numerical range.

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

[First Embodiment]
The manufacturing method of the light-polarizing laminated film of this embodiment performs a protective film edge part removal process (S70) and a stretched film edge part removal process (S80) before a bonding process (S30). FIG. 5 schematically shows a protective film end portion removing step (S70), a stretched film end portion removing step (S80), and a laminating step (S30) in the method for producing a polarizing laminated film of the first embodiment. FIG.

As shown in FIG. 5, in the protect film end removing step (S70), the end is cut so that the width of the protect film 2 becomes a predetermined width, and in the stretched film end removing step (S80), the stretched film The width of the protective film 2 used in the subsequent bonding step (S30) is adjusted so that the width of the stretched film 1 is smaller than the width of the stretched film 1. And in the bonding process (S30), the stretched film 1 and the protect film 2 are bonded, and the stretched film 3 with a protect film is produced. In the stretched film 3 with a protect film after the bonding step (S30), both ends in the width direction of the protect film 2 are in the width direction of the stretched film 1 in the same manner as the stretched film 3 with a protect film shown in FIG. Are located on the inner side than the both end portions (corresponding to the positions of both end portions of the polyvinyl alcohol-based resin layer).

[Second Embodiment]
The manufacturing method of the light-polarizing laminated film of this embodiment performs a protective film edge part removal process (S70) before a bonding process (S30), and a stretched film edge part removal process after a bonding process (S30). (S80) is performed. FIG. 6 schematically shows a protective film edge removal step (S70), a bonding step (S30), and a stretched film edge removal step (S80) in the method for producing a polarizing laminated film of the second embodiment. FIG.

As shown in FIG. 6, in the protective film edge removing step (S70), the width of the protective film 2 is a predetermined width shorter than the width of the stretched film 1 bonded in the bonding step (S30). The end is cut off. And in the bonding process (S30), the stretched film 1 and the protective film 2 are bonded, and the stretched film 3 with a protective film is produced. Thereafter, in the stretched film end removing step (S80), the stretched film 1 is cut and removed so that the width becomes a predetermined width. In the stretched film 3 with a protective film after the stretched film end removing step (S80), both ends in the width direction of the protect film 2 are stretched film 1 as in the stretched film 3 with a protective film shown in FIG. It is located inside the both ends of the width direction (which coincides with the positions of both ends of the polyvinyl alcohol-based resin layer).

[Third Embodiment]
The manufacturing method of the light-polarizing laminated film of this embodiment performs a stretched film edge part removal process (S80) before a bonding process (S30), and protect film edge part removal process after a bonding process (S30). (S70) is performed. FIG. 7 schematically shows a stretched film edge removing step (S80), a bonding step (S30), and a protective film edge removing step (S70) in the method for producing a polarizing laminated film of the third embodiment. FIG.

As shown in FIG. 7, in the stretched film edge removal step (S80), the width of the stretched film 1 becomes a predetermined width that is narrower than the width of the protect film 2 to be pasted in the pasting step (S30). The end is cut off. And in the bonding process (S30), the stretched film 1 and the protective film 2 are bonded, and the stretched film 3 with a protective film is produced. Thereafter, in the protect film end removing step (S70), the end of the protect film 2 is cut and removed so that the width becomes a predetermined width. In the stretched film 3 with a protective film after the protective film edge removing step (S70), both ends in the width direction of the protective film 2 are stretched film 1 as in the stretched film 3 with a protective film shown in FIG. It is located outside the both ends of this width direction (it corresponds with the position of the both ends of a polyvinyl alcohol-type resin layer).

As mentioned above, although embodiment of this invention was described, this invention is not limited to these embodiment. Hereinafter, each process common to all the embodiments will be described in detail.

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

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

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

In order to improve the adhesion between the base film and the polyvinyl alcohol resin, a primer layer may be provided on the surface of the base film on which the polyvinyl alcohol resin layer is formed. The primer layer is preferably formed from a composition containing a crosslinking agent or the like in a polyvinyl alcohol resin from the viewpoint of adhesion.

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

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

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

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

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

The polyester resin is a polymer having an ester bond, and is mainly a polycondensate of a polyvalent carboxylic acid and a polyhydric alcohol. The polyvalent carboxylic acid used is mainly a dicarboxylic acid, that is, a divalent carboxylic acid, or a lower alkyl ester thereof, and examples thereof include terephthalic acid, isophthalic acid, dimethyl terephthalate, and dimethyl naphthalenedicarboxylate. The polyhydric alcohol used is also mainly a diol, that is, a divalent alcohol, and examples thereof include propanediol, butanediol, neopentyl glycol, and cyclohexanedimethanol.

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

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

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

Various products are commercially available as cyclic polyolefin resins. Specific examples include TOPAS (registered trademark) (Topas Advanced Polymers GmbH), Arton (registered trademark) (manufactured by JSR Corporation), ZEONOR (registered trademark) (manufactured by Nippon Zeon Corporation), Zeonex ( ZEONEX (registered trademark) (manufactured by ZEON Corporation), Apel (registered trademark) (manufactured by Mitsui Chemicals, Inc.).

Any appropriate (meth) acrylic resin can be adopted as the (meth) acrylic resin. For example, polymethacrylate such as polymethylmethacrylate, methyl methacrylate- (meth) acrylic acid copolymer, methyl methacrylate- (meth) acrylic acid ester copolymer, methyl methacrylate-acrylic acid ester- (meta ) Acrylic acid copolymer, methyl methacrylate-styrene copolymer (MS resin, etc.), polymer having alicyclic hydrocarbon group (for example, methyl methacrylate- (meth) acrylic acid cyclohexyl copolymer, methacrylic acid) Methyl- (meth) acrylate norbornyl copolymer, etc.). Preferably, a polymer mainly composed of a C ₁ -C ₆ alkyl ester of methacrylic acid such as polymethyl methacrylate is used. As the (meth) acrylic resin, a methyl methacrylate resin containing methyl methacrylate as a main component (50 to 100% by weight, preferably 70 to 100% by weight) is more preferably used.

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

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

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

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

The thickness of the base film can be determined as appropriate, but generally it is preferably 1 to 500 μm, more preferably 1 to 300 μm, and even more preferably 5 to 200 μm from the viewpoint of workability such as strength and handleability. The thickness of the base film is most preferably 5 to 150 μm.

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

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

Examples of the polyvinyl alcohol resin giving such characteristics include PVA124 (degree of saponification: 98.0 to 99.0 mol%) and PVA117 (degree of saponification: 98.0 to 99.0) manufactured by Kuraray Co., Ltd. Mol%), PVA624 (degree of saponification: 95.0-96.0 mol%), PVA617 (degree of saponification: 94.5-95.5 mol%), etc .; for example, AH manufactured by Nippon Synthetic Chemical Industry Co., Ltd. -26 (degree of saponification: 97.0 to 98.8 mol%), AH-22 (degree of saponification: 97.5 to 98.5 mol%), NH-18 (degree of saponification: 98.0 to 99) 0.0 mol%), N-300 (degree of saponification: 98.0 to 99.0 mol%) and the like; for example, JF-17 (Nihon Vinegar Poval Co., Ltd.) (degree of saponification: 98.0 to 99.99). 0 mol%), JF-17L (degree of saponification: 98.0 to 99.0 mol%), J -20 (saponification degree: 98.0 to 99.0 mol%) can be preferably used include such.

[Stretching step (S20)]
Here, the laminated film composed of the base film and the polyvinyl alcohol-based resin layer is preferably uniaxially stretched. Preferably, uniaxial stretching is performed so that the stretching ratio is more than 5 times and not more than 17 times. More preferably, it is uniaxially stretched so that the stretch ratio is more than 5 times and not more than 8 times. When the draw ratio is 5 times or less, the resin layer made of the polyvinyl alcohol-based resin is not sufficiently oriented, and as a result, the degree of polarization of the polarizer layer may not be sufficiently high. On the other hand, if the draw ratio exceeds 17 times, the laminated film is likely to break during stretching, and at the same time, the thickness of the stretched film becomes unnecessarily thin, and the workability and handling properties in the subsequent process may be reduced. The thickness of the stretched film after the stretching step (S20) is preferably 5 to 150 μm.

The stretching process in the stretching step (S20) is not limited to one-stage stretching, and can be performed in multiple stages. In this case, the second and subsequent stretching processes may be performed in the stretching process (S20), but may be performed simultaneously with the subsequent dyeing process (S60), the crosslinking process, and the like. Thus, when extending | stretching in multiple steps, extending | stretching process is performed so that it may become a draw ratio exceeding 5 times combining all the steps of an extending | stretching process.

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

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

[Bonding process (S30)]
Here, a protective film is bonded to the surface of the polyvinyl alcohol resin layer opposite to the surface on the base film side to obtain a stretched film with a protective film. In the resin layer forming step (S10), when the polyvinyl alcohol resin layer is formed on both surfaces of the base film, the protective film may be bonded to the surface of one polyvinyl alcohol resin layer.

Examples of the method for bonding the protective film to the stretched film include a method in which the stretched film and the protective film are stacked and pressed with a nip roll and bonded. In this case, the material of the nip roll can be metal, rubber or the like.

(Protect film)
The protective film is not particularly limited as long as it is a film that is in close contact with the stretched film and can be wound in the winding step (S40), and a commercially available protective film can be used. The adhesion strength of the protective film to the stretched film is preferably 0.02 to 0.08 N / 25 mm. The thickness of the protective film is preferably 1 to 100 μm, more preferably 1 to 80 μm, and even more preferably 1 to 50 μm from the viewpoint of workability such as strength and handleability. Examples of commercially available protect films include Tretec 7332 (manufactured by Toray Film Processing Co., Ltd.), protect tape # 625T (manufactured by Sekisui Chemical Co., Ltd.), and the like.

[Protect Film Edge Removal Step (S70), Stretched Film Edge Removal Step (S80)]
The cutting of the edge of the protective film or the stretched film in the protective film edge removing step (S70) or the stretched film edge removing step (S80) is not particularly limited. For example, a slit method using a slitter is used. Can be mentioned. This method is preferable in that the end of the long film can be continuously cut and removed.

Examples of the slitting method include a method in which two circular blades called shear blades are used to rotate the film according to the conveyance of the film while making contact with the lower blade with the upper blade, and a razor blade called a leather blade. There are a method of using, a method of pressing a blade called a score blade against a quenching roll or the like and slitting. Even with the method using a leather blade, there is a hollow cut that slits in the air without providing a backup guide, and a groove roll method that stabilizes the meandering of the slit by inserting the blade into a roll with a groove as a backup guide . Among them, a slit method using a shear blade that can easily change the slit position of the film is preferably used.

The part removed by the slit is discharged from the production line. The discharging method can be arbitrarily selected as long as the effect of the present invention is obtained. The portion removed by the slit may be discharged from the production line as it is, or may be discharged from the production line after passing through the same route as the cut film in a certain section.

[Winding process (S40)]
Here, the stretched film with a protective film is wound in a roll shape so that the protective film is on the upper surface. At the time of winding, the film is wound so as to be in contact with the protective film, so that the polyvinyl alcohol resin layer or the like can be wound up without being contaminated, and the subsequent unwinding can be performed cleanly and smoothly.

[Peeling step (S50)]
After the winding step (S40), the stretched film with the protective film is unwound from the wound roll, and the peeling step (S50) for peeling the protective film from the stretched film is performed, followed by stretching to the dyeing step (S60). Send out the film. The protective film peeling method is not particularly limited. The protective film peeled off from the stretched film is preferably wound on a winding shaft. At this time, the protective film may be peeled off by hand and wound around the take-up shaft, or may be adsorbed by a suction roll and conveyed to the take-up shaft and taken up. It is preferable to spray static elimination air on the peeling site.

[Dyeing step (S60)]
Here, the polyvinyl alcohol resin layer of the stretched film is dyed with a dichroic dye. Examples of the dichroic dye include iodine and organic dyes. Examples of organic dyes include Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Spura Blue G, Spura Blue GL, Spura Orange GL, Direct Sky Blue, Direct First Orange S, First Black, etc. can be used. One kind of these dichroic substances may be used, or two or more kinds may be used in combination.

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

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

The immersion time of the stretched film in the dyeing solution is not particularly limited, but it is usually preferably in the range of 15 seconds to 15 minutes, and more preferably 30 seconds to 3 minutes. The temperature of the dyeing solution is preferably in the range of 10 to 60 ° C., more preferably in the range of 20 to 40 ° C.

[Crosslinking process]
After the dyeing step (S60), a crosslinking step is usually performed. The cross-linking step can be performed, for example, by immersing the laminated film that has undergone the dyeing step (S60) in a solution containing a cross-linking agent (cross-linking solution). Conventionally known substances can be used as the crosslinking agent. Examples thereof include boron compounds such as boric acid and borax, glyoxal, and glutaraldehyde. One kind of these may be used, or two or more kinds may be used in combination.

As the crosslinking solution, a solution in which a crosslinking agent is dissolved in a solvent can be used. As the solvent, for example, water can be used, but an organic solvent compatible with water may be further included. The concentration of the crosslinking agent in the crosslinking solution is not limited to this, but is preferably in the range of 1 to 20% by weight, and more preferably 6 to 15% by weight.

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

The immersion time of the laminated film in the crosslinking solution is usually preferably from 15 seconds to 20 minutes, and more preferably from 30 seconds to 15 minutes. The temperature of the crosslinking solution is preferably in the range of 10 to 90 ° C.

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

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

In the washing step, washing treatment with an iodide solution and water washing treatment may be combined, and a solution in which liquid alcohol such as methanol, ethanol, isopropyl alcohol, butanol, propanol or the like is appropriately blended may be used. Through the above steps, the polyvinyl alcohol-based resin layer has a function as a polarizer, and a polarizing laminated film is obtained. In this specification, the polyvinyl alcohol-type resin layer which has a function as a polarizer is called a polarizer layer.

[Usage]
The polarizing laminated film manufactured by the above manufacturing method can be used as it is or further processed to obtain a polarizing plate having a polarizer layer. Such a polarizing plate can be used as a polarizing plate for various display devices including a liquid crystal display device.

[Example 1]
(1) Production of base film On both sides of a resin layer comprising a random copolymer of propylene / ethylene containing about 5% by weight of an ethylene unit (“Sumitomo Noblen W151” manufactured by Sumitomo Chemical Co., Ltd., melting point Tm = 138 ° C.) A base film roll having a three-layer structure in which a resin layer made of homopolypropylene (“Sumitomo Nobrene FLX80E4” manufactured by Sumitomo Chemical Co., Ltd., melting point Tm = 163 ° C.), which is a homopolymer of propylene, is disposed on a multilayer extruder. It was produced by the coextrusion molding used. The total thickness of the obtained base film roll was 90 μm, and the thickness ratio (FLX80E4 / W151 / FLX80E4) of each layer was 3/4/3.

(2) Formation of primer layer Polyvinyl alcohol powder (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., average polymerization degree 1100, average saponification degree 99.5 mol%, trade name: Z-200) is dissolved in 95 ° C. hot water. An aqueous polyvinyl alcohol solution having a concentration of 3% by weight was prepared. A crosslinking agent (manufactured by Taoka Chemical Co., Ltd., trade name: Sumire's Resin 650) was mixed at a ratio of 5 parts by weight with respect to 6 parts by weight of the polyvinyl alcohol powder in the obtained aqueous solution. The obtained mixed aqueous solution was coated on the base film subjected to the corona treatment using a small diameter gravure coater and dried at 80 ° C. for 10 minutes to form a primer layer having a thickness of 0.2 μm.

(3) Resin layer forming step Polyvinyl alcohol powder (manufactured by Kuraray Co., Ltd., average polymerization degree 2400, average saponification degree 98.0 to 99.0 mol%, trade name: PVA124) is dissolved in hot water at 95 ° C. A polyvinyl alcohol aqueous solution having a concentration of 8% by weight was prepared. The obtained aqueous solution was applied onto the primer layer using a lip coater and dried at 80 ° C. for 20 minutes to produce a laminated film consisting of a base film, a primer layer, and a polyvinyl alcohol resin layer. .

(4) Stretching process While continuously transporting the obtained laminated film, a free end uniaxial at a stretching ratio of 160 ° C. in the longitudinal direction (film transport direction) at a stretching temperature of 160 ° C. using a roll-to-roll stretching apparatus. A stretched film was obtained by stretching.

(5) Stretched film edge removal step, protect film edge removal step The edge of the obtained stretched film was slit with a shear blade (stretched film edge removal step). In addition, the end of a polyethylene protective film (manufactured by Toray Film Processing Co., Ltd., trade name: TRETECH 7332, thickness 30 μm) was slit with a shear blade so as to be 10 mm narrower than the width after slitting of the stretched film (protect Film edge removal step). In this way, the widths of the stretched film and the protective film used in the bonding process were adjusted.

(6) Bonding process The protective film was bonded to the polyvinyl alcohol resin layer side of the stretched film using a nip roll. At this time, the protect film was made to be the upper surface when the stretched film with the protect film was wound, and the misalignment between the end of the protect film and the end of the stretched film was 5 mm at both ends.

(7) Winding process, peeling process The stretched film with a protective film is wound up in a roll shape so that the protective film is on the upper surface, and then the stretched film with a protective film is unwound, and after peeling the protective film, the stretched film is continuously Sent to the dyeing process. The adhesion of the protective film to the stretched film was 0.02 N / 25 mm.

(8) Dyeing process and cross-linking process The dyeing process and cross-linking process were performed in the following procedure. First, the stretched film is changed to 90 ° C. dyeing solution (solution containing 0.6 parts by weight of iodine and 10 parts by weight of potassium iodide with respect to 100 parts by weight of water), which is an aqueous solution containing iodine and potassium iodide. After dipping for 2 seconds and dyeing the polyvinyl alcohol-based resin layer, excess iodine solution was washed away with pure water at 10 ° C. Subsequently, a 76 ° C. crosslinking solution (solution containing 9.5 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) as an aqueous solution containing boric acid and potassium iodide for 300 seconds. Soaked. Thereafter, it was washed with pure water at 10 ° C. for 10 seconds, and finally dried at 80 ° C. for 200 seconds.

Through the above steps, a polarizer layer was formed from the polyvinyl alcohol-based resin layer to obtain a polarizing laminated film. When the protective film was peeled off, no troubles such as peeling off the polyvinyl alcohol resin layer were confirmed.

[Comparative Example 1]
In Comparative Example 1, the same steps as in (1) to (4) of Example 1 were performed, and the protective film was removed using the nip roll without performing the stretched film edge removal step and the protection film edge removal step. The pasting process of pasting to a stretched film was performed. Then, about the stretched film with a protective film produced by the bonding process, the edge part of the stretched film and the protective film was slit simultaneously, and the process which aligns an edge part was performed.

For the stretched film with a protective film produced as described above, the same steps as in the above (7) and (8) of Example 1 were performed. However, when the protective film is peeled off in the peeling step, the polyvinyl alcohol-based resin layer is peeled off from the base film starting from the slit end, and the polyvinyl alcohol-based resin layer can be dyed in the dyeing step. There wasn't.

The polarizing laminated film produced by the production method of the present invention can be applied as it is or processed as a polarizing plate for various display devices including liquid crystal display devices.

1 stretched film, 1a, 1b stretched film end, 2 protect film, 2a, 2b protect film end, 3 stretched film with protect film.

Claims

A resin layer forming step of obtaining a laminated film by forming a polyvinyl alcohol-based resin layer on the base film;
A stretching step of stretching the laminated film to obtain a stretched film;
In the stretched film, a lamination step of obtaining a stretched film with a protective film by laminating a protective film on the surface opposite to the base film of the polyvinyl alcohol-based resin layer;
A winding step for winding the stretched film with the protective film;
Unwinding the stretched film with the protective film, and a peeling step of peeling the protective film from the stretched film,
Including in this order the dyeing step of dyeing the stretched film to obtain a polarizing laminated film,
In the winding step, the stretched film with a protective film is a polarizing laminated film in which the positions of both end portions in the width direction of the polyvinyl alcohol-based resin layer and both end portions in the width direction of the protect film are not coincident. Method.
In the winding process, in the stretched film with a protective film, a shift in position between an end in the width direction of the polyvinyl alcohol-based resin layer and an end in the width direction of the protect film is 1 mm or more. The manufacturing method of the polarizing laminated film of description.
The stretched film with a protective film after the pasting step has both end portions in the width direction of the protect film positioned inside both end portions in the width direction of the polyvinyl alcohol-based resin layer. Manufacturing method of the polarizing laminated film.
Before the pasting step, including a protective film end removal step of cutting and removing the end portion in the width direction of the protective film,
The manufacturing method of the polarizing laminated film of Claim 3 whose width | variety of the said protective film is narrower than the width | variety of the said polyvinyl alcohol-type resin layer in the said bonding process.
The manufacturing method of the polarizing laminated film of Claim 4 further including the stretched film edge part removal process which cut | disconnects and removes the edge part of the width direction of the stretched film before the said bonding process.
The stretched film with a protective film after the pasting step has both end portions in the width direction of the protect film positioned outside both end portions in the width direction of the polyvinyl alcohol-based resin layer. Manufacturing method of the polarizing laminated film.
Before the bonding step, including a stretched film end removing step of cutting and removing the end in the width direction of the stretched film,
The manufacturing method of the polarizing laminated film of Claim 6 whose width | variety of the said protective film is wider than the width | variety of the said polyvinyl alcohol-type resin layer in the said bonding process.
A base film; a stretched polyvinyl alcohol-based resin layer provided on the base film; and a protective film provided on a surface of the polyvinyl alcohol-based resin layer opposite to the base film. A stretched film with a long protective film,
A stretched film with a protective film, wherein the positions of both end portions in the width direction of the polyvinyl alcohol-based resin layer are not aligned with the positions of both end portions in the width direction of the protect film.
The stretched film with a protective film according to claim 8, wherein a displacement between an end of the polyvinyl alcohol-based resin layer and an end of the protective film in the width direction is 1 mm or more.