JP6216848B2 - Polyvinyl alcohol polymer film roll - Google Patents

Description

  The present invention is a polyvinyl alcohol polymer film (hereinafter, “polyvinyl alcohol” may be abbreviated as “PVA”) useful as a raw film for producing a polarizing film, a method for producing a polarizing film using the same, and The present invention relates to a polarizing film, a film roll formed by continuously winding a PVA polymer film, and a method for producing a PVA polymer film.

  PVA polymer films are used in various applications by utilizing unique properties such as transparency, optical properties, mechanical strength, and water solubility. Applications as a raw material for producing a polarizing film (raw film) constituting a polarizing plate which is a basic component of a display (LCD) are expanding. In the fields of LCD monitors and LCD TVs, screens are rapidly increasing. However, if there are defects in the polarizing plate, it cannot be incorporated into the product and the yield (product yield) decreases. Accordingly, there is a demand for a polarizing plate with a small amount of light and a polarizing film.

  By the way, various techniques have been known so far in relation to optical films including not only polarizing films but also protective films and retardation films. For example, when a thermoplastic resin such as polyester, polyamide, or polyolefin is heated to a melting point or higher to form a molten polymer, which is then extruded from a die and cooled to produce a film for use in optical applications, it is present in the polymer. As a means to solve the problem that the oligomer (low polymer) that precipitates on the surface during film production and adheres to the surface of the casting drum or roll and causes surface defects of the film, the outer peripheral surface has a surface roughness of 1S or less. In addition, it is known to use a film production apparatus using a film production drum or roll having a chromium plating film containing 0.5 to 5% of carbon atoms as the number of atoms relative to chromium atoms on the surface. (See Patent Document 1). In Patent Document 1, polyethylene terephthalate is melted at 275 ° C., extruded from a T-die and rapidly cooled with a casting drum cooled to 25 ° C. to form an amorphous sheet, and then a plurality of sheets arranged downstream of the casting drum. It is specifically described that when a metal roll is heated or cooled, a roll having a specific chromium plating film is used as a part of the plurality of metal rolls.

  In addition, when producing a polymer film by casting a polymer resin solution on a support, the surface defects (defects that protrude in the shape of protrusions on the film surface) are eliminated, and transparency that is useful for optical applications. In order to obtain a polymer resin film excellent in surface flatness, it is known that the number per unit area of defects of a specific size present on the surface of a support to be used is not more than a specific numerical value (see Patent Document 2). reference). In Patent Document 2, a solution obtained by dissolving an aromatic polycarbonate resin in a mixed solvent of ethanol and methylene chloride and a support having a specific surface characteristic (a mirror polishing plate made of SUS-316) are used. Specifically, it is specifically described that an aromatic polycarbonate film was prepared by adjusting the temperature to about 15 ° C., hand-coating the solution on a support, and drying.

  Further, when manufacturing an optical film by a melt casting film forming method in which a film-like thermoplastic resin (such as an alicyclic structure-containing polymer or cellulose ester) melt-extruded from an extruder is cooled by a cooling drum, a cooling drum is used. As a means to solve the problem of appearance defects called `` pressed scratches '' due to strong adhesion of dirt and foreign matter to the surface, an organic solvent is attached to the surface of the cooling drum, and then the wiping means is used to wipe the cooling drum. The surface of the cooling drum is wiped with an organic solvent to remove dirt on the surface of the cooling drum, and then the film-shaped thermoplastic resin melt-extruded from the extruder is adhered to the surface of the cooling drum after wiping, and then cooled. It is known to produce a film (see Patent Document 3). In Patent Document 3, a mixture containing a hydrogenated norbornene-based ring-opening polymer and cellulose acetate propionate is melt-extruded, and a film-like resin melt is cooled with a specific cleaning means (with a Vickers hardness of 800). It is described that a resin sheet is obtained by cooling and solidifying while being in close contact with a hard chrome plating film surface or an amorphous chrome plating film surface having a Vickers hardness of 1200.

JP-A-9-207210 JP 2000-84960 A JP 2006-82261 A Japanese Patent Publication No. 1-194777 JP 2005-238833 A Japanese Patent Laid-Open No. 9-1568 JP 2001-315138 A

  However, it has been difficult to produce a polarizing film and a polarizing plate with few defects at a level required in recent years by simply adopting the above-described conventional technique. That is, in the method of Patent Document 1, it is necessary to heat the thermoplastic resin to a melting point or higher to obtain a molten polymer, but the PVA polymer is a thermoplastic resin except for a special modified PVA polymer. In addition, it is difficult to adopt such a film forming method for the production of a PVA polymer film, and even if it can be adopted, a film having excellent surface characteristics cannot be obtained. In addition, as a method for forming a PVA polymer film, a film-forming stock solution obtained by dissolving a PVA-based polymer in a liquid medium or a film-forming stock solution containing a PVA-based polymer and a liquid medium and melted by the PVA-based polymer is used. A method is known in which the film is cast on a metal support and dried to form a film. However, the method is a melt substantially free of a liquid medium as described in Patent Document 1. Since the method of forming a film by cooling a polymer on a casting drum is greatly different, the film manufacturing drum described in Patent Document 1 is simply used, and the film is prepared using the above-described film forming stock solution. Even if it is cast on a production drum and dried to form a PVA polymer film, the fine defects based on the fine cracks present on the surface of the chromium plating film of the film production drum are sufficient. Can not be controlled, the polarizing plate or polarizing film produced using the PVA based polymer film obtained can not be fully achieved the quality level required in recent years.

  On the other hand, Patent Document 2 relates to a film forming method in which a solution containing a polymer resin and a solvent as main components is cast on a support and then dried to remove the solvent. Even if the defects raised in the shape of protrusions on the film surface can be eliminated by adopting the film, the defects recessed from the film surface cannot be controlled sufficiently and are produced using the obtained PVA polymer film. In addition, the polarizing plates and polarizing films cannot sufficiently achieve the quality level required in recent years.

  Moreover, since the method of patent document 3 cools the melt of a thermoplastic resin with a cooling drum like the method of patent document 1, the method of patent document 3 is employ | adopted for manufacture of a PVA polymer film. It is difficult to obtain a film having excellent surface characteristics even if it can be adopted. Further, if the wiping means described in Patent Document 3 is simply adopted, a film-forming stock solution in which the PVA polymer is dissolved in the liquid medium or the PVA polymer and the liquid medium is melted. Even if the PVA polymer film was formed by casting and drying this on the metal support and forming the PVA polymer film, the concave defects could not be sufficiently controlled, rather, the metal support By bringing the wiping means into contact with the body surface, defects such as scratches are produced on the surface of the metal support, and the surface properties of the resulting PVA polymer film may be deteriorated.

  Under the circumstances as described above, an object of the present invention is to provide a PVA-based polymer film that can produce a polarizing film with few defects and thus a polarizing plate with high yield. In addition, the present invention is a film roll in which a long PVA polymer film is continuously wound, and the difference in surface characteristics from the winding start portion to the winding end portion of the PVA polymer film is small. An object of the present invention is to provide a film roll capable of producing a polarizing film having a stable quality and thus a polarizing plate.

  In addition, the PVA polymer film is often in the form of a film roll in which a long PVA polymer film is continuously wound for reasons such as ease of storage and transportation and continuous use. In such a film roll, wrinkles are likely to occur on the film due to poor slip properties between the films, and such wrinkles tend to cause a deterioration in the quality of the polarizing film to be produced. On the other hand, the polarizing film may be required to reduce stained spots different from the above-described defects. Accordingly, the present invention provides, as another aspect, a PVA polymer film capable of easily producing a polarizing film in which wrinkles are unlikely to occur in a film roll and the dyeing spots are reduced, and the film is continuously wound. It aims at providing the film roll formed.

  When a polarizing film is produced using a PVA polymer film as a raw film, the PVA polymer film is usually dyed, uniaxially stretched, fixed, etc., but is dry and uniaxially stretched. In the dyeing process and the fixing process, and in the case of wet uniaxial stretching, in addition to these processes, in the swelling process and uniaxial stretching process before uniaxial stretching, A part of the coalescence may be eluted, and the eluted PVA polymer is deposited in the treatment bath and adheres to the film, or deposits on the film and remains as a foreign substance in the obtained polarizing film. May reduce quality and yield. Then, this invention aims at providing the manufacturing method of the polarizing film for manufacturing such a polarizing film with few foreign materials, and a polarizing film with few foreign materials manufactured by it.

  Furthermore, this invention aims at providing the manufacturing method of the PVA type | system | group polymer film which can manufacture the above PVA type | system | group polymer films and film rolls simply.

  As a result of intensive studies to achieve the above object, the present inventors have cast a PVA polymer in a solution state or a molten state on the surface of a metal support such as a drum or a belt, and then dried the PVA polymer to obtain a PVA. In the case of forming a polymer film, a foreign substance that appears to be a resin deposit adheres to a very small part of the innumerable cracks that existed on the surface of the metal support, and the resulting convex shape is formed on the film. It becomes a PVA polymer film having a large number of defects that are recessed from the film surface by being transferred, and such a PVA polymer film has many defects in a polarizing film and a polarizing plate produced therefrom. Thus, it has been found that there is a problem that the quality level required in recent years cannot be sufficiently achieved or the yield of the polarizing film or polarizing plate is reduced.

  If a metal support having a chrome plating layer on the surface and having a surface hardness within a specific range is used, it is possible to perform a general process such as buffing on the surface of the metal support before starting film formation. The number of cracks existing on the surface of the metal support can be easily reduced, and the number of defects recessed from the film surface of the obtained PVA polymer film can be reduced as compared with the conventional PVA system. It has been found that when a polymer film is used as a raw film for producing a polarizing film, a polarizing film and a polarizing plate having few defects and satisfying a recently required quality level can be produced with high yield.

  In addition to the above knowledge, when a metal support having a chromium plating layer on the surface and having a surface hardness within a specific range is used, the film surface can be formed even if a PVA polymer film is continuously formed over a long period of time. The variation in the number of defects recessed from the surface can be kept at a lower level than before. For example, when manufacturing a film roll in which a long PVA polymer film is continuously wound, It has been found that it is possible to easily obtain a film roll that can reduce the difference in surface characteristics from the winding start portion to the winding end portion of the combined film, and can produce a polarizing film having a stable quality and thus a polarizing plate. It was.

Further, when a metal support having a chromium plating layer on the surface and having a surface hardness in a specific range is used, a PVA polymer film having surface characteristics on both sides of the film in a specific range can be easily obtained. In a film roll in which a polymer film is continuously wound, wrinkles are unlikely to occur and the deterioration of the quality of the polarizing film can be suppressed, and according to the PVA polymer film, a polarizing film with reduced staining spots is obtained. It was found that it can be easily obtained, and that when a polarizing film is produced by a specific method using the PVA polymer film, a polarizing film with few foreign matters can be easily obtained.
The present inventors have further studied based on such knowledge and completed the present invention.

That is, the present invention
[1] A PVA polymer film (hereinafter referred to as this PVA) in which the number of defects that are recessed from the film surface and have an area of 400 μm ² or more and a depth of 0.3 μm or more is 0.25 / m ² or less. System polymer film may be referred to as “PVA polymer film (1)”);
[2] The PVA polymer film of the above [1], wherein the number of the defects is 0.15 / m ² or less;
[3] The PVA polymer film of the above [1] or [2], wherein the polymerization degree of the PVA polymer contained in the PVA polymer film is 3,000 or more and 10,000 or less;
[4] The PVA polymer film according to any one of the above [1] to [3], which is a long PVA polymer film;
[5] The PVA polymer film of [4], having a length of 6,000 m or more;
[6] The PVA-based weight according to [4] or [5] above, wherein the defects include defects that exist at substantially the same position in the width direction of the film at substantially constant intervals in the length direction of the film. Coalesced film;

[7] A film roll formed by continuously winding a long PVA polymer film, which is a defect that is recessed from the film surface and has an area of 400 μm ² or more and a depth of 0.3 μm or more. About the film roll in which the number of defects in the winding end portion of the PVA polymer film is 1.4 times or less with respect to the number of defects in the winding start portion of the PVA polymer film (hereinafter referred to as this film roll) Sometimes referred to as “film roll (1)”);
[8] The film roll of [7], wherein the number of the defects is 0.25 / m ² or less;
[9] The film roll of the above [7], wherein the number of the defects is 0.15 / m ² or less;
[10] The film roll according to any one of the above [7] to [9], wherein the polymerization degree of the PVA polymer contained in the PVA polymer film is from 3,000 to 10,000.
[11] The film roll according to any one of the above [7] to [10], wherein the length of the PVA polymer film is 6,000 m or more;
[12] Any one of the above-mentioned [7] to [11], wherein the defects include defects existing at substantially the same position in the width direction of the film at substantially constant intervals in the length direction of the film. Two film rolls;

[13] When the root mean square roughness is measured on each of both surfaces of the film, the difference between the two root mean square roughness obtained is 0.3 nm to 10 nm, and the smaller root mean roughness is 10 nm or less. A PVA polymer film (hereinafter, this PVA polymer film may be referred to as “PVA polymer film (2)”);
[14] The PVA polymer film according to [13], wherein the larger root mean square roughness is 1 nm or more and 20 nm or less;
[15] The PVA polymer film of the above [13] or [14], which is a long PVA polymer film;
[16] A film roll obtained by continuously winding the PVA polymer film of the above [15] (hereinafter, this film roll may be referred to as “film roll (2)”);
[17] A method for producing a polarizing film using the PVA polymer film according to any one of [13] to [15] as a raw film, comprising a dyeing step, a uniaxial stretching step, a fixing treatment step, and a drying step. And when exiting the last treatment bath before entering the drying step, the angle formed between the liquid surface of the treatment bath and the film surface is 30 ° to 85 °, and the upper surface of the film is polyvinyl alcohol. A production method, which is a surface having a smaller root mean square roughness in a polymer film;
[18] A polarizing film produced by the production method of [17] above;

[19] On the surface of a metal support having a chromium plating layer on the surface, having a surface hardness of 550 HV or more and less than 900 HV in terms of Vickers hardness, and in a solution state or a molten state A method for producing a PVA polymer film comprising a step of casting and drying the PVA polymer to form a film, and immediately before casting the solution or molten PVA polymer. A production method wherein the number of cracks having an area (the product of the maximum width and the maximum distance between end portions) on the surface of the body of 200 μm ² or more is 0.7 pieces / mm ² or less;
[20] The production method of the above [19], wherein the PVA polymer in a solution state or a molten state is in the form of a film forming stock solution containing a PVA polymer and water;
[21] The production method of the above [19] or [20], wherein the degree of polymerization of the PVA polymer is 3,000 or more and 10,000 or less;
[22] The method according to any one of [19] to [21] above, wherein the surface hardness of the metal support is Vickers hardness of 600HV or more and less than 800HV;
[23] The surface temperature of the metal support having a chromium plating layer on the surface and having a surface hardness of 550 HV or more and less than 900 HV in terms of Vickers hardness is 50 ° C. or more and 115 ° C. or less at a temperature change rate of 0.5 ° C./hour or more. The process according to any one of [19] to [22] above, comprising the step of:
[24] The production method according to any one of [19] to [23], wherein the PVA polymer film according to any one of [1] to [6] and [13] to [15] is produced;
About.

  ADVANTAGE OF THE INVENTION According to this invention, the PVA-type polymer film which can manufacture a polarizing film with few defects, and a polarizing plate with a sufficient yield can be provided. Moreover, according to this invention, it is a film roll by which a long PVA polymer film is wound up continuously, Comprising: The difference in the surface characteristics from the winding start part of a PVA polymer film to the winding completion part The film roll which can manufacture a polarizing film with small and stable quality and by extension, a polarizing plate can be provided.

  Further, according to the present invention, a PVA polymer film capable of easily producing a polarizing film in which wrinkles hardly occur in a film roll and dyeing spots are reduced, and the film is continuously wound. It is possible to provide a film roll, a method for producing a polarizing film for producing a polarizing film with little foreign matter, and a polarizing film with little foreign matter produced thereby.

  Furthermore, according to this invention, the manufacturing method of the PVA type | system | group polymer film which can manufacture the above-mentioned PVA type | system | group polymer film and film roll simply can be provided.

The present invention is described in further detail below.
[PVA polymer film (1)]
The PVA polymer film of the present invention (PVA polymer film (1)) is a defect that is recessed from the film surface and has an area of 400 μm ² or more and a depth of 0.3 μm or more (hereinafter referred to as this defect). The number of “defects A” may be 0.25 / m ² or less. Disadvantages that exist in plastic films are: voids (bubbles) in the film; so-called fish eyes caused by foreign matter adhering to and sticking; scratches (mostly groove-shaped dents) that occur during film handling; However, the present inventors are excellent in that a polarizing film and a polarizing plate with few defects can be produced with high yield by controlling the number of the defects A in particular. It was found that the effect was achieved. This defect A is considered to be caused by the convex transfer on the film forming apparatus described above. In particular, as described later, a PVA polymer film is formed using a metal support such as a drum or a belt. In this case, it is considered that one of the causes is that the convex shape due to the foreign matter that seems to be a resin deposit adhered on the metal support is transferred to the film. When the defect A occurs in the long PVA polymer film due to such a cause, at least a part of the defect A is at a substantially constant interval in the length direction of the film and in the width direction of the film. There is a tendency that a plurality (for example, three or more) are arranged at substantially the same position. Here, the substantially constant interval typically corresponds to the length of one round of a metal support such as a drum or a belt (the total circumference). May correspond to an integer multiple of the length. Moreover, since the convex shape by a foreign material can be formed in multiple numbers on a metal support body, the group of the fault A arranged as mentioned above may also exist.

As described above, in the PVA polymer film (1) of the present invention, it is necessary that the number of defects A is 0.25 / m ² or less. If the number of defects A exceeds 0.25 / m ² , the polarizing film or polarizing plate produced therefrom has a large number of defects, and the quality level required in recent years cannot be sufficiently achieved, or a polarizing film having many defects. If the polarizing plate is discarded, the yield of these products may be reduced. From such a viewpoint, the number of defects A is preferably 0.20 piece / m ² or less, more preferably 0.15 piece / m ² or less, and 0.10 piece / m ² or less. More preferably, it is particularly preferably 0.075 / m ² or less.
On the other hand, the lower limit of the number of defects A is not necessarily limited, but in order to extremely reduce the number of defects A, there is a risk that the cost for installing the film-forming equipment may become extremely high. The number of defects A is preferably 0.001 piece / m ² or more, more preferably 0.003 piece / m ² or more, and further preferably 0.005 piece / m ² or more.

Defect A is a defect that is recessed from the film surface and has an area of 400 μm ² or more and a depth of 0.3 μm or more. Here, the defect A only needs to be recessed from either one of both sides of the film toward the inside of the film, but most of the defect A is usually in contact with a metal support described later used during film formation. It is recessed toward the inside of the film from the surface where it was done. The area of the defect A means the area of the opening of the defect A. Further, the depth of the defect A means the depth in the direction perpendicular to the film surface from the opening of the defect A and the depth at the deepest position.
The number of defects A (in units / m ² ) is the PVA polymer film in which the defect A is searched from one end of the target PVA polymer film and examined until 10 defects A are found. Can be obtained by dividing 10 (units) by the area (unit: m ² ), specifically, by the method described later in the examples. Here, the determination as to whether or not each defect is the defect A can be performed using a non-contact surface shape measuring machine.

Although there is no restriction | limiting in particular in the shape of a PVA type | system | group polymer film (1), When using the said PVA type | system | group polymer film (1) as a raw film for polarizing film manufacture, a polarizing film is continuous with sufficient productivity. It is preferable that the film is a long PVA polymer film.
The length of the long PVA polymer film is not particularly limited, and can be appropriately set according to the use of the PVA polymer film (1). Specifically, the length is 1,000 m. Is preferably 4,000 m or more, more preferably 6,000 m or more, particularly preferably 7,000 m or more, and most preferably 8,000 m or more. . In particular, according to the method for producing a PVA polymer film, which will be described later, the number of defects A of the PVA polymer film can be reduced, and even if the PVA polymer film is continuously formed over a long period of time, Since the fluctuation of the number can be kept at a low level, it is possible to easily obtain a PVA polymer film with a reduced number of defects A even when the length is longer (for example, 6,000 m or more). it can. According to such a longer PVA polymer film, it is possible to stably produce a product satisfying the quality level required in recent years with few defects when producing a polarizing film continuously over a long period of time with a high yield. In addition, it is possible to reduce the complexity and time loss associated with switching the film roll. The upper limit of the length of the long PVA polymer film is not particularly limited. However, if it is too long, the handling property is deteriorated due to excessive increase in weight and roll diameter when used as a film roll, and storage and transportation are reduced. The length is preferably 30,000 m or less, more preferably 25,000 m or less, and even more preferably 20,000 m or less because it may be difficult.

  There is no restriction | limiting in particular in the width | variety of a long PVA-type polymer film, For example, although it can be 0.5 m or more, since a wide polarizing film is calculated | required in recent years, it is preferable that it is 1 m or more. More preferably, it is more preferably 4 m or more. Although there is no restriction | limiting in particular in the upper limit of the width | variety of the said elongate PVA-type polymer film, when the said width | variety is too wide, when manufacturing a polarizing film with the apparatus currently put into practical use etc., it can extend | stretch uniformly. Since it tends to be difficult, the width of the PVA polymer film is preferably 7 m or less.

  The thickness of the PVA polymer film (1) is not particularly limited and can be appropriately set according to the use of the PVA polymer film. Specifically, the thickness is preferably 300 μm or less, and 150 μm. Or less, more preferably 100 μm or less. In recent years, a thinner polarizing film may be required. From such a viewpoint, the thickness of the PVA polymer film (1) is preferably 45 μm or less, and more preferably 35 μm or less. Preferably, it is 25 μm or less. Although there is no restriction | limiting in particular in the minimum of the thickness of a PVA type | system | group polymer film (1), Since the polarizing film can be manufactured more smoothly etc., the said thickness is preferably 3 micrometers or more, and it is 5 micrometers or more. More preferred.

  As the PVA polymer constituting the PVA polymer film (1), one produced by saponifying a vinyl ester polymer obtained by polymerizing a vinyl ester monomer can be used. Examples of vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate, and the like. Among these, vinyl acetate is preferable.

  The vinyl ester polymer is preferably obtained by using only one or two or more vinyl ester monomers as a monomer, and using only one vinyl ester monomer as a monomer. Although what was obtained is more preferable, the copolymer of 1 type, or 2 or more types of vinyl-ester type monomers and the other monomer copolymerizable with this may be sufficient.

  Other monomers copolymerizable with such vinyl ester monomers include, for example, ethylene; olefins having 3 to 30 carbon atoms such as propylene, 1-butene and isobutene; acrylic acid or salts thereof; methyl acrylate, acrylic Ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc. Acrylic acid ester; methacrylic acid or salt thereof; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, methacrylic acid 2-ethylhexyl, dodecyl methacrylate Methacrylic acid esters such as octadecyl methacrylate; acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide, acrylamide propane sulfonic acid or salt thereof, acrylamidopropyldimethylamine or salt thereof, N- Acrylamide derivatives such as methylolacrylamide or derivatives thereof; methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropanesulfonic acid or salt thereof, methacrylamidepropyldimethylamine or salt thereof, N-methylolmethacrylamide or salt thereof Methacrylamide derivatives such as derivatives; N such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone Vinyl amides; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; cyan such as acrylonitrile and methacrylonitrile Vinyl halides; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; maleic acid or salts thereof, esters or acid anhydrides; itaconic acid or salts thereof; Examples thereof include esters or acid anhydrides; vinylsilyl compounds such as vinyltrimethoxysilane; and isopropenyl acetate. The vinyl ester polymer can have a structural unit derived from one or more of these other monomers.

  The proportion of the structural unit derived from the other monomer in the vinyl ester polymer is not particularly limited, but based on the number of moles of all structural units constituting the vinyl ester polymer, it is 15 mol% or less. It is preferable that it is 5 mol% or less.

The degree of polymerization of the PVA polymer is not necessarily limited, but is preferably 200 or more, more preferably 300 or more, more preferably 400 or more, because the film strength tends to decrease as the degree of polymerization decreases. Particularly preferred is 500 or more. Further, if the degree of polymerization is too high, the viscosity of the aqueous solution or melted PVA polymer tends to be high, and film formation tends to be difficult. Therefore, it is preferably 10,000 or less, more preferably 9,000. Hereinafter, it is more preferably 8,000 or less, and particularly preferably 7,000 or less. Here, the polymerization degree of the PVA polymer means an average polymerization degree measured according to the description of JIS K6726-1994. After re-saponifying and purifying the PVA polymer, it is measured in water at 30 ° C. The intrinsic viscosity [η] (unit: deciliter / g) is obtained by the following formula.
Degree of polymerization = ([η] × 10 ³ /8.29) ^{(1 / 0.62)}

  Further, when a PVA polymer film is produced by a method described later using a PVA polymer having a polymerization degree in the range of 3,000 to 10,000, a PVA polymer film having a very small number of defects A is obtained. Is obtained, and even if the PVA polymer film is continuously formed for a long time, the fluctuation of the number of defects A can be kept at a lower level, which is preferable. From such a viewpoint, the degree of polymerization of the PVA polymer is more preferably 4,000 or more, and further preferably 5,000 or more. The reason why the above effect is achieved by using a PVA polymer having a degree of polymerization in the range of 3,000 to 10,000 is not always clear, but the number of defects A in the PVA polymer film is not necessarily clear. Is considered to increase so that a PVA polymer in a solution state or a molten state easily enters a crack existing on the surface of the metal support, and this penetration occurs when a PVA polymer having the above degree of polymerization is used. Presumed to be suppressed.

  There is no particular limitation on the degree of saponification of the PVA polymer. For example, 60 mol% or more of the PVA polymer can be used, but the PVA polymer film is a raw film for producing an optical film such as a polarizing film. In the case of using as a PVA polymer, the degree of saponification of the PVA polymer is preferably 95 mol% or more, more preferably 98 mol% or more, and further preferably 99 mol% or more. Here, the degree of saponification of the PVA polymer is the total number of moles of structural units (typically vinyl ester monomer units) that can be converted into vinyl alcohol units by saponification and the vinyl alcohol units of the PVA polymer. Is the ratio (mol%) occupied by the number of moles of the vinyl alcohol unit. The degree of saponification of the PVA polymer can be measured according to the description of JIS K6726-1994.

  In producing the PVA polymer film (1), one PVA polymer may be used alone, or one or more of the degree of polymerization, the degree of saponification, the degree of modification, and the like. Two or more types of PVA polymers different from each other may be used in combination. The content of the PVA polymer in the PVA polymer film (1) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 85% by mass or more.

The PVA polymer film (1) preferably contains a plasticizer. By including a plasticizer in the PVA polymer film (1), it is possible to prevent generation of wrinkles when forming a film roll or improve process passability during secondary processing. The plasticizer is preferably a polyhydric alcohol, and specific examples include ethylene glycol, glycerin, diglycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and trimethylolpropane. These plasticizers may be used alone or in combination of two or more. Among these plasticizers, ethylene glycol or glycerin is preferable from the viewpoint of compatibility with PVA-based polymers and availability.
The content of the plasticizer in the PVA polymer film (1) is preferably in the range of 1 to 30 parts by mass, and in the range of 3 to 25 parts by mass with respect to 100 parts by mass of the PVA polymer. More preferably, it is further in the range of 5 to 20 parts by mass.

The PVA polymer film (1) preferably contains a surfactant from the viewpoint of improving the peelability from the metal support used in the production and improving the handleability of the PVA polymer film. Although there is no restriction | limiting in particular in the kind of surfactant, Anionic or nonionic surfactant can be used preferably.
Examples of the anionic surfactant include carboxylic acid types such as potassium laurate, sulfate ester types such as octyl sulfate, and sulfonic acid types such as dodecylbenzene sulfonate.
Nonionic surfactants include, for example, alkyl ether types such as polyoxyethylene oleyl ether, alkylphenyl ether types such as polyoxyethylene octylphenyl ether, alkyl ester types such as polyoxyethylene laurate, and polyoxyethylene laurylamino. Alkylamine type such as ether, alkylamide type such as polyoxyethylene lauric acid amide, polypropylene glycol ether type such as polyoxyethylene polyoxypropylene ether, alkanolamide type such as lauric acid diethanolamide, oleic acid diethanolamide, polyoxy Examples include allyl phenyl ether type such as alkylene allyl phenyl ether.
These surfactants may be used alone or in combination of two or more.

  The content of the surfactant in the PVA polymer film (1) is 0. 0 with respect to 100 parts by mass of the PVA polymer from the viewpoints of peelability from the metal support and handleability of the PVA polymer film. It is preferably within the range of 01 to 1 part by mass, more preferably within the range of 0.02 to 0.5 part by mass, and further preferably within the range of 0.05 to 0.3 part by mass. preferable.

  The PVA polymer film (1) may further contain other components other than the PVA polymer, the plasticizer, and the surfactant as necessary. Examples of such other components include moisture, antioxidants, ultraviolet absorbers, lubricants, colorants, fillers (inorganic particles, starch, etc.), preservatives, antifungal agents, and other components other than those described above. Examples thereof include polymer compounds.

[Film roll (1)]
The film roll of the present invention (film roll (1)) is a film roll in which a long PVA polymer film is continuously wound, and the winding start portion (PVA system) of the PVA polymer film The winding end portion of the PVA polymer film (when the winding of the PVA polymer film is finished as a film roll) with respect to the number of defects A in the film portion when the polymer film is started as a film roll) The number of the defects A in the film portion) is 1.4 times or less. In such a film roll, since the difference in surface characteristics from the winding start portion to the winding end portion of the PVA polymer film is small, a polarizing film with a stable quality and thus a polarizing plate can be manufactured according to the film roll. Is possible. From such a viewpoint, the number of the defects A in the winding end portion of the PVA polymer film with respect to the number of the defects A in the winding start portion of the PVA polymer film is 1.3 times or less. Preferably, it is 1.2 times or less, more preferably 1.1 times or less. In addition, since the number of defects A tends to increase with time in the formation of a long PVA polymer film, the PVA weight relative to the number of defects A in the winding start portion of the PVA polymer film is increased. In many cases, the number of the defects A at the end of winding of the combined film is usually 0.6 times or more, and from the viewpoint of producing a polarizing film having a stable quality and thus a polarizing plate, The number of defects A in the winding end portion of the PVA polymer film relative to the number of defects A in the winding start portion is preferably 0.7 times or more, and more preferably 0.75 times or more. 0.8 times or more is more preferable, and 0.9 times or more is particularly preferable.

In the PVA polymer film in the film roll (1) of the present invention, the number of defects A per unit area is not particularly limited, but the number of defects A in the PVA polymer film (1) of the present invention is described above. The number of defects A is 0.25 / m ² or less (with respect to the upper limit, preferably 0.20 / m ² or less, more preferably 0.15 / m ² or less, Preferably it is 0.10 piece / m ² or less, particularly preferably 0.075 piece / m ² or less, and regarding the lower limit, it is preferably 0.001 piece / m ² or more, more preferably 0.003 piece / m ² or more, More preferably, 0.005 pieces / m ² or more) When a polarizing film is continuously produced, a product satisfying a quality level required in recent years with few defects can be stably obtained with a high yield over a long period of time. Manufacture Bets since it is possible, preferably. If the number of defects A per unit area satisfies the number described above in both the winding start portion and the winding end portion of the PVA polymer film, the number is satisfied in the entire PVA polymer film. Can be considered.

  The length (winding length) of the PVA polymer film used in the film roll (1) of the present invention is not particularly limited, and can be appropriately set according to the use of the PVA polymer film, Specifically, the length can be 1,000 m or more. However, in recent years, a PVA polymer film longer than the conventional length of about 4,000 m may be required in order to reduce the complexity and time loss associated with film roll switching in the production of polarizing films. The length of the PVA polymer film is 6,000 m or more because the quality of the product can be stabilized even if the polarizing film is produced continuously for a long time using a longer PVA polymer film. It is preferably 7,000 m or more, and more preferably 8,000 m or more. The upper limit of the length of the long PVA polymer film is not particularly limited. However, if it is too long, the handling property is deteriorated due to excessive increase in weight and roll diameter when used as a film roll, and storage and transportation are reduced. The length is preferably 30,000 m or less and may be 25,000 m or less because it may be difficult and it may be difficult to produce a film roll that satisfies the provisions of the present invention. It is more preferable that it is 20,000 m or less. In addition, if the said length is 14,000 m or less, Furthermore, if it is 10,000 m or less, manufacture of the film roll which satisfy | fills the prescription | regulation of this invention will become easier.

  The other configuration relating to the PVA polymer film used in the film roll (1) of the present invention can be the same as that described above for the explanation of the PVA polymer film (1) of the present invention. Therefore, the overlapping description is omitted here.

  In the film roll (1) of the present invention, a long PVA polymer film is continuously wound, for example, a long PVA polymer film is continuously wound around a cylindrical core. Become. When a cylindrical core is used, it is preferable that both ends of the core form protrusions that protrude from the end face of the film roll.

  There is no restriction | limiting in particular in the kind of said cylindrical core, For example, a metal thing, a plastic thing, a paper thing, a wooden thing etc. are mentioned. It is also possible to use a core in the form of a composite, such as one using both metal and plastic, one using both metal and paper, and one using both plastic and paper. Among these, in consideration of strength, durability, low dust generation, etc., a metal and / or plastic core is preferable, and a metal core is more preferable because it is not easily affected by wear and the like even when used repeatedly. . Examples of the metal include iron, stainless steel, and aluminum. One of these may be used alone, or two or more may be used in combination. Examples of the plastic include polyvinyl chloride, polyvinylidene chloride, polyester, polycarbonate, polyamide, epoxy resin, polyurethane, polyurea, and silicone resin. One of these is used alone. Moreover, you may use 2 or more types together. The plastic may be fiber reinforced plastic (FRP) such as carbon fiber reinforced plastic from the viewpoint of strength and the like.

[PVA polymer film (2)]
In the PVA polymer film of the present invention (PVA polymer film (2)), when the root mean square roughness was measured on each of both surfaces of the film, the difference between the two root mean square roughnesses obtained was 0. 3 nm or more and 10 nm or less, and the smaller root mean square roughness is 10 nm or less. In the conventional film roll in which the PVA polymer film is continuously wound, wrinkles are likely to occur in the film due to poor slip between the films, etc., but according to the PVA polymer film (2) of the present invention, Generation | occurrence | production of the said wrinkle can be reduced. It should be noted that the film roll wrinkles occur when the PVA polymer film is wound up, and the stress remaining in the PVA polymer film when the film roll is stored in a warehouse or the like once In this case, the squeezing is caused by the poor slipping property between the films. According to the PVA polymer film (2) of the present invention, the former wrinkles are effectively generated. Although it can be reduced, the occurrence of the latter soot can also be reduced. In addition to this, according to the PVA polymer film (2) of the present invention, it is possible to easily produce a polarizing film in which stained spots different from the above-described defects are reduced.

  The root mean square roughness in the present invention means the root mean square roughness (Rq) described in JIS B0601: 2001, and the deviation from the mean line to the roughness curve in the roughness curve obtained from the surface of the film. It is obtained by averaging the squares. The root mean square roughness on each side of the PVA polymer film can be measured by the method described later in the examples.

  In the PVA polymer film (2) of the present invention, when the root mean square roughness is measured on each of both surfaces of the film, the difference between the two root mean square roughness obtained is 0.3 nm or more and 10 nm or less. is necessary. Generation | occurrence | production of the wrinkle in a film roll can be effectively reduced because both difference is 0.3 nm or more. On the other hand, when the difference between the two is 10 nm or less, stained spots in the polarizing film can be effectively reduced. From such a viewpoint, the difference between the two is preferably 0.5 nm or more, more preferably 0.8 nm or more, further preferably 1.2 nm or more, and 1.5 nm or more. Particularly preferred is 2 nm or more, most preferred is 7 nm or less, and more preferred is 5 nm or less.

  In the PVA polymer film (2) of the present invention, it is necessary that the smaller root mean square roughness is 10 nm or less. When the smaller root mean square roughness is 10 nm or less, stained spots in the polarizing film can be effectively reduced. From such a viewpoint, the smaller root mean square roughness is preferably 8 nm or less, more preferably 6 nm or less, and further preferably 4 nm or less. In addition, in order to extremely reduce the root mean square roughness, it is necessary to perform special processing, and the manufacturing cost of the PVA polymer film is likely to increase. Therefore, the root mean square roughness of the smaller one is 0.3 nm or more. Is preferably 0.6 nm or more, more preferably 0.9 nm or more, and particularly preferably 1.2 nm or more.

  In the PVA polymer film (2), the larger root mean square roughness is preferably 1 nm or more and 20 nm or less. Generation | occurrence | production of the wrinkle in a film roll can be more effectively reduced because the larger mean square roughness is 1 nm or more. On the other hand, when the larger root mean square roughness is 20 nm or less, stained spots in the polarizing film can be more effectively reduced. From such a viewpoint, the larger root mean square roughness is more preferably 2 nm or more, further preferably 4 nm or more, more preferably 15 nm or less, and further preferably 11 nm or less. 8 nm or less is particularly preferable, and 6 nm or less is most preferable.

Although there is no restriction | limiting in particular in the shape of a PVA type | system | group polymer film (2), When using the said PVA type | system | group polymer film (2) as a raw film for polarizing film manufacture, a polarizing film is continuous with sufficient productivity. It is preferable that the film is a long PVA polymer film.
The length of the long PVA polymer film is not particularly limited, and can be appropriately set according to the use of the PVA polymer film (2). Specifically, the length is 1,000 m. Is preferably 4,000 m or more, more preferably 6,000 m or more, particularly preferably 7,000 m or more, and most preferably 8,000 m or more. . According to such a longer PVA polymer film, it is possible to reduce complexity and time loss associated with film roll switching. The upper limit of the length of the long PVA polymer film is not particularly limited. However, if it is too long, the handling property is deteriorated due to excessive increase in weight and roll diameter when used as a film roll, and storage and transportation are reduced. The length is preferably 30,000 m or less, more preferably 25,000 m or less, and even more preferably 20,000 m or less because it may be difficult. In addition, as one of the causes of wrinkles generated when the film roll is stored, there is a winding squeezing due to the stress remaining in the PVA polymer film, but this winding squeezing is longer and wider. Since it tends to appear strongly in the PVA polymer film, the effect of the present invention is more remarkably exhibited in a longer PVA polymer film.

  There is no restriction | limiting in particular in the width | variety of a long PVA-type polymer film, For example, although it can be 0.5 m or more, since a wide polarizing film is calculated | required in recent years, it is preferable that it is 1 m or more. More preferably, it is more preferably 4 m or more. Although there is no restriction | limiting in particular in the upper limit of the width | variety of the said elongate PVA-type polymer film, when the said width | variety is too wide, when manufacturing a polarizing film with the apparatus currently put into practical use etc., it can extend | stretch uniformly. Since it tends to be difficult, the width of the PVA polymer film is preferably 7 m or less. Note that, as described for the length of the PVA polymer film, since the winding squeezing tends to appear strongly in the longer and wider PVA polymer film, the present invention is applied to the wider PVA polymer film. The effect is more remarkable.

  The thickness of the PVA polymer film (2) is not particularly limited and can be appropriately set according to the use of the PVA polymer film. Specifically, the thickness is preferably 300 μm or less, and 150 μm. Or less, more preferably 100 μm or less. In recent years, a thinner polarizing film may be required. From such a viewpoint, the thickness of the PVA polymer film (2) is preferably 45 μm or less, and more preferably 35 μm or less. Preferably, it is 25 μm or less. Although there is no restriction | limiting in particular in the minimum of the thickness of a PVA type | system | group polymer film (2), Since the polarizing film can be manufactured more smoothly etc., the said thickness is preferably 3 micrometers or more, and it is 5 micrometers or more. More preferred. In addition, since the wrinkle in a film roll is easy to generate | occur | produce, so that the thickness of a PVA polymer film is thinner, the effect of this invention is show | played more notably in a thinner PVA polymer film.

  The other configuration relating to the PVA polymer film (2) of the present invention can be the same as that described above for the description of the PVA polymer film (1) of the present invention, and therefore overlaps here. Description is omitted.

  Although there is no restriction | limiting in particular in the manufacturing method of a PVA-type polymer film (2), According to the manufacturing method of the PVA-type polymer film of this invention mentioned later, the target PVA-type polymer film (2) is simply manufactured. It is preferable because In this case, the side in contact with the surface of the metal support tends to be a surface having the larger root mean square roughness. In addition to the manufacturing method, a method of allowing a PVA polymer film formed between metal rolls having different surface roughness to pass through, or a foreign matter (deterioration in a film forming stock solution used for manufacturing a PVA polymer film). Resin and contamination from outside) are removed using a filter, etc., and ultrafine particles of inorganic substances are added to the film forming stock solution to form a film on a smooth surface to adjust the root mean square roughness on both sides, etc. Can be considered.

[Film roll (2)]
The film roll of the present invention (film roll (2)) is the PVA polymer film (2) described above, and is formed by continuously winding a long PVA polymer film. A long PVA polymer film (2), which is a PVA polymer film (2), is continuously wound around the core. When a cylindrical core is used, it is preferable that both ends of the core form protrusions that protrude from the end face of the film roll. As said core, what was mentioned above as description of a film roll (1) can be used, and the overlapping description is abbreviate | omitted here.

  Other configurations relating to the film roll (2) of the present invention can also be the same as those described above for the description of the film roll (1) of the present invention, and therefore, redundant description is omitted here.

  In the film roll (2) of the present invention, it is possible to reduce the occurrence of wrinkles that tend to occur when the conventional film roll is stored. The temperature when storing the film roll is preferably 40 ° C. or lower, more preferably 35 ° C. or lower, because if the temperature is too high, the PVA polymer film is deformed and wrinkles are likely to occur. Preferably, it is 30 degrees C or less. On the other hand, the lower limit of the temperature when storing the film roll is not particularly limited, but the temperature is preferably −10 ° C. or higher, more preferably −5 ° C. or higher, and 0 ° C. or higher. Further preferred.

[Method for producing PVA polymer film]
The production method of the present invention for producing a PVA polymer film has a chromium plating layer on the surface, the surface hardness is 550 HV or more and less than 900 HV in terms of Vickers hardness, and the surface temperature is 50 ° C. or more and 115 ° C. or less. A process of casting a solution or molten PVA polymer on the surface of a metal support and drying it to form a film. The number of cracks having an area (the product of the maximum width and the maximum end-to-end distance) of 200 μm ² or more on the surface of the metal support immediately before starting to cast the PVA polymer in the solution state or the molten state is 0. 7 pieces / mm ² or less. According to the production method, in the above-described PVA polymer film (PVA polymer films (1) and (2)) of the present invention and the film roll (film rolls (1) and (2)) of the present invention. A long PVA polymer film that is continuously wound can be easily produced.

  Examples of the metal support used in the present invention include a drum and a belt, and the surface thereof has a chromium plating layer. Here, the surface of the metal support means a surface (film-forming surface) on which a PVA polymer in a solution state or a molten state is cast. When the metal support is a drum, chromium is formed on the outer peripheral surface of the drum. What is necessary is just to have a plating layer, and in the case of a belt, it is only necessary to have a chromium plating layer on the outer surface of the continuous surface of the belt.

  The thickness of the chrome plating layer is not particularly limited, but it can be more effectively prevented from corroding the surface of the metal support, and the number of cracks described later can be easily reduced. preferable. Note that the chrome plating layer may be formed at one time or may be formed in multiple times. For example, when the chrome plating layer is formed in multiple times, After forming the chrome plating layer, the irregularities on the surface thereof may be removed by polishing or the like, and a chrome plating layer may be further formed thereon. In this way, pinholes in the chrome plating layer can be reduced. Moreover, as described in Patent Document 4 and the like, if a nickel plating layer is provided under the chromium plating layer, cracks in the chromium plating layer can be further reduced.

  In the metal support having a chromium plating layer on the surface, the surface hardness is required to be 550 HV or more and less than 900 HV in terms of Vickers hardness. Although the metal support which has a general chromium plating layer is well-known (for example, refer patent documents 4-7 etc.), when a metal support which has specific surface hardness like this invention is used, a reason is unknown. However, it is possible to easily reduce the number of cracks existing on the surface of the metal support by a general treatment performed on the surface of the metal support before starting film formation such as buffing. The number of the defects A in the PVA polymer film can be reduced as compared with the prior art, and even if the PVA polymer film is continuously formed over a long period of time, the variation in the number of the defects A can be reduced. Can also be kept at a low level. Moreover, the root mean square roughness of both surfaces of the film can be adjusted to a desired range. When the surface hardness is 900 HV or higher in terms of Vickers hardness, it becomes difficult to reduce the number of cracks present on the surface of the metal support, and a PVA polymer film is continuously formed over a long period of time. In this case, the fluctuation of the number of the defects A becomes large. In addition, the root mean square roughness on both sides of the film tends to deviate from the desired range. From the above viewpoint, the surface hardness is Vickers hardness, preferably less than 800 HV, and more preferably less than 780 HV. On the other hand, when the surface hardness is less than 550 HV in terms of Vickers hardness, it is easy to cause problems such as scratches during continuous film formation or cleaning of the surface of the metal support, and the PVA polymer film is continued for a long time. When the film is formed, the fluctuation of the number of the defects A is also increased. In addition, the root mean square roughness on both sides of the film tends to deviate from the desired range. From such a viewpoint, the surface hardness is preferably 600 HV or more, more preferably 650 HV or more, and further preferably 700 HV or more in terms of Vickers hardness.

  The surface hardness of the metal support can be obtained by measuring the Vickers hardness of the surface of the chrome plating layer at a plurality of locations using a hardness meter or the like and averaging them. The surface hardness (Vickers hardness) may be measured on the surface (film-formed surface) on which a PVA polymer in a solution state or a molten state is cast, but a PVA from which scratches generated during the measurement can be obtained. Since the quality of the polymer film may be lowered, the surface on which the PVA polymer in the solution state or the molten state is cast, such as a portion where the chromium plating layer is formed at the end of the drum or belt ( Corresponds to the film part that is removed by ear cutting etc. after film formation, even in the vicinity of the film formation surface) or the surface (film formation surface) on which the PVA polymer in solution or melt is cast The surface hardness of the surface to be measured is measured, and the value may be set as the surface hardness defined in the present invention. Specifically, the surface hardness of the metal support can be determined by the method described later in Examples.

Adjustment of the surface hardness of the metal support having a chrome plating layer on the surface can be easily performed by a known method. Specifically, the temperature of the chrome plating bath used for chrome plating is specified. Method of adjusting within the range; Method of adjusting the current density during chrome plating within a specific range; Method of adjusting the composition of the chrome plating bath; Chromium plating after heat treatment (annealing) or exposure to hydrogen gas, etc. It can be performed by a method of adjusting the hydrogen concentration occluded in the plating layer. Among these, the method of adjusting the temperature of the chromium plating bath within a specific range because the operation is simple; the method of adjusting the current density during the chromium plating treatment within a specific range; after the chromium plating treatment A method of adjusting the hydrogen concentration occluded in the chromium plating layer is preferable, and a method of adjusting the temperature of the chromium plating bath within a specific range is more preferable. Regarding the above method, using a chromic acid-sulfuric acid aqueous solution, which is a general chromium plating bath, the temperature of the chromium plating bath is in the range of 40 ° C. or higher and 70 ° C. or lower, and the current density is in the range of 60 A / dm ² or lower. Taking the case of performing chrome plating as an example, the surface hardness tends to be generally lower as the temperature of the chrome plating bath is higher and the current density is lower. In addition, regarding the hydrogen concentration occluded in the chrome plating layer, the surface hardness tends to generally decrease as the heat treatment temperature is increased or the treatment time is lengthened to decrease the concentration.

The method for forming the chromium plating layer is not particularly limited as long as the surface hardness can be a metal support that satisfies the above range, and a known method can be adopted. First, the surface of the metal support is polished by a method such as buffing or grinder polishing to remove surface irregularities as much as possible, and then surface treatment such as immersion degreasing, electrolytic degreasing, and aqueous hydrochloric acid immersion is performed, and then chromium Examples thereof include a method of performing a chrome plating process using a plating bath and further performing a heat treatment. As a chromium plating bath, a surge bath is typical and can be preferably used. Examples of the composition of the Sargent bath and the conditions of the chrome plating treatment are shown below.
<Composition of surge bath>
Chromic anhydride: 100 to 300 g / L (concentration based on chemicals used)
Sulfuric acid: 1/50 to 1/150 (mass ratio) of chromic anhydride used
<Conditions for chrome plating>
Current density 10-60A / dm ²

  The temperature of the chromium plating bath greatly affects the surface hardness of the metal support obtained as described above. The specific temperature of the chrome plating bath is preferably 50 ° C. or more, more preferably 53 ° C. or more, although it depends on other conditions employed in the chrome plating process and heat treatment conditions after the chrome plating process. More preferably, it is more preferably 54 ° C. or higher. If the temperature of the chrome plating bath is too low, the surface hardness of the obtained metal support tends to be excessively high. On the other hand, the temperature of the chromium plating bath is preferably 66 ° C. or less, more preferably 63 ° C. or less, further preferably 61 ° C. or less, and particularly preferably 58 ° C. or less. If the temperature of the chrome plating bath is too high, the surface hardness of the obtained metal support tends to be excessively low.

  Heat treatment (annealing) is preferably performed after the chromium plating treatment. When the heat treatment is performed at a high temperature, the time required for the heat treatment can be shortened, but if the temperature is too high, cracks are likely to occur in the chrome plating layer. Therefore, the heat treatment temperature is preferably 130 ° C. or less, more preferably 120 ° C. or less. On the contrary, when the heat treatment is performed at a low temperature, the risk of cracking is reduced, but the time required for the heat treatment is increased. Therefore, the temperature of the heat treatment is preferably 70 ° C. or higher, more preferably 90 ° C. or higher. The heat treatment time can be set within a range of 24 to 120 hours, although it depends on the conditions of the chromium plating treatment and the temperature of the heat treatment.

  As a PVA polymer in a solution state or a molten state, a film-forming stock solution obtained by dissolving a PVA-based polymer in a liquid medium, or a film-forming stock solution obtained by melting a PVA polymer containing a PVA-based polymer and a liquid medium And the like in the form of a film-forming stock solution containing a PVA polymer and a liquid medium. The film-forming stock solution may further contain a plasticizer, a surfactant, and other components as described above, if necessary.

  Examples of the liquid medium in the film-forming stock solution include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, Examples thereof include ethylenediamine and diethylenetriamine, and one or more of these can be used. Among these, water is preferable from the viewpoint of a small environmental load and recoverability. That is, as a preferable example of the PVA polymer in a solution state or a molten state, one in the form of a film forming stock solution containing a PVA polymer and water can be mentioned.

  The volatile fraction of the film-forming stock solution (the content ratio of volatile components such as a liquid medium removed by volatilization or evaporation during film formation in the film-forming stock solution) varies depending on the film-forming method, film-forming conditions, etc. It is preferably in the range of 90% by mass, and more preferably in the range of 55-80% by mass. When the volatile fraction of the film-forming stock solution is 50% by mass or more, the viscosity of the film-forming stock solution does not become too high, and filtration and defoaming are smoothly performed when preparing the film-forming stock solution, and there are few foreign matters and defects. Manufacture of a polymer film becomes easy. On the other hand, when the volatile fraction of the film-forming stock solution is 90% by mass or less, the concentration of the film-forming stock solution does not become too low, and the production of an industrial PVA polymer film becomes easy.

  There is no particular limitation on the method for preparing the above film forming stock solution. For example, a PVA polymer is dissolved in a liquid medium such as water, and at that time, a plasticizer, a surfactant, and other components as necessary. A method of adding at least one, or a PVA polymer containing a liquid medium such as water is melt-kneaded using an extruder, and at that time, a plasticizer, a surfactant, etc. And a method in which at least one of these components is melt-kneaded together.

  In the production method of the present invention for producing a PVA polymer film, the above-mentioned solution or melted PVA polymer is formed on the surface of the metal support having a surface temperature of 50 ° C. or higher and 115 ° C. or lower. The film is cast and dried to form a film. When the surface temperature of the metal support exceeds 115 ° C., the number of defects A increases in the resulting PVA polymer film. Moreover, the root mean square roughness of both surfaces of the film tends to be out of the desired range. From this viewpoint, the surface temperature of the metal support is preferably 105 ° C. or lower, more preferably 102 ° C. or lower, further preferably 99 ° C. or lower, particularly preferably 96 ° C. or lower, Most preferably, it is 95 degrees C or less. On the other hand, when the surface temperature of the metal support is less than 50 ° C., problems such as difficulty in peeling the film from the metal support or loss of transparency of the film are likely to occur. From such a viewpoint, the surface temperature of the metal support is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 80 ° C. or higher. In addition, what is necessary is just to employ | adopt the average value (average temperature) of the surface temperature of arbitrary several places (for example, 10 places or more) on the surface of a metal support body as a surface temperature of a metal support body.

  There is no particular limitation on the method of bringing the surface temperature of the metal support within the above range before the start of film formation. For example, when a drum is used as the metal support, a heat medium such as water, oil, or water vapor is provided inside the drum. It is possible to employ a method of passing through, heating with a dielectric heater installed inside the drum, or heating with an infrared heater or hot air heater installed so as to face the surface of the drum.

  Regarding the temperature change rate when the surface temperature of the metal support is within the above range before the start of film formation, for example, as described in Patent Document 5, it can be 3 ° C./hour or less. In the production method of the present invention using a metal support having a plating layer and having the above surface hardness, the reason is unknown, but it exists on the surface of the metal support even if the temperature change rate is relatively high. The number of the defects A in the PVA polymer film obtained can be controlled to a low level even if the increase in the number of cracks to be suppressed can be suppressed and the productivity is improved by reducing the temperature adjustment time. I found. From such a viewpoint, the temperature change rate when the surface temperature of the metal support is within the above range before the start of film formation is preferably 0.5 ° C./hour or more, and preferably 1 ° C./hour or more. More preferably, it may be 3.5 ° C./hour or more, 4 ° C./hour or more, 4.5 ° C./hour or more, and further 5 ° C./hour or more. The temperature change rate is preferably 10 ° C./hour or less, more preferably 7 ° C./hour or less, from the viewpoint of reducing the number of cracks.

  Further, when the surface temperature of the metal support is set within the above range before the start of film formation, it is preferable to reduce the temperature difference in the width direction of the metal support from the viewpoint of reducing cracks. When the surface temperature of the support is continuously measured in the width direction, and the obtained temperature distribution data is plotted in a graph with the position in the width direction on the horizontal axis and the temperature on the vertical axis, the absolute value of the slope is the maximum. The value is preferably 10 ° C./m or less, more preferably 5 ° C./m or less, further preferably 4 ° C./m or less, and particularly preferably 3 ° C./m or less.

Further, in the production method of the present invention for producing a PVA polymer film, a crack having an area on the surface of the metal support of 200 μm ² or more immediately before casting a solution or molten PVA polymer. Is 0.7 pieces / mm ² or less. Here, the area of the crack means the product of the maximum width of the crack and the maximum distance between the end portions. Usually, cracks such as cracks in the chromium plating layer exist on the surface of the metal support before the start of film formation. During film formation, it is considered that a foreign substance that seems to be a resin deposit gradually adheres to such a crack to form a convex shape, which is transferred to the film and a defect A is formed on the film. In particular, PVA-based polymers have high hydrophilicity compared to other polymers and have a good affinity with the metal, so it is considered that they easily enter into cracks existing on the surface of the metal support and adhere as resin deposits. It is considered that it is easy to form and grow a convex shape when the dried film is peeled off from the metal support. For this reason, in order to reduce the number of defects A, it is preferable to reduce the number of cracks present on the surface of the metal support as much as possible, but as described above, the surface has a chromium plating layer, When the metal support having the above surface hardness is used, the reason is unclear, but by a general treatment applied to the surface of the metal support before starting film formation such as buffing, the metal support The number of cracks existing on the surface can be easily reduced, and the number of the above-mentioned defects A in the obtained PVA polymer film can be reduced as compared with the conventional case. Moreover, the PVA polymer film is continuously used for a long time. Even if the film is formed, the fluctuation of the number of the defects A can be kept at a lower level than before. When the number of the cracks on the surface of the metal support exceeds 0.7 / mm ² , the number of defects A increases in the obtained PVA polymer film. From the viewpoint of reducing the number of defects A in the obtained PVA polymer film, the number of cracks on the surface of the metal support is 0. 0 immediately before casting the solution or molten PVA polymer. The number is preferably 3 pieces / mm ² or less, and more preferably 0.15 pieces / mm ² or less. On the other hand, since it is cumbersome to reduce the number of cracks on the surface of the metal support and the effect tends to reach its peak, the number is 0.005 pieces / mm ² or more, and further 0.01. It is preferable that it is at least pieces / mm ² .

The number of cracks having an area of 200 μm ² or more on the surface of the metal support is defined as 25 arbitrary positions on the surface of the metal support, and each is in a range of ² mm × 2 mm (4 mm ² ) using a microscope. area identifies the 200 [mu] m ² or more cracks ", determine the number of" area 200 [mu] m ² or more cracks "in the range × 25 locations of the 4 mm ^2, can be determined by calculating the number per 1 mm ² now . Here, the area of the crack means the product of the maximum width and the maximum end-to-end distance in each crack, and the maximum end-to-end distance is the distance between those ends when there are only two crack ends. It means a distance (straight line distance), and when there are a plurality of distances, it means a maximum distance among a plurality of end-to-end distances. Specifically, the number of cracks having an area of 200 μm ² or more on the surface of the metal support can be determined by the method described later in Examples.

  The width of the metal support can be appropriately set according to the width of the target PVA polymer film. Although the specific width of the metal support depends on the width of the target PVA polymer film, it is, for example, 0.5 m or more, and a wide PVA-based weight capable of producing a wide polarizing film. From the viewpoint of efficiently producing the combined film, it is preferably 4.5 m or more, more preferably 5.0 m or more, and further preferably 5.5 m or more. In consideration of the cost and ease of maintenance of the metal support, the width of the metal support is preferably 7.5 m or less, preferably 7.0 m or less, and 6.5 m or less. It is more preferable that

  There is no particular limitation on the method of casting the solution or molten PVA polymer on the surface of the metal support, and a known method using a T-type slit die, hopper plate, I-die, lip coater die or the like. Can be done according to. The temperature of the molten or solution PVA polymer is preferably in the range of 50 ° C. or more and 105 ° C. or less.

  Drying after casting can be performed by a known method, and can be performed by drying with heat applied from a metal support or applying hot air. Further, a desired PVA polymer film may be produced only by drying on the surface of the metal support, but after partially drying on the surface of the metal support by a known method, the One or two or more drying rolls arranged on the downstream side of the metal support and whose rotation axes are parallel to each other, or a PVA polymer film desired by further drying with a hot air dryer Can also be manufactured.

  The PVA polymer film thus obtained can be subjected to heat treatment or cut at both ends (ear portions) in the width direction as necessary. Moreover, it is good also as a film roll by winding up continuously as mentioned above.

[Usage]
PVA polymer film of the present invention (PVA polymer film (1) and (2)) and PVA polymer film unwound from the film roll of the present invention (film roll (1) and (2)) Can be used for various applications by taking advantage of the small number of defects A, stable quality, hardly generating wrinkles, etc., but the effect of the present invention is more remarkable. Therefore, it is preferably used as an original film for producing an optical film such as a polarizing film or a retardation film, and more preferably used as an original film for producing a polarizing film.

  There is no restriction | limiting in particular in the method of manufacturing a polarizing film using said PVA type | system | group polymer film as a raw fabric film, A well-known method can be employ | adopted, for example, dyeing | staining, using said PVA type | system | group polymer film, Uniaxial stretching, fixing treatment, drying, and washing or heat treatment may be performed as necessary. Here, the order of each process such as dyeing, uniaxial stretching, and fixing process is not particularly limited, and one or two or more processes can be simultaneously performed. Further, one or more of each treatment can be performed twice or more. For example, uniaxial stretching may be performed twice or more times. Before performing each step such as dyeing, uniaxial stretching, and fixing treatment, a swelling treatment may be performed as necessary.

  Dyeing may be performed at any stage before uniaxial stretching, during uniaxial stretching, or after uniaxial stretching. As dyes used for dyeing, iodine-potassium iodide; direct black 17, 19, 154; direct brown 44, 106, 195, 210, 223; direct red 2, 23, 28, 31, 37, 39, 79, 81 240, 242, 247; Direct Blue 1, 15, 22, 78, 90, 98, 151, 168, 202, 236, 249, 270; Direct Violet 9, 12, 51, 98; Direct Green 1, 85; Direct One or two or more of dichroic dyes such as yellow 8, 12, 44, 86, 87; direct orange 26, 39, 106, 107 can be used. Dyeing can be performed by immersing the PVA polymer film in a solution (dye bath) containing the dye. In addition, when forming a PVA-type polymer film, you may contain said dye previously.

Uniaxial stretching may be performed by either a wet stretching method or a dry heat stretching method, and may be performed in warm water (including the above-described dyeing bath and a fixed treatment bath described later), or a PVA polymer after water absorption. It can also be carried out in air using a film.
The temperature at the time of uniaxial stretching is not particularly limited, but when the PVA polymer film is uniaxially stretched (wet stretching) in warm water, it is preferably within a range of 30 ° C. or more and 90 ° C. or less, and dry heat stretching. When it does, it is preferable that it exists in the range of 50 to 180 degreeC.
The stretching ratio of uniaxial stretching (total stretching ratio when uniaxial stretching is performed in multiple stages) is preferably 4 times or more and more preferably 5 times or more from the viewpoint of polarization performance. Although there is no restriction | limiting in particular in the upper limit of a draw ratio, since it is easy to perform uniaxial stretching stably stably if it is 8 times or less. Although the thickness of the film after uniaxial stretching depends on the thickness of the PVA polymer film to be used, it is preferably in the range of 3 μm to 75 μm, and more preferably in the range of 5 μm to 50 μm.

  Fixing treatment is often performed for the purpose of strengthening the adsorption of the dye to the PVA polymer film. As the fixing treatment bath used for the fixing treatment, an aqueous solution containing one or more of boron compounds such as boric acid and borax can be used. An iodine compound may be added to the fixed treatment bath as necessary.

  After each treatment such as dyeing, uniaxial stretching, and fixing treatment, washing is preferably performed in order to remove the treatment bath liquid and foreign matters attached to the film surface before drying. Pure water may be used for the cleaning liquid used for cleaning, or water containing a small amount of these chemicals may be used in order to suppress the outflow of dyes and boron compounds due to cleaning. The cleaning liquid may be performed by spraying the surface of the film that has undergone each treatment in a shower or the like, or by immersing the film that has undergone each treatment in a washing bath.

  Drying and heat treatment are preferably performed within a range of 30 ° C. or higher and 150 ° C. or lower, and more preferably performed within a range of 50 ° C. or higher and 150 ° C. or lower.

  Using the PVA polymer film (2) and the PVA polymer film unwound from the film roll (2) as a raw film for producing a polarizing film, a dyeing process, a uniaxial stretching process, a fixing process, and drying. When manufacturing a polarizing film through each step of the process, when leaving the last processing bath (for example, a fixed processing bath or a washing bath) before entering the drying step, the liquid level of the processing bath and the film surface The angle formed (angle on the acute angle side) was 30 ° or more and 85 ° or less, and the upper surface of the film had the smaller root mean square roughness in the PVA polymer film used as the raw film. It is preferable to have a surface because a polarizing film with few foreign substances can be easily obtained.

  The reason why the above effect is achieved is not necessarily clear, but the production of the polarizing film as described above reduces the adhesion of the PVA polymer precipitated in each treatment bath and the treatment liquid used in each treatment. It is thought to be done. The angle formed between the liquid surface of the treatment bath and the film surface when exiting the last treatment bath before entering the drying process is not too large or too small. In order to facilitate, the angle is preferably 35 ° or more, more preferably 40 ° or more, further preferably 50 ° or more, and preferably 80 ° or less, and 75 ° or less. It is more preferable that it is 70 ° or less.

  The polarizing film obtained as described above is usually used as a polarizing plate by attaching a protective film that is optically transparent and has mechanical strength on both sides or one side. As the protective film, a cellulose triacetate (TAC) film, an acetic acid / cellulose butyrate (CAB) film, an acrylic film, a polyester film, or the like is used. Examples of the adhesive for bonding include PVA adhesives and urethane adhesives, among which PVA adhesives are suitable.

  EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to these examples. In addition, each measurement or evaluation method employ | adopted in the following preparation examples, an Example, a reference example, and a comparative example is shown below.

[Measurement of surface hardness of film-forming drum]
On the surface (circumferential surface) of the film-forming drum, a total of 8 points are determined for each of the four end portions so as to divide the total length of the film-forming drum into four equal parts on the lines that penetrate 5 mm from both ends. It was. At each point, the Vickers hardness of the chrome plating layer surface is measured with a UCI hardness meter MIC10 (manufactured by GE Sensing & Inspection Technologies, Inc .; the probe uses MIC-2101-A), and the average value thereof is calculated. It was set as the surface hardness of the film forming drum.

[Measurement of the number of cracks having an area of 200 μm ² or more on the surface of the film-forming drum]
Arbitrary 25 points are defined on the surface (circumferential surface) of the film-forming drum, and in each case, a digital video microscope VHX-900 (manufactured by Keyence Corporation) is used with a magnification of 1000 × and a size of 2 mm × 2 mm (4 mm ² ). Photographs of cracks within the range (cracks on the chrome plating layer) were taken. And the maximum width and maximum end-to-end distance of each crack seen on the photo (if there are only two ends, it means the end-to-end distance, and if there are more than one end-to-end distance, The maximum distance among them is calculated in units of μm, and these products are calculated. A crack having the product of 200 μm ² or more is defined as “a crack having an area of 200 μm ² or more”. In this way, the number of “cracks having an area of 200 μm ² or more” in the 4 mm ² range × 25 locations was determined, and the number per 1 mm ² was calculated therefrom.

[Measurement of surface temperature of film-forming drum]
One straight line in the width direction passing through an arbitrary point on the surface (peripheral surface) of the film-forming drum, and three other straight lines that are parallel to this straight line and that divide the peripheral surface into four equally with this straight line ( That is, every time the film-forming drum makes a quarter turn, a straight line located on the same straight line) is defined, and the temperature distribution on these four straight lines is measured using a thermotracer TH9100MR (manufactured by NEC Abio Infrared Technology Co., Ltd.). did. Next, from the obtained temperature distribution data, the temperature of each of the three points (total 12 points) at a position of 20 cm from the center in the width direction and from both ends toward the center is obtained for each straight line. The average value was defined as the surface temperature of the film-forming drum at that time. Further, the obtained temperature distribution data for each straight line is made into four graphs with the position in the width direction as the horizontal axis and the temperature as the vertical axis, and the maximum value of the absolute value of the slope is obtained. The maximum temperature gradient of the film forming drum was used.

[Measurement of number of defects in PVA film]
The defect of the film was found from the distortion of the image of the fluorescent lamp when the fluorescent lamp placed behind the PVA film was unwound from the film roll, and the circumference was circled with an oil-based magic pen. Next, the found defect is observed using a non-contact surface shape measuring instrument “NewView” 6300 (manufactured by Zygo), and is a defect that is recessed from the film surface and has an area (opening area) of 400 μm ² or more and a depth. Is a defect (defect A) of 0.3 μm or more. The above operation is started from the winding end portion of the manufactured film roll (still excluding the portion up to 10 m from the end in the length direction of the film in order to reduce the error), and the number of defects A is 10 By calculating the area of the PVA film up to the time (the length from the start of operation to the tenth defect A × the width of the film; the unit is m ² ), and dividing 10 (pieces) by that area, The number of defects A (unit: pieces / m ² ) at the end of winding was calculated. Further, among the ten defects A, it is substantially equal to an integral multiple of the entire circumference of the film-forming drum that is located at substantially the same position in the width direction of the film and in which the distance in the length direction of the film is used. Two or more defects (hereinafter referred to as “rotational cycle defects”) that are in a coincident relationship. Such defects, including parts other than the part subjected to measurement, are observed in the length direction of the film. The number of substantially the same (it can be considered that three or more are arranged at an interval of an integral multiple of the entire circumference of the film-forming drum) is obtained, and this is the above-mentioned area (unit is m ² ). The number of rotation cycle defects at the end of winding (unit: pieces / m ² ) was calculated.
Then, after manufacturing a polarizing film (a polarizing film manufactured from the PVA film on the winding end portion side) as described later using the remaining film roll, the remaining PVA film in an unused state is used. By unwinding the PVA film from the film roll and newly rewinding it on the film roll, the initial film roll start-up portion was positioned outside the new film roll. Using this new film roll, the same operation as described above was performed to determine the number of defects A and the number of rotation period defects (both in units / m ² ) at the initial winding start portion of the film roll, and the remaining film. A polarizing film (a polarizing film manufactured from the PVA film on the winding start portion side) was manufactured using a roll as described later.

[Evaluation of film roll wrinkles]
The film roll was visually observed and wrinkles were evaluated according to the following criteria.
Rank A: No wrinkles are recognized. Rank B: There are slight wrinkles, but there are no practical problems. Rank C: There is a level of wrinkles that causes practical problems.

[Measurement of root mean square roughness of PVA film]
Arbitrary 10 root mean square roughnesses on one side of the PVA film were measured using a white interference microscope NV6300 (manufactured by Zygo Corp.), and the average value was defined as the root mean square roughness of the side. Subsequently, the mean square roughness was obtained in the same manner for the other surface of the PVA film.

[Evaluation of polarizing film (20 sheets test)]
The PVA film unwound from the film roll was continuously processed in the order of pre-swelling / dying / uniaxial stretching / fixing / drying / heat treatment to prepare a polarizing film.
That is, the PVA film was immersed in 30 ° C. water for 30 seconds to be pre-swelled, and then immersed in an aqueous solution (dyeing bath) having a iodine concentration of 0.4 g / L and a potassium iodide concentration of 40 g / L for 3 minutes. And stained. Subsequently, uniaxial stretching was carried out in an aqueous solution (stretching bath) having a boric acid concentration of 4% at a stretching ratio of 5 times in the length direction, and further potassium iodide concentration 40 g / L, boric acid concentration 40 g / L and chloride. The fixing treatment was performed by immersing in a 30 ° C. aqueous solution (fixing treatment bath) having a zinc concentration of 10 g / L for 5 minutes. Thereafter, the film was dried with hot air at 40 ° C., and further heat-treated at 100 ° C. for 5 minutes.
Twenty test pieces of 50 cm in the length direction and 25 cm in the width direction were collected from arbitrary positions of the obtained polarizing film. On the other hand, a polarizing plate of 50 cm × 50 cm with few defects is prepared, and the above-mentioned test pieces are stacked on this polarizing plate so that the orientation axis is vertical, and placed on the Schaukasen for X-ray photography observation. The defect in each test piece was confirmed. In addition, when there is no defect in the test piece, the stacked polarizing plate / test piece looks black, but when the test piece has a defect, light leaks from that portion and can be recognized as a spot-like bright defect. The test piece in which two or more of these bright defects were observed was rejected, and the pass rate among the 20 test pieces was calculated.

[Evaluation of polarizing film (100 sheets test)]
In the 100 test pieces, the number of test pieces was changed from 20 to 100, and a test piece in which one or more bright defects were observed was rejected. The pass rate was calculated.

[Evaluation of stained spots and foreign matter on polarizing film]
A test piece of 50 cm in the length direction and 25 cm in the width direction was collected from an arbitrary position of the obtained polarizing film. On the other hand, a polarizing plate of 50 cm × 50 cm with few staining spots and foreign matters is prepared, and the above test piece is stacked on this polarizing plate so that the orientation axis is vertical, and this is placed on the shawkasen for X-ray photography observation. Then, the stained spots and foreign matters in the test piece were evaluated according to the following criteria.
-Dyeing spot A rank: Dyeing spot is not recognized B rank: Dyeing spot is slightly present, but there is no problem in practical use C rank: There is a dyeing spot at a level that causes practical problem-Foreign matter A rank: Foreign matter Not recognized B rank: There is a slight amount of foreign matter, but there is no practical problem C rank: There is a level of foreign matter that causes practical problems

[Preparation Example 1]
<< Preparation of drum 1 >>
After buffing the surface (circumferential surface) of a carbon steel film-forming drum having a width of 1.0 m and performing a base treatment such as a degreasing treatment, a chrome plating bath is used on the drum surface under the following conditions. Chrome plating was performed. In addition, what dissolved these chemical | medical agents in distilled water so that it might become 200 g / L of chromic anhydride and 2 g / L of sulfuric acid by the density | concentration of a chemical | medical agent used was used as the chromium plating bath.
・ Chromium plating bath temperature: 55 ℃
Current density: 20 A / dm ²
-Chrome plating layer thickness (after polishing): 50 μm
And after completion | finish of chromium plating process, the said drum for film forming was heat-processed at 102 degreeC for 50 hours, and stood to cool.
The surface hardness of the film-forming drum having the chromium plating layer formed on the surface (circumferential surface) by the above chromium plating treatment and heat treatment was measured according to the method described above, and was 760 HV. Hereinafter, this film-forming drum is referred to as “drum 1”.

[Preparation Example 2]
<< Preparation of drum 2 >>
A chrome plating treatment and heat treatment were performed in the same manner as in Preparation Example 1 except that the chrome plating bath temperature was changed to 52 ° C. to prepare a film-forming drum having a chrome plating layer formed on the surface (peripheral surface). With respect to this film-forming drum, its surface hardness was measured according to the method described above, and it was 840 HV. Hereinafter, this film-forming drum is referred to as “drum 2”.

[Preparation Example 3]
<< Preparation of drum 3 >>
A chrome plating treatment and heat treatment were performed in the same manner as in Preparation Example 1 except that the chrome plating bath temperature was changed to 48 ° C., and a film-forming drum having a chrome plating layer formed on the surface (circumferential surface) was prepared. With respect to this film-forming drum, its surface hardness was measured according to the method described above, and it was 950 HV. Hereinafter, this film-forming drum is referred to as “drum 3”.

[Preparation Example 4]
<< Preparation of drum 4 >>
Except that the chrome plating bath temperature was changed to 67 ° C., a chrome plating treatment and a heat treatment were performed in the same manner as in Preparation Example 1 to prepare a film-forming drum in which a chrome plating layer was formed on the surface (circumferential surface). With respect to this film-forming drum, its surface hardness was 525 HV as measured according to the method described above. Hereinafter, this film-forming drum is referred to as “drum 4”.

[Example 1]
The drum 1 was attached to a cast film forming facility and connected to a hot water circulation device. Next, the peripheral surface of the drum 1 was buffed. When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above-described method, it was 0.10 / mm ² . Thereafter, the surface temperature of the drum 1 was increased at a temperature change rate of 1 ° C./hour by a hot water circulation device and maintained at a surface temperature of 90 ° C. The maximum temperature gradient at this time was 3.8 ° C./m at the maximum.
On the other hand, after immersing 100 parts by mass of PVA (saponified product of vinyl acetate homopolymer) having a saponification degree of 99.9 mol% and a polymerization degree of 2,400 in 2,500 parts by mass of distilled water at 35 ° C. for 24 hours. Then, centrifugal dehydration was performed to obtain a PVA water-containing chip. The volatile content in the PVA water-containing chip was 70% by mass. After adding 333 parts by mass of the PVA hydrous chip (100 parts by mass in terms of dry PVA), 12 parts by mass of glycerin and 0.3 parts by mass of a surfactant (containing 95% by mass of lauric acid diethanolamide) The mixture was mixed to obtain a mixture, which was heated and melted in a vented twin screw extruder having a maximum temperature of 130 ° C. The obtained molten PVA was cooled to 100 ° C. with a heat exchanger, and then extruded from the 900 mm width coat hanger die onto the drum 1 having a surface temperature of 90 ° C., and further dried in a hot air drying furnace. And the elongate PVA film of width 0.7m was continuously manufactured by cutting the width direction both ends (ear part). The film forming speed was 8 m / min. The PVA film (thickness 60 μm, length 8,000 m) after the film formation was stabilized was continuously wound around an aluminum cylindrical core having a diameter of 6 inches to form a film roll.
Using the obtained film roll, the number of defects in the PVA film was measured and the polarizing film was evaluated by the above-described method (20 sheets test). As a result, the number of defects A in the winding start portion was 0.102. / M ² (of which the rotation period defect is 0.031 pieces / m ² ), the passing rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start side is 100%, the defect on the winding end part The number of A is 0.098 pieces / m ² (of which the rotation period defect is 0.029 pieces / m ² ), and the pass rate in the 20 sheet test of the polarizing film produced from the PVA film on the winding start side is 100. %Met. The number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 0.96 times.

[Example 2]
A PVA film was continuously produced as a film roll in the same manner as in Example 1 except that the length of the PVA film was changed from 8,000 m to 3,000 m. When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above method, it was 0.11 / mm ² .
When the number of defects of the PVA film was measured and the polarizing film was evaluated by the above-described method using the obtained film roll (20 sheets test), the number of defects A in the winding start portion was 0.110. / M ² (of which the rotation period defect is 0.044 pieces / m ² ), the pass rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start part side is 100%, and the defect in the winding end part The number of A is 0.121 pieces / m ² (of which the rotation period defect is 0.036 pieces / m ² ), and the pass rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start portion side is 100. %Met. The number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.10 times.

[Reference Example 1]
A PVA film was continuously produced as a film roll in the same manner as in Example 1 except that the length of the PVA film was changed from 8,000 m to 15,000 m. The number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the method described above and found to be 0.10 / mm ² .
When the number of defects of the PVA film was measured by the above-described method using the obtained film roll, the number of defects A in the winding start portion was 0.108 / m ² (of which the rotation period defects were 0.032 pieces / m ² ), and the number of defects A at the end of winding was 0.160 pieces / m ² (of which the rotation period defects were 0.096 pieces / m ² ). The number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated as 1.48 times.

[Example 3]
The PVA film was continuously changed in the same manner as in Example 1 except that the polymerization degree of PVA was changed from 2,400 to 3,300 and the length of the PVA film was changed from 8,000 m to 15,000 m. The film roll was manufactured. The number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the method described above and found to be 0.10 / mm ² .
Using the obtained film roll, the number of defects in the PVA film was measured and the polarizing film was evaluated (100 sheets test) by the above-described method. As a result, the number of defects A in the winding start portion was 0.088. / M ² (of which the rotation period defects are 0.018 pieces / m ² ), the pass rate in the 100-sheet test of the polarizing film manufactured from the PVA film on the winding start portion side is 98%, and the defects in the winding end portion The number of A is 0.118 pieces / m ² (of which the rotation period defect is 0.024 pieces / m ² ), and the pass rate in the 100 sheet test of the polarizing film manufactured from the PVA film on the winding start side is 95. %Met. The number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.34 times.

[Example 4]
The PVA film was continuously changed in the same manner as in Example 1 except that the polymerization degree of PVA was changed from 2,400 to 6,000 and the length of the PVA film was changed from 8,000 m to 15,000 m. The film roll was manufactured. When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above method, it was 0.13 / mm ² .
Using the obtained film roll, the number of defects of the PVA film was measured and the polarizing film was evaluated (100 sheets test) by the above-described method. As a result, the number of defects A in the winding start portion was 0.067. / M ² (of which the rotation period defect is 0.007 / m ² ), the pass rate in the 100 sheet test of the polarizing film manufactured from the PVA film on the winding start side is 99%, the defect in the winding end part The number of A is 0.074 pieces / m ² (of which the rotation cycle defect is 0.007 pieces / m ² ), and the pass rate in the 100 sheet test of the polarizing film manufactured from the PVA film on the winding start side is 99. %Met. The number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.10 times.

[Example 5]
While using the drum 2 instead of the drum 1 and changing the length of the PVA film from 8,000 m to 3,000 m, the PVA film was continuously produced as a film roll in the same manner as in Example 1. . When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 2 after buffing was measured by the method described above, it was 0.39 / mm ² .
Using the obtained film roll, the number of defects in the PVA film was measured and the polarizing film was evaluated (20 sheets test) by the above-described method. As a result, the number of defects A in the winding start portion was 0.172. / M ² (of which the rotation period defect is 0.052 pieces / m ² ), the polarizing film manufactured from the PVA film on the winding start part side has a pass rate of 90% in the 20-sheet test, and the defect at the winding end part The number of A is 0.224 pieces / m ² (of which the rotation period defect is 0.134 pieces / m ² ), and the pass rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start portion side is 85. %Met. The number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.30 times.

[Example 6]
The PVA film was continuously produced in the same manner as in Example 1 except that the surface temperature of the drum 1 was changed from 90 ° C. to 110 ° C. and the length of the PVA film was changed from 8,000 m to 3,000 m. And a film roll. When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above method, it was 0.13 / mm ² .
Using the obtained film roll, the number of defects in the PVA film was measured and the polarizing film was evaluated by the above-described method (20 sheets test). As a result, the number of defects A in the winding start portion was 0.132. / M ² (of which the rotation period defect is 0.053 pieces / m ² ), the passing rate in the 20 sheet test of the polarizing film produced from the PVA film on the winding start part side is 95%, the defect in the winding end part The number of A is 0.180 pieces / m ² (of which the rotation period defect is 0.090 pieces / m ² ), and the pass rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start side is 90. %Met. The number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.36 times.

[Example 7]
A PVA film was continuously produced as a film roll in the same manner as in Example 1 except that the temperature change rate was changed from 1 ° C./hour to 5 ° C./hour. The number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the method described above and found to be 0.10 / mm ² .
When the number of defects of the PVA film was measured by the above-described method using the obtained film roll, the number of defects A in the winding start portion was 0.110 / m ² (of which the rotation period defects were 0.044 pieces / m ² ), and the number of defects A at the end of winding was 0.122 pieces / m ² (of which the rotation period defects were 0.049 pieces / m ² ). The number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.11 times.

[Comparative Example 1]
A PVA film was continuously produced as a film roll in the same manner as in Example 1 except that the drum 3 was used instead of the drum 1. When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 3 after buffing was measured by the above method, it was 0.73 / mm ² .
Using the obtained film roll, the number of defects of the PVA film was measured and the polarizing film was evaluated (20 sheets test) by the above-described method. As a result, the number of defects A in the winding start portion was 0.291. / M ² (of which the rotation period defects are 0.175 pieces / m ² ), the pass rate in the 20-sheet test of the polarizing film produced from the PVA film on the winding start side is 80%, and the defects on the winding end portion The number of A is 0.938 pieces / m ² (of which 0.750 pieces / m ² is the rotation period defect), and the pass rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start portion side is 50. %Met. The number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 3.22 times.

[Comparative Example 2]
The PVA film was continuously produced in the same manner as in Example 1 except that the surface temperature of the drum 1 was changed from 90 ° C. to 120 ° C. and the length of the PVA film was changed from 8,000 m to 3,000 m. And a film roll. When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above method, it was 0.11 / mm ² .
Using the obtained film roll, the number of defects of the PVA film was measured and the polarizing film was evaluated (20 sheets test) by the above-described method. As a result, the number of defects A in the winding start portion was 0.252. / M ² (of which the rotation period defect is 0.101 piece / m ² ), the passing rate in the 20 sheet test of the polarizing film manufactured from the PVA film on the winding start part side is 80%, the defect in the winding end part The number of A is 0.358 pieces / m ² (of which the rotational period defect is 0.251 pieces / m ² ), and the pass rate in the 20-sheet test of the polarizing film produced from the PVA film on the winding start portion side is 65. %Met. The number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 1.42 times.

[Comparative Example 3]
In Example 1, an attempt was made to produce a PVA film by changing the surface temperature of the drum 1 from 90 ° C. to 40 ° C., but the drying on the drum was insufficient and it was difficult to peel the film from the drum. As a result, each evaluation was not performed.

[Comparative Example 4]
A PVA film was continuously produced as a film roll in the same manner as in Comparative Example 1 except that the temperature change rate was changed from 1 ° C./hour to 5 ° C./hour. When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 3 after buffing was measured by the above method, it was 0.73 / mm ² .
When the number of defects of the PVA film was measured by the above-described method using the obtained film roll, the number of defects A in the winding start portion was 0.332 pieces / m ² (of which the rotation period defects were 0.166 pieces ^{/ m} 2), and a number of drawbacks a in the winding termination portion 1.349 pieces / ^{m 2} (of which, the rotation cycle drawback 1.214 pieces / ^{m 2).} The number of defects A in the winding end portion relative to the number of defects A in the winding start portion was calculated to be 4.06 times.

[Example 8]
The drum 1 was attached to a cast film forming facility and connected to a hot water circulation device. Next, the peripheral surface of the drum 1 was buffed. When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 1 after buffing was measured by the above-described method, it was 0.10 / mm ² . Thereafter, the surface temperature of the drum 1 was raised by a hot water circulation device and maintained at a surface temperature of 90 ° C.
On the other hand, after immersing 100 parts by mass of PVA (saponified product of vinyl acetate homopolymer) having a saponification degree of 99.9 mol% and a polymerization degree of 2,400 in 2,500 parts by mass of distilled water at 35 ° C. for 24 hours. Then, centrifugal dehydration was performed to obtain a PVA water-containing chip. The volatile content in the PVA water-containing chip was 70% by mass. After adding 333 parts by mass of the PVA hydrous chip (100 parts by mass in terms of dry PVA), 12 parts by mass of glycerin and 0.3 parts by mass of a surfactant (containing 95% by mass of lauric acid diethanolamide) The mixture was mixed to obtain a mixture, which was heated and melted in a vented twin screw extruder having a maximum temperature of 130 ° C. The obtained molten PVA was cooled to 100 ° C. with a heat exchanger, and then extruded from the 900 mm width coat hanger die onto the drum 1 having a surface temperature of 90 ° C., and further dried in a hot air drying furnace. And the elongate PVA film of width 0.7m was continuously manufactured by cutting the width direction both ends (ear part). The film forming speed was 8 m / min. The PVA film (thickness 60 μm, length 12,000 m) after the film formation was stabilized was continuously wound around an aluminum cylindrical core having a diameter of 6 inches to form a film roll.
It was A rank when the above-mentioned method evaluated the wrinkle of the obtained film roll (wrinkle produced when winding up a PVA film). Moreover, when the mean square roughness of the PVA film was measured by the above-described method using the PVA film unwound from the obtained film roll, the mean square roughness on the surface in contact with the surface of the drum 1 was 4 The mean square roughness on the other surface was 1.9 nm. The difference between the two was calculated to be 2.2 nm.
The PVA film unwound from the film roll was continuously processed in the order of pre-swelling / dying / fixing / uniaxial stretching / washing / drying to prepare a polarizing film. That is, the PVA film was immersed in water at 30 ° C. for 60 seconds to be pre-swelled, and then immersed in an aqueous solution (dye bath) having an iodine concentration of 0.4 g / L and a potassium iodide concentration of 40 g / L for 110 seconds. Stained. Subsequently, the substrate was immersed for 90 seconds in a 30 ° C. aqueous solution (fixing treatment bath) having a boric acid concentration of 30 g / L, and further fixed in a 50% aqueous solution (stretching bath) having a boric acid concentration of 4%. Uniaxial stretching was performed in the direction at a stretching ratio of 5 times. Thereafter, the film was immersed in a 30 ° C. aqueous solution (cleaning bath) having a boric acid concentration of 15 g / L for 10 seconds for cleaning, and dried with hot air at 55 ° C. to obtain a polarizing film. The angle between the liquid surface of the cleaning bath and the film surface when leaving the cleaning bath, which is the last treatment bath before entering the drying process, is set to 60 ° by changing the position of the guide roll, and at that time The upper surface of the film was the surface having the smaller root mean square roughness of the PVA film used.
It was A rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method, it was A rank.

[Example 9]
A PVA film was continuously produced as a film roll in the same manner as in Example 8 except that the drum 2 was used instead of the drum 1. When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 2 after buffing was measured by the above method, it was 0.37 / mm ² .
It was B rank when the above-mentioned method evaluated the wrinkle (wrinkle produced when winding up a PVA film) of the obtained film roll. Moreover, when the mean square roughness of the PVA film was measured by the above-described method using the PVA film unwound from the obtained film roll, the mean square roughness on the surface in contact with the surface of the drum 2 was 6 0.72 and the root mean square roughness on the other surface was 2.0 nm. The difference between the two was calculated to be 4.7 nm.
A polarizing film was produced in the same manner as in Example 8 for the PVA film unwound from the film roll. It was B rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method, it was B rank.

[Comparative Example 5]
A PVA film was continuously produced as a film roll in the same manner as in Example 8 except that the drum 3 was used instead of the drum 1. When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 3 after buffing was measured by the above method, it was 0.73 / mm ² .
It was A rank when the wrinkle of the obtained film roll (wrinkle produced when winding up a PVA film) was evaluated by the above-mentioned method. Moreover, when the mean square roughness of the PVA film was measured by the above-described method using the PVA film unwound from the obtained film roll, the mean square roughness on the surface in contact with the surface of the drum 3 was 28. And the root mean square roughness on the other side was 2.6 nm. The difference between the two was calculated to be 25.7 nm.
A polarizing film was produced in the same manner as in Example 8 for the PVA film unwound from the film roll. It was C rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, it was C rank when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method.

[Comparative Example 6]
A PVA film was continuously produced as a film roll in the same manner as in Example 8 except that the drum 4 was used instead of the drum 1. When the number of cracks having an area of 200 μm ² or more on the surface (circumferential surface) of the drum 4 after buffing was measured by the method described above, it was 0.15 / mm ² .
It was C rank when the above-mentioned method evaluated the wrinkle of the obtained film roll (wrinkle produced when winding up a PVA film). Moreover, when the mean square roughness of the PVA film was measured by the above-described method using the PVA film unwound from the obtained film roll, the mean square roughness on the surface in contact with the surface of the drum 4 was 2 And the root mean square roughness on the other surface was 2.6 nm. The difference between the two was calculated to be 0.2 nm.
A polarizing film was produced in the same manner as in Example 8 for the PVA film unwound from the film roll. It was A rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method, it was A rank.

[Example 10]
Using the film roll obtained in Example 8, polarized light in the same manner as in Example 8 except that the angle formed between the liquid surface of the cleaning bath and the film surface when leaving the cleaning bath was changed from 60 ° to 45 °. A film was prepared. It was A rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method, it was B rank.

[Comparative Example 7]
Using the film roll obtained in Example 8, the upper surface of the film when leaving the washing bath was changed to be the surface having the larger root mean square roughness in the PVA film used A polarizing film was produced in the same manner as Example 8 except for the above. It was A rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, it was C rank when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method.

[Comparative Example 8]
Using the film roll obtained in Example 8, polarized light in the same manner as in Example 8 except that the angle formed between the liquid surface of the cleaning bath and the film surface when leaving the cleaning bath was changed from 60 ° to 25 °. A film was prepared. It was A rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, it was C rank when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method.

[Comparative Example 9]
Using the film roll obtained in Example 8, polarized light in the same manner as in Example 8 except that the angle formed between the liquid surface of the cleaning bath and the film surface when leaving the cleaning bath was changed from 60 ° to 88 °. A film was prepared. It was A rank when the dyeing spot of the obtained polarizing film was evaluated by the above-mentioned method. Moreover, it was C rank when the foreign material of the obtained polarizing film was evaluated by the above-mentioned method.

Claims (5)

A film roll formed by continuously winding a long polyvinyl alcohol polymer film,
The length of the polyvinyl alcohol polymer film is 6,000 m or more,
Regarding the defects that are recessed from the film surface and have an area of 400 μm ² or more and a depth of 0.3 μm or more, the polyvinyl alcohol polymer film corresponds to the number of defects at the winding start portion of the polyvinyl alcohol polymer film. A film roll in which the number of the defects in the winding end portion is 1.4 times or less. The number of shortcomings in the winding termination portion is 0.25 pieces / m ² or less, a film roll according to claim 1. The number of shortcomings in the winding termination portion is 0.15 pieces / m ² or less, a film roll according to claim 1. The film roll of any one of Claims 1-3 whose polymerization degree of the polyvinyl alcohol-type polymer contained in a polyvinyl alcohol-type polymer film is 3,000 or more and 10,000 or less. A disadvantage of the winding termination portion includes a defect present in substantially the same position in the width direction of the film at a substantially constant interval in the longitudinal direction of the film, any one of claims 1-4 The film roll as described in.