JPWO2017010178A1 - Polarizing plate, manufacturing method thereof, liquid crystal display device, and organic electroluminescence display device - Google Patents

Abstract

An object of the present invention is to provide a thin polarizing plate having reduced depolarization and an improved degree of polarization, and a display device having an improved contrast provided with the polarizing plate. The polarizing plate of the present invention has a polarizer (A) having a hydrophilic polymer layer dyed with a dichroic substance and an indentation elastic modulus of 4.5 GPa or more on at least one surface of the polarizer (A). And a transparent substrate (B) having a total light transmittance of 80% or more.

Description

  The present invention relates to a polarizing plate, a method for manufacturing the same, a liquid crystal display device, and an organic electroluminescence display device. More particularly, the present invention relates to a thin polarizing plate with reduced depolarization and an improved degree of polarization, a method for manufacturing the same, and a display device having an improved contrast provided with the polarizing plate.

  With the demand for thin display devices, there is a demand for thin polarizing plates.

  Thinning the polarizing plate includes a method of forming a thin film of polyvinyl alcohol (also referred to as PVA in the present application) into a thin film, but a group capable of stretching the PVA in a step of producing a PVA polarizer. A method of producing a thin polarizer by applying to a material, then stretching and dyeing the whole substrate, and peeling off the PVA coating film portion is known (for example, see Patent Documents 1 to 3).

  However, when a PVA polarizer is produced by coating, the polarization degree is scattered due to the uneven shape on the surface of the PVA coating film and depolarization occurs, resulting in a decrease in the degree of polarization, and a decrease in contrast when used in a liquid crystal display device. It was found that would occur.

  A coating-type PVA polarizer usually applies PVA to a base material and performs stretching and dyeing, but an uneven shape is generated on the surface. This is because the surface opposite to the substrate (that is, the surface that comes into contact with air during coating) has a concavo-convex shape because the surface shape of the PVA coating is controlled only by the surface tension of the coating solution. It is easy to suppress the shape.

  If there is an uneven shape between a polarizer and a cell of a display device (for example, a liquid crystal cell), as described above, the polarization is scattered and depolarization occurs, so that the degree of polarization decreases and the contrast of the display device is increased. Since it has a great influence, it is important to control the surface shape of the coating type PVA polarizer.

JP 2000-338329 A JP 2011-1000016 A JP 2012-073570 A

  The present invention has been made in view of the above-described problems and circumstances, and a solution to the problem is a thin polarizing plate with reduced depolarization and an improved degree of polarization, and a contrast provided with the polarizing plate. An improved display device is provided.

  In order to solve the above problems, the present inventor, in the process of studying the cause of the above problems, etc., by the polarizing plate composed of a polarizer and a transparent substrate having a specific indentation elastic modulus, depolarization is reduced, The inventors have found that a thin polarizing plate having an improved degree of polarization can be obtained, and have reached the present invention.

  That is, the said subject which concerns on this invention is solved by the following means.

  1. A polarizer (A) having a hydrophilic polymer layer dyed with a dichroic material, and an indentation elastic modulus of 4.5 GPa or more and a total light transmittance of 80 on at least one surface of the polarizer (A). % Of the transparent substrate (B) which is at least%.

  2. 2. The polarizing plate according to item 1, wherein the transparent substrate (B) contains a transparent heat resistant resin having an imide structure.

  3. In the predetermined rectangular area where the transparent base material (B) is cut out from the projected image of the transparent base material, the gray value standard deviation σ is in the range of 0.50 to 1.10, and the rectangular area The polarizing plate according to item 1 or 2, wherein the area occupied by the black portion in the binarized image is 50% or less.

  4). The polarizing plate according to any one of Items 1 to 3, wherein the polarizer (A) is a coating-type polarizer.

5. A method for producing a polarizing plate comprising a polarizer (A) having a hydrophilic polymer layer and a transparent substrate (B) having an indentation elastic modulus of 4.5 GPa or more and a total light transmittance of 80% or more,
A step of casting a coating solution containing a hydrophilic polymer on a substrate to form a hydrophilic polymer layer;
Stretching the hydrophilic polymer layer and dyeing with a dichroic material;
A process of forming a polarizing plate by laminating the transparent base material (B) with a nip roller on the air interface side surface of the hydrophilic polymer layer,
The manufacturing method of the polarizing plate characterized by having.

  6). The said transparent base material (B) contains the transparent heat resistant resin which has an imide structure, The manufacturing method of the polarizing plate of Claim 5 characterized by the above-mentioned.

  7). A liquid crystal display device comprising the polarizing plate according to any one of items 1 to 4.

  8). An organic electroluminescence display device comprising the polarizing plate according to any one of items 1 to 4.

  By the above means of the present invention, it is possible to provide a thin polarizing plate having reduced depolarization and an improved degree of polarization, a method for producing the same, and a display device having an improved contrast provided with the polarizing plate. .

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  As described above, the coating-type PVA polarizer has a surface opposite to the substrate whose surface shape is controlled only by flattening due to the surface tension of the coating solution, and the surface of the polarizer when it is made into a polarizing plate. When there is a problem that it is difficult to suppress the uneven shape of the PVA polarizer, the surface of the PVA polarizer opposite to the base material is sandwiched by a transparent base material having a high indentation elastic modulus with a nip roller. By smoothing, it is presumed that light scattering on the surface is suppressed, depolarization is less likely to occur, and the degree of polarization is improved.

Sectional drawing which shows an example of a structure of the polarizing plate of this invention The schematic diagram which shows the example which clamps and bonds a polarizer (A) and a transparent base material (B) with a nip roller. Schematic diagram for analyzing a film projection image according to the present invention Schematic diagram of a bending processing apparatus preferably applicable to the present invention Projected image of transparent substrate (B) of the present invention Binary image of the transparent substrate (B) of the present invention Gray value standard deviation of the transparent substrate (B) of the present invention Schematic diagram of organic EL display

  The polarizing plate of the present invention has a polarizer (A) having a hydrophilic polymer layer dyed with a dichroic substance and an indentation elastic modulus of 4.5 GPa or more on at least one surface of the polarizer (A). And a transparent substrate (B) having a total light transmittance of 80% or more. This feature is a technical feature common to the claimed invention.

  As an embodiment of the present invention, from the viewpoint of manifesting the effects of the present invention, the transparent base material (B) contains a transparent heat resistant resin having an imide structure, in order to realize a specific indentation elastic modulus. preferable.

  In addition, in the predetermined rectangular area where the transparent base material (B) is cut out from the projected image of the transparent base material, the gray value standard deviation σ is in the range of 0.50 to 1.10. From the viewpoint of improving the depolarization by making the surface of the coating type polarizer (A) smooth and remarkably smooth that the area occupied by the black portion in the binarized image of the rectangular area is 50% or less. ,preferable.

  The method for producing a polarizing plate of the present invention comprises a polarizer (A) having a hydrophilic polymer layer and a transparent substrate (B) having an indentation elastic modulus of 4.5 GPa or more and a total light transmittance of 80% or more. A process for forming a hydrophilic polymer layer by casting a coating liquid containing a hydrophilic polymer on a substrate, stretching the hydrophilic polymer layer, and A step of dyeing with a chromatic substance, and then a step of bonding the transparent base material (B) to a surface of the hydrophilic polymer layer on the air interface side with a nip roller to form a polarizing plate, It is preferable from the viewpoint of smoothing the uneven shape on the surface of the coating type polarizer (A) and improving depolarization.

  Since the polarizing plate of the present invention is a thin polarizing plate with reduced depolarization and an improved degree of polarization, it is particularly suitable for a thin liquid crystal display device and an organic electroluminescence display device.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<< Outline of Polarizing Plate of the Present Invention >>
The polarizing plate of the present invention has a polarizer (A) having a hydrophilic polymer layer dyed with a dichroic substance and an indentation elastic modulus of 4.5 GPa or more on at least one surface of the polarizer (A). And a transparent substrate (B) having a total light transmittance of 80% or more.

  Although the structure of the polarizing plate of this invention is demonstrated with a figure, it is not limited to this.

  FIG. 1 is a cross-sectional view showing an example of the configuration of the polarizing plate of the present invention.

  A transparent polymer layer in which a hydrophilic polymer layer 2 is coated on a substrate 1 to form a polarizer (A) 3, and an indentation elastic modulus is 4.5 GPa or more and a total light transmittance is 80% or more. The material (B) 4 is laminated to constitute the polarizing plate 10.

  When the polarizing plate of the present invention is actually used, the substrate 1 is peeled from the hydrophilic polymer layer 2, and the hydrophilic polymer layer 2 is bonded as a polarizer (A) 3 to a display device or the like. Is done. Therefore, since the polarizer (A) 3 has only the layer thickness of the hydrophilic polymer layer 2, it becomes a thin polarizer and contributes to the thinning of the member.

  When the transparent base material (B) according to the present invention can function as a protective film for the polarizer, and the transparent base material (B) is a polyimide film containing a transparent heat-resistant resin having an imide structure, Because of its excellent heat resistance and moisture resistance, the polarizing performance stability, environmental fluctuation resistance and dimensional stability of the polarizing plate are higher than those of protective films using conventional triacetyl cellulose (TAC) films. It can be greatly improved.

[1] Polarizing plate In the polarizing plate of the present invention, a hydrophilic polymer layer is laminated on a substrate by a coating method, and then subjected to a stretching treatment to form a stretched laminate. After the polymer layer is dyed and imparted with a polarizing function to form a polarizer (A), the hydrophilic polymer layer has an indentation elastic modulus of 4.5 GPa or more on the air interface side surface to transmit all light. The transparent base material (B) having a rate of 80% or more is bonded while being sandwiched between nip rollers. The “coating polarizer” in the present invention refers to a hydrophilic polymer layer coated on the substrate.

  Since the substrate is peeled off in use, the polarizer (A) according to the present invention finally refers to the hydrophilic polymer layer, and the layer thickness can be reduced to 10 μm or less. is there. A preferred layer thickness is in the range of 0.5 to 10 μm.

[1.1] Substrate The substrate according to the present invention functions as a substrate for supporting the hydrophilic polymer layer, and is preferably a thermoplastic resin layer.

  The thermoplastic resin used in the present invention includes a crystalline thermoplastic resin in which polymers are regularly arranged, and an amorphous or amorphous state in which the polymers do not have a regular arrangement or only a small part. Can be broadly classified into a thermoplastic resin, and either can be used.

  Regardless of whether the resin is a crystalline resin or an amorphous resin, a resin that is not in a crystalline state or a resin that does not reach a crystalline state is referred to as an amorphous or amorphous resin. Here, an amorphous or amorphous resin is used in distinction from an amorphous resin having a property of not producing a crystalline state.

  Examples of the crystalline thermoplastic resin include olefin resins including polyethylene (PE) and polypropylene (PP), and ester resins including polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). One of the characteristics of the crystalline thermoplastic resin is that it generally has a property that crystallization proceeds due to alignment of polymers by heating or stretching orientation. The physical properties of the resin vary depending on the degree of crystallization. On the other hand, for example, even with a crystalline thermoplastic resin such as polypropylene (PP) and polyethylene terephthalate (PET), crystallization can be suppressed by inhibiting the arrangement of the polymers caused by heat treatment or stretching orientation. . These polypropylene (PP) and polyethylene terephthalate (PET) whose crystallization is suppressed are called amorphous polypropylene and amorphous polyethylene terephthalate. These are collectively called amorphous olefin resin and amorphous ester type. It is called resin. For example, in the case of polypropylene (PP), amorphous polypropylene (PP) in which crystallization is suppressed can be produced by using an atactic structure without stereoregularity. Further, for example, in the case of polyethylene terephthalate (PET), as a polymerization monomer, a molecule that inhibits crystallization of polyethylene terephthalate (PET) by copolymerizing a modifying group such as isophthalic acid or 1,4-cyclohexanedimethanol. By copolymerization, amorphous polyethylene terephthalate (PET) with suppressed crystallization can be produced.

  Among the ester resins that are polycondensates of polyvalent carboxylic acids (dicarboxylic acids) and polyhydric alcohols (diols), examples of crystalline ester resins that can be used in the present invention include polyethylene terephthalate (PET). ), Polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and the like. These crystalline ester resins have the property of being easily crystallized when formed into a film, but they are not rapidly crystallized and are stretchable when produced at a temperature that maintains an amorphous state. Therefore, it can be used as a thermoplastic resin. If the film is crystallized during film formation, the stretchability of the film naturally decreases. In order to ensure the stretchability of the film, it is preferable to use a film formed in an amorphous state by suppressing crystallization during film formation.

  The base material according to the present invention may contain a plasticizer or an elastomer in order to improve the workability / stretchability of the film. Examples of the plasticizer include phthalates and polycondensates thereof, fatty acid esters such as adipic acid and polycondensates thereof, polyester plasticizers, epoxy plasticizers, styrene polymers, acrylic polymers, terphenyl compounds, and the like. Examples thereof include substituted derivatives thereof. Examples of the elastomer include styrene, olefin, acrylic, vinyl chloride, urethane, ester, and nylon.

  The thickness of the substrate (before stretching) can be determined as appropriate, but is generally about 1 to 500 μm from the viewpoints of workability such as strength and handleability and thin layer properties. The range of 1-300 micrometers is especially preferable, and the range of 5-200 micrometers is more preferable. The thickness of the substrate is particularly suitable when it is 5 to 150 μm. On the other hand, the thickness of the base material (after stretching) in the stretched laminate is about 1 to 400 μm, preferably in the range of 1 to 200 μm, preferably 5 to 100 μm from the viewpoint of workability such as strength and handleability. More preferably, it is the range. The thickness of the base material in the stretched laminate is determined by the thickness of the base material (before stretching) and the stretch ratio.

[1.2] Polarizer (A)
The polarizer (A) according to the present invention includes a hydrophilic polymer layer on a substrate. The hydrophilic polymer layer is a layer containing a hydrophilic polymer as a main component, and the hydrophilic polymer layer adsorbs a dichroic substance by a dyeing process described later. Thereby, a hydrophilic polymer layer functions as a polarizer (A) in the polarizing plate of the present invention.

  Although there is no restriction | limiting in particular about the hydrophilic polymer which comprises a hydrophilic polymer layer, A polyvinyl alcohol-type material is illustrated preferably. Examples of the polyvinyl alcohol-based material include polyvinyl alcohol and derivatives thereof. Examples of polyvinyl alcohol derivatives include polyvinyl formal, polyvinyl acetal, etc., olefins such as ethylene and propylene, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, alkyl esters thereof, acrylamide, and the like. Can be mentioned. The degree of polymerization of polyvinyl alcohol is preferably about 100 to 10,000, and more preferably 1,000 to 10,000. A saponification degree of about 80 to 100 mol% is generally used. In addition to the above, examples of the hydrophilic polymer include partially saponified ethylene / vinyl acetate copolymer, dehydrated polyvinyl alcohol and dehydrochlorinated polyvinyl chloride. Of the polyvinyl alcohol materials, polyvinyl alcohol is preferably used as the hydrophilic polymer.

  The hydrophilic polymer layer may contain additives such as a plasticizer and a surfactant in addition to the above-described hydrophilic polymer. Examples of the plasticizer include polyols and condensates thereof, and examples include glycerin, diglycerin, triglycerin, ethylene glycol, propylene glycol, and polyethylene glycol. The amount of the plasticizer used is not particularly limited, but is preferably 20% by mass or less with respect to the total solid content (100% by mass) of the hydrophilic polymer layer.

  As said polyvinyl alcohol-type material, you may use a commercial item, for example. Examples of the commercially available products include the product name “JC40” manufactured by Nippon Vinegar Pover Co., Ltd., the product name “Poval PVA124” manufactured by Kuraray Co., Ltd., and the product name “GOHSENOL” manufactured by Nippon Synthetic Chemical Industry Co., Ltd. NH-18 "and the like.

[Production Method of Polarizer (A)]
In the polarizer (A) according to the present invention, the hydrophilic polymer layer is laminated on the base material to form a laminate, and further stretched to form a stretched laminate. The stretching treatment may be carried out after or simultaneously with the dyeing treatment. However, if the drawing treatment is carried out before the dyeing treatment, it is possible to dye along the oriented hydrophilic polymer molecules, so that uniform polarization characteristics are imparted. This is also preferable.

  Therefore, in the method for producing a polarizer (A) according to the present invention, a hydrophilic polymer layer is laminated on a substrate by a coating method, and then stretched in the TD direction (width direction) or MD direction (longitudinal direction). It is preferable to pass through and form the extending | stretching laminated body which has a polarizer.

  There is no restriction | limiting in particular about the manufacturing method of the said extending | stretching laminated body, It can manufacture suitably, referring the description of the column of the conventionally well-known knowledge and the Example mentioned later.

  An example of a method for producing a stretched laminate can be obtained, for example, by applying a solution containing the hydrophilic polymer (preferably polyvinyl alcohol) on the substrate, followed by drying and stretching. .

  The solvent of the solution is not particularly limited, and examples thereof include water, alcohol, dimethyl sulfoxide (DMSO) and the like. Any appropriate method can be adopted as a method of applying the solution. Examples of the coating method include spin coating, roll coating, flow coating, dip coating, and bar coating. The coating temperature is preferably not higher than the glass transition temperature (Tg) of the substrate.

  After the application, the hydrophilic polymer layer is dried. For example, natural drying, air drying, heat drying and the like are preferable. In the case of heat drying, the temperature is preferably in the range of 50 to 75 ° C, more preferably in the range of 60 to 70 ° C. The drying time is usually about 5 to 30 minutes.

  The base material used for the production of the stretched laminate may have been subjected to a stretching treatment in advance before applying the aqueous solution containing the hydrophilic polymer.

  As the stretching treatment for forming the stretched laminate, either an air stretching method or an underwater stretching method (for example, a method described in International Publication No. 2010/100917) can be employed. The said extending | stretching process can be implemented using arbitrary appropriate extending machines, such as a roll extending machine and a tenter extending machine, for example. The stretching temperature is, for example, in the range of 75 to 150 ° C. in the case of air stretching, preferably in the range of 80 to 150 ° C., and more preferably in the range of 90 to 130 ° C. In the case of stretching in water, the stretching temperature is preferably 85 ° C. or lower, more preferably in the range of 40 to 85 ° C. When the temperature exceeds 85 ° C., the dichroic substance such as iodine adsorbed on the polyvinyl alcohol resin is used in the case where the polyvinyl alcohol resin is dissolved in water or the dyeing process described later is performed before the stretching process. There is a risk of problems such as elution in water. Therefore, particularly when the polyvinyl alcohol resin layer is thin (when the resulting polarizing film is thin), the optical properties of the resulting thin polarizing film may be significantly reduced. It is more preferable that the stretching temperature is 65 ° C. or less because stretching in water can be performed satisfactorily and more excellent optical properties (for example, polarizing film contrast ratio) can be obtained.

  As the stretching treatment, uniaxial stretching, biaxial stretching, oblique stretching, or the like is performed. Uniaxial stretching may be either longitudinal stretching performed in the MD direction of the laminate or transverse stretching performed in the TD direction of the laminate. In transverse stretching, the film can be contracted in the longitudinal direction while stretching in the width direction. Examples of the transverse stretching method include a fixed end uniaxial stretching method in which one end is fixed via a tenter, and a free end uniaxial stretching method in which one end is not fixed. Examples of the longitudinal stretching method include an inter-roller stretching method, a compression stretching method, and a stretching method using a tenter. The stretching process can be performed in multiple stages. In addition, when the extending | stretching process with respect to a laminated body is uniaxial stretching, it is preferable that it is longitudinal stretching.

In the present invention, as the configuration of the stretching step, for example,
1) Preheating zone / stretching zone / holding zone / cooling zone 2) Preheating zone / stretching zone / shrinking zone / holding zone / cooling zone 3) Preheating zone / lateral stretching zone / longitudinal stretching zone / holding zone / cooling zone 4) Preheating Examples include a combination of zone / lateral stretching zone / longitudinal stretching zone / shrinking zone / holding zone / cooling zone.

  The preheating zone refers to a section that runs while maintaining a constant interval between gripping tools that grip both ends of the laminated body at the oven inlet.

  The transverse stretching zone refers to a section in which the interval between the gripping tools that grip both ends of the laminate starts to reach a predetermined interval. At this time, the opening angle of the rail on which the gripping tools at both ends run may be opened at the same angle for both rails, or may be opened at different angles.

  The longitudinal stretching zone refers to a section in which a gripper that grips both ends of the laminate extends the laminate in the transport direction while changing the gripper interval.

  The contraction zone refers to a section in which the interval between gripping tools gripping both ends of the laminate is narrowed in a direction perpendicular to the stretching axis and reaches a predetermined interval.

  The holding zone refers to a section in which the gripping tools at both ends travel while being parallel to each other in a period in which the interval between the gripping tools after the transverse stretching zone or the longitudinal stretching zone is constant again.

  The cooling zone refers to a section where the temperature in the zone is set to the glass transition temperature Tg ° C. or lower of the thermoplastic resin constituting the laminate in the section after the holding zone.

  At this time, in consideration of shrinkage of the laminated body due to cooling, a rail pattern that narrows the gap between the opposing grippers in advance may be used.

  The temperature of each zone is within the range of Tg to Tg + 30 ° C., the temperature of the stretching zone is Tg to Tg + 30 ° C., and the temperature of the cooling zone is Tg−30 ° C. to Tg with respect to the glass transition temperature Tg of the substrate. It is preferable to set to.

  Subsequently, the stretched laminate obtained above is dyed with a dichroic substance, so that the dichroic substance is adsorbed on the hydrophilic polymer layer and functions as a polarizer (A). .

  The dyeing process is performed by adsorbing the dichroic substance to the hydrophilic polymer layer of the laminate. The dyeing process is performed, for example, by immersing the laminate in a solution (dyeing solution) containing a dichroic substance. As the staining solution, a solution in which a dichroic substance is dissolved in a solvent can be used. As the solvent, water is generally used, but an organic solvent compatible with water may be further added.

  Although there is no restriction | limiting in particular about the specific structure of the dichroic substance adsorb | sucked to a hydrophilic polymer layer, For example, an iodine, an organic dye, etc. are mentioned. Organic dyes include, for example, Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, Lemon Yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Spura Blue G, Spura Blue GL, Spura Orange GL, Direct Sky Blue, Direct First orange S, first black, etc. are used. Among these, from the viewpoints of water solubility and process suitability, it is preferable to use iodine as the dichroic substance, and it is preferable to further add iodide because dyeing efficiency can be further improved. Examples of the iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and iodide. Examples include titanium. The addition ratio of these iodides is preferably 0.01 to 10% by mass and more preferably 0.1 to 5% by mass in the dyeing solution. Among them, it is preferable to add potassium iodide, and the ratio (mass ratio) of iodine and potassium iodide is preferably in the range of 1: 5 to 1: 100, and in the range of 1: 6 to 1:80. More preferably, it is in a range of 1: 7 to 1:70.

  The immersion time of the stretched laminate in the dyeing solution is not particularly limited, but usually it is preferably in the range of 15 seconds to 5 minutes, more preferably 1 minute to 3 minutes. Moreover, it is preferable that it is in the range of 10-60 degreeC, and, as for the temperature of a dyeing | staining solution, it is more preferable that it exists in the range of 20-40 degreeC.

  After the dyeing treatment, the dichroic material is fixed by sequentially immersing the laminate in a decolorizing solution containing potassium iodide and a crosslinking solution containing boric acid or a boron compound and potassium iodide. Then, when it dries with a dryer, a coating type polarizer (A) is obtained.

[Production Method of Polarizing Plate of the Present Invention]
The method for producing a polarizing plate of the present invention is a method for producing a polarizing plate having the polarizer (A) and a transparent base material (B) described later, wherein the hydrophilic polymer layer of the polarizer (A) A polarizing plate is obtained by laminating a transparent base material (B) having an indentation elastic modulus of 4.5 GPa or more and a total light transmittance of 80% or more, sandwiched by a nip roller, on the surface on the air interface side. It is characterized by.

  FIG. 2 is a schematic view showing an example in which the polarizer (A) and the transparent substrate (B) are sandwiched and bonded by a nip roller.

  With the hydrophilic polymer layer 2 side of the polarizer (A) 3 facing inward, the transparent base material (B) 4 is bonded to the hydrophilic polymer layer 2 surface side by a pair of nip rollers 5, and the polarizing plate 10 Is made.

  When the nip pressure in the nip roller 5 is preferably in the range of 0.1 to 20 MPaPa, the surface of the hydrophilic polymer layer can be smoothed and wrinkles and peeling of the polarizing plate can be prevented. it can. More preferably, it is the range of 0.5-15Pa.

[1.3] Transparent substrate (B)
The transparent base material (B) according to the present invention is characterized in that the indentation elastic modulus is 4.5 GPa or more and the total light transmittance is 80% or more, and the outermost surface of the PVA polarizer has a high indentation elastic modulus. By being sandwiched by a material with a nip roller, the uneven shape on the outermost surface is smoothed, and light scattering on the surface is suppressed, so that the effect of depolarization hardly occurs.

  The indentation elastic modulus is a value measured by Martens hardness in the present invention, and the Martens hardness is measured by the following method.

[1.3.1] Physical properties of transparent substrate (B) [Martens hardness]
Martens hardness as used in the field of this invention is the hardness measured in the state (indentation) with which the test load was loaded, and is calculated | required from the value of the load-indentation depth curve at the time of load increase. Martens hardness includes both plastic and elastic deformation components.

  Martens hardness is defined for square and triangular pyramid indenters. Specifically, as shown by the following formula (B1), it is defined as a value obtained by dividing the test load F by the surface area As where the indenter enters from the contact zero point.

Formula (B1) Martens hardness = F / As
The Martens hardness is obtained, for example, from a load-indentation depth test in accordance with a method defined in ISO14577-1 Annex A. An example of a specific measurement method is shown below.

  This is performed according to the procedure of the indentation test specified by ISO14577-1 Annex A. As the testing machine, an ultra-micro hardness meter (for example, “Fischer Scope 100C” manufactured by Fischer Instruments) is used, and as the indenter, a pyramidal diamond indenter having a square base and a facing angle of 136 ° is used.

  The temperature during the test is 23 ° C., and a load of 10 mN is applied by pressing the indenter at a constant speed into the transparent base material (B) formed to a thickness of 25 μm. The Martens hardness is measured using a square pyramidal diamond indenter for the test piece. The Martens hardness is calculated by applying a load (10 mN) to the transparent substrate (B) and dividing it by the surface area of the indenter that has entered beyond the contact zero point.

  In the present invention, the Martens hardness is required to be 4.5 GPa or more in order to smooth the unevenness of the surface of the polarizer (A), preferably in the range of 4.5 to 10.0 GPa, Preferably, it is the range of 4.7-7.0GPa.

  As a method for controlling the Martens hardness of the transparent substrate (B) within the range defined in the present invention, it can be controlled by appropriately selecting a resin contained in the transparent substrate (B).

[Total light transmittance]
The total light transmittance of the transparent substrate (B) according to the present invention is required to be 80% or more when used as a polarizing plate.

  The total light transmittance in the transparent substrate (B) according to the present invention is preferably as high as possible, but is preferably higher than 85%, more preferably 90% or more, and still more preferably 92% or more. The total light transmittance can be calculated using the method described in JIS K 7105: 1981, that is, using an integrating sphere light transmittance measuring device, on the transparent base material (B) formed to a thickness of 25 μm. it can. As a measuring device, for example, a haze meter NDH5000 manufactured by Tokyo Denshoku Co., Ltd. can be used.

[Degree of polarization]
Specifically, the degree of polarization in the present invention can be determined according to the following method.

  After subjecting the polarizing plate sample to a humidity control treatment for 24 hours in an environment of 23 ° C. and 55% RH, the parallel transmittance and the orthogonal transmittance of light having a light wavelength of 550 nm were measured using an automatic polarizing film measuring device (VAP-7070, Measured using JASCO Corporation. Next, based on the obtained measured values, the degree of polarization (%) is obtained based on the following mathematical formula (B2). The degree of polarization (%) is preferably 99.995 or more.

[Film length, width, film thickness]
The transparent base material (B) according to the present invention is preferably long, specifically, preferably has a length of about 100 to 10,000 m, and is wound into a roll. The width of the transparent substrate (B) according to the present invention is preferably 1 m or more, more preferably 1.4 m or more, and particularly preferably 1.4 to 4 m.

  The film thickness of the transparent substrate (B) is preferably in the range of 5 to 200 μm from the viewpoint of strength and transparency, and more preferably in the range of 25 to 100 μm from the viewpoint of providing a thin film device. preferable. If the film thickness is 5 μm or more, a certain level of film strength can be developed. If the film thickness is 200 μm or less, flexibility can be exhibited.

[1.3.2] Transparent heat-resistant resin having an imide structure The transparent substrate (B) according to the present invention has an indentation elastic modulus of 4.5 GPa or more and a total light transmittance of 80% or more. Although a constituent material is not ask | required, it is preferable to contain the transparent heat resistant resin which has an imide structure.

  The transparent substrate (B) contains a compound having an imide structure, and the transparent heat-resistant resin having the imide structure has a structure represented by the following formula (1), the following formula (2), or the following It is preferably selected from polyimide, polyamideimide and polyetherimide having a structure represented by the formula (3). Hereinafter, the transparent substrate (B) may be referred to as a polyimide film.

(1) Transparent heat resistant resin having an imide structure (1.1) Polyimide having a structure represented by the formula (1) The transparent heat resistant resin having an imide structure according to the present invention (hereinafter also referred to as a polyimide resin). It is preferable that it is a polyimide resin represented by following formula (1) obtained by chemically imidizing a polyimide precursor.

[Polymerization of polyimide precursor]
An example of a method for producing a polyimide precursor having a structure represented by the formula (1) used in the present invention is shown below.

  First, diamine 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (TFMB) is dissolved in a polymerization solvent in a polymerization vessel. To this diamine solution, a powder of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanoic acid dianhydride (6FDA) is gradually added, and a mechanical stirrer is used to adjust the temperature to -20 to 100 ° C. In the range, preferably in the range of 20 to 60 ° C. for 1 to 72 hours. By using TFMB and 6FDA, visible light permeability and solubility are improved. The number of moles of diamine and the number of moles of tetracarboxylic dianhydride are charged at substantially equal moles. The total monomer concentration during the polymerization is 5 to 40% by mass, preferably 10 to 30% by mass. By carrying out polymerization in this monomer concentration range, a polyimide precursor solution having a uniform and high degree of polymerization can be obtained. When the polymerization is performed at a concentration lower than the above monomer concentration range, the degree of polymerization of the polyimide precursor is not sufficiently high, and the finally obtained polyimide film may be brittle, which is not preferable.

  The polymerization solvent is not particularly limited, but N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, hexamethylphosphoramide, dimethylsulfoxide, γ- Butyrolactone, 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane-bis (2-methoxyethyl) ether, terahydrofuran, 1,4-dioxane, picoline, pyridine, acetone, chloroform, toluene, Aprotic solvents such as xylene and protic solvents such as phenol, o-cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, and p-chlorophenol can be used. These solvents may be used alone or in combination of two or more.

[Production method of polyimide resin]
The polyimide resin represented by the formula (1) can be produced by a dehydration ring-closing reaction (imidation reaction) of the polyimide precursor obtained by the above method. For the imidization reaction, chemical imidization is used in which the resulting polyimide resin exhibits better dimensional stability. Chemical imidization can be performed using a dehydrating cyclization agent (chemical imidization agent) comprising an acid anhydride of an organic acid and an organic tertiary amine. For example, by using the polyimide precursor varnish as it is or after appropriately diluting with a solvent, a dehydration cyclization reagent is added thereto, and the mixture is stirred at 0 to 100 ° C., preferably 20 to 60 ° C. for 0.5 to 48 hours. It can be easily imidized.

  The acid anhydride of the organic acid used at that time is not particularly limited, and acetic anhydride, propionic anhydride, maleic anhydride, phthalic anhydride, etc. can be used, but the cost and ease of post-treatment are not limited. In view of the above, acetic anhydride is preferably used. The organic tertiary amine is not particularly limited, and pyridine, 1,5-dimethylpyridine, β-picoline, γ-picoline, lutidine, isoquinoline, triethylamine, N, N-dimethylaniline and the like can be used.

  In the chemical imidation reaction, the amount of acid anhydride used in the dehydration cyclization reagent is preferably in the range of 1 to 10 times the theoretical dehydration amount of the polyimide precursor, and the basicity in the dehydration cyclization reagent is The amount of catalyst used is preferably in the range of 0.1 to 2 moles relative to the acid anhydride. If the chemical imidization is carried out outside these ranges, the imidation reaction may not be completed, or the imidization may not be completed in the reaction solution and the imidization may be insufficient.

  After the imidization is completed, the reaction solution can be used for coating (casting) as it is, or the reaction solution is dropped into a large amount of poor solvent, or a poor solvent is added to the reaction solution to precipitate a polyimide resin. In the case of washing and removing the reaction solvent or chemical imidization, the excess chemical imidizing agent is removed, followed by drying under reduced pressure to obtain a polyimide resin powder. The poor solvent that can be used is not particularly limited as long as it does not dissolve the polyimide resin, but water, methanol, ethanol, from the viewpoint of affinity with the reaction solvent and chemical imidizing agent and ease of removal by drying. n-propanol, isopropanol and the like are preferably used.

  The weight average molecular weight of the polyimide resin is not particularly limited, but is preferably 5,000 to 2,000,000, more preferably 10,000 to 1,000,000, and further preferably 50,000 to 500,000. When the weight average molecular weight is 5000 or more, sufficient strength can be obtained in the case of a film, and dimensional stability tends to be improved, so that sufficient dimensional stability can be obtained. On the other hand, if it is 2,000,000 or less, the solution viscosity does not become too high and it is easy to handle. In addition, the said weight average molecular weight means the value of polyethyleneglycol conversion by size exclusion chromatography (SEC).

(1.2) Polyimide having a structure represented by Formula (2) or Formula (3) The polyimide resin according to the present invention is a polyimide having a repeating unit represented by the following Formula (2) (hereinafter, polyimide P and Or a polyimide composed of a repeating unit represented by the formula (2) and a repeating unit represented by the following formula (3) (hereinafter, both are referred to as polyimide P).

（式（３）中、Ｘは炭素数が２〜３９の２価の脂肪族基、炭素数が３〜３９の２価の脂環族基、炭素数が６〜３９の２価の芳香族基又はこれらの組み合わせからなる２価の基であり、Ｘの主鎖には、−Ｏ−、−ＳＯ_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＯＳｉ（ＣＨ_３）_２−、−Ｃ_２Ｈ_４Ｏ−及び−Ｓ−からなる群から選ばれた少なくとも１種の結合基が介在していてもよく、Ｘはカルボキシ基、ヒドロキシ基又はカルボニル基からなる群から選ばれた少なくとも１種の官能基を有していてもよい。）
前記ポリイミド樹脂は、前記式（２）で表される繰り返し単位、又は前記式（２）で表される繰り返し単位と前記式（３）で表される繰り返し単位からなり、式（２）で表される繰り返し単位の割合が全繰り返し単位の５０モル％を超え、好ましくは７０モル％以上、より好ましくは８０モル％以上（それぞれ１００モル％を含む）である。式（２）で表される繰り返し単位の割合が全繰り返し単位の５０モル％を超えると低吸水性を達成できるが、５０モル％以下であると、式（３）の構造によっては吸水率が高くなる。前記ポリイミドＰは、ブロックコポリマー又はランダムコポリマーのどちらでも良い。

(In the formula (3), X is a divalent aliphatic group having 2 to 39 carbon atoms, a divalent alicyclic group having 3 to 39 carbon atoms, and a divalent aromatic group having 6 to 39 carbon atoms. A divalent group consisting of a group or a combination thereof, and the main chain of X includes —O—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —OSi (CH ₃ ). _At least one linking group selected from the group consisting of _2- , -C ₂ H ₄ O- and -S- may be interposed, and X is selected from the group consisting of a carboxy group, a hydroxy group or a carbonyl group. And may have at least one functional group.)
The polyimide resin is composed of a repeating unit represented by the formula (2), or a repeating unit represented by the formula (2) and a repeating unit represented by the formula (3). The ratio of the repeating units to be used is more than 50 mol% of all repeating units, preferably 70 mol% or more, more preferably 80 mol% or more (each including 100 mol%). When the ratio of the repeating unit represented by the formula (2) exceeds 50 mol% of all the repeating units, low water absorption can be achieved, but when it is 50 mol% or less, depending on the structure of the formula (3), the water absorption may be Get higher. The polyimide P may be either a block copolymer or a random copolymer.

とは異なり、炭素数２〜３９の２価の脂肪族基、炭素数３〜３９の２価の脂環族基、炭素数６〜３９の２価の芳香族基又はこれらの組み合わせからなる２価の基である。Ｘの主鎖には、−Ｏ−、−ＳＯ_２−、−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−、−ＯＳｉ（ＣＨ_３）_２−、−Ｃ_２Ｈ_４Ｏ−、及び−Ｓ−からなる群から選ばれた少なくとも１の結合基が介在していてもよい。また、Ｘはカルボキシ基、ヒドロキシ基及びカルボニル基（Ｘの主鎖に含まれる）からなる群から選ばれた少なくとも一つの官能基を有していてもよい。Ｘの具体例としては、ポリアルキレン、ポリオキシアルキレン、キシリレン及びそれらのアルキル置換体、ハロゲン置換体、カルボキシ置換体及びヒドロキシ置換体などの２価の脂肪族基；シクロヘキサン、ジシクロヘキシルメタン、ジメチルシクロヘキサン、イソフォロン、ノルボルナン及びそれらのアルキル置換体、ハロゲン置換体、カルボキシ置換体及びヒドロキシ置換体等から誘導される２価の脂環族基；及び、ベンゼン、ナフタレン、ビフェニル、ジフェニルメタン、ジフェニルエーテル、ジフェニルスルホン、ベンゾフェノン及びそれらのアルキル置換体、ハロゲン置換体、カルボキシ置換体及びヒドロキシ置換体等から誘導される２価の芳香族基が挙げられる。また、Ｘは、樹脂強度の観点から、下記式（５）で表される構造であるのが好ましい。X in the above formula (3) is the following formula (4);

2 which is composed of a divalent aliphatic group having 2 to 39 carbon atoms, a divalent alicyclic group having 3 to 39 carbon atoms, a divalent aromatic group having 6 to 39 carbon atoms, or a combination thereof. Is a valent group. The main chain of X includes —O—, —SO ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —OSi (CH ₃ ) ₂ —, —C ₂ H ₄ O—, and —S. At least one linking group selected from the group consisting of — may intervene. X may have at least one functional group selected from the group consisting of a carboxy group, a hydroxy group, and a carbonyl group (included in the main chain of X). Specific examples of X include polyalkylene, polyoxyalkylene, xylylene and their alkyl-substituted, halogen-substituted, carboxy-substituted, and hydroxy-substituted divalent aliphatic groups; cyclohexane, dicyclohexylmethane, dimethylcyclohexane, Divalent alicyclic groups derived from isophorone, norbornane and their alkyl-substituted, halogen-substituted, carboxy-substituted, hydroxy-substituted, etc .; and benzene, naphthalene, biphenyl, diphenylmethane, diphenyl ether, diphenylsulfone, benzophenone And divalent aromatic groups derived from these alkyl-substituted, halogen-substituted, carboxy-substituted, hydroxy-substituted and the like. Moreover, it is preferable that X is a structure represented by following formula (5) from a viewpoint of resin strength.

When the polyimide P is used as a solution, the molecular weight is preferably expressed by viscosity, particularly logarithmic viscosity. The logarithmic viscosity η (measured at 30 ° C. using a 0.5 g / cm ³ N-methyl-2-pyrrolidone solution) of polyimide P is preferably 0.3 to 2 cm ³ / g. If it is less than 0.3 cm ³ / g, the strength of the polyimide resin itself is weak, and an optical film having sufficient peel strength cannot be obtained. If it exceeds 2.0 cm ³ / g, the solution becomes highly viscous and difficult to cast, requires significant dilution, and is difficult to handle.

  Usually, the molecular terminal of the polyimide P is an amino group, a carboxy group, or a carboxylic anhydride group. By reacting a compound having a carboxylic acid anhydride group or an amino group at the molecular end, the functional group at the molecular end is reduced as much as possible, or an intentionally functional group such as an amino group or a carboxy group is present at the molecular end. Groups and other substituents can be introduced. In order to reduce the water absorption rate, a substituent having a small polarity (substituent having no functionality) may be introduced at the molecular end. The water absorption of the polyimide P measured by the method described later is preferably 2.5% or less. The minimum value of water absorption that can be achieved industrially is usually about 1%.

  The water absorption rate in the present invention represents a mass increase rate after immersing the resin in 23 ° C. water for 24 hours. Next, a specific method for obtaining the water absorption rate according to the present invention will be described.

  After the film made from the resin is left in a room adjusted to 23 ° C. and 55% RH for 4 hours or more, the mass of the film is measured, and this is defined as W1. Next, after immersing the film in distilled water at 23 ° C. for 24 hours, the mass of the film taken out is measured, and this is defined as W2. The water absorption rate is calculated based on the following formula.

Water absorption rate (%) = (W2−W1) ÷ W1 × 100
Polyimide P consists of 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA) and 1,2,4,5-cyclohexanetetracarboxylic acid esters. It is obtained by reacting at least one tetracarboxylic acid component (Y) selected from reactive derivatives such as diamine and at least one diamine component (Z) selected from diamines and reactive derivatives thereof. As the tetracarboxylic acid component (Y), HPMDA is preferable. In addition, the tetracarboxylic acid component (Y) and the diamine component (Z) include isomers.

Examples of the diamine component (Z) include diamine, diisocyanate, and diaminodisilane, and diamine is preferred. The diamine component (diamine component (Z1)) for forming the repeating unit of the above formula (2) is 4,4′-bis (4-aminophenoxy) biphenyl (BAPB) and a reactive derivative thereof. The diamine component (diamine component (Z2)) for forming the repeating unit (3) is NH ₂ —X—NH ₂ (X is the same as described above) and a reactive derivative thereof.

  The diamine component (Z2) may be an aromatic diamine, an aliphatic diamine, an alicyclic diamine, a reactive derivative of the above diamine, or a mixture thereof, including a carboxy group, a hydroxy group, and a carbonyl group (in the main chain of X). It may have at least one functional group selected from the group consisting of: In the present invention, the “aromatic diamine” represents a diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic group, alicyclic group, aromatic group, other It may contain a substituent. The term “aliphatic diamine” refers to a diamine in which an amino group is directly bonded to an aliphatic group, and an aliphatic group, an alicyclic group, an aromatic group, and other substituents are included in a part of the structure. May be. “Alicyclic diamine” refers to a diamine in which an amino group is directly bonded to an alicyclic group, and an aliphatic group, an alicyclic group, an aromatic group, and other substituents are added to a part of the structure. It may be included. For example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) is an aromatic diamine because the amino group is directly bonded to the aromatic ring (benzene ring), and m-xylyl. Range amine (MXDA) is an aliphatic diamine because the amino group is directly bonded to an aliphatic group (methylene group).

  In general, when tetracarboxylic dianhydride is reacted with an aliphatic diamine or alicyclic diamine, the polyamic acid as an intermediate product and the amino group derived from the aliphatic diamine or alicyclic diamine form a strong salt. In addition, it is difficult to obtain a high molecular weight polyimide. Therefore, it is necessary to devise such as using a solvent having a relatively high salt solubility, such as cresol. However, when 1,2,4,5-cyclohexanetetracarboxylic dianhydride is used as the tetracarboxylic dianhydride, the amino acid group derived from the polyamic acid and the aliphatic diamine or alicyclic diamine has a relatively weak bond. Thus, the imidization reaction proceeds relatively easily and can be easily increased in molecular weight.

  Examples of the aliphatic diamine include ethylene diamine, hexamethylene diamine, polyethylene glycol-bis (3-aminopropyl) ether, polypropylene glycol bis (3-aminopropyl) ether, 1,3-bis (aminomethyl) cyclohexane, 1, Examples include 4-bis (aminomethyl) cyclohexane, p-xylylenediamine, m-xylylenediamine, and siloxane diamines.

  Examples of the alicyclic diamine include 4,4′-diaminodicyclohexylmethane, isophorone diamine, norbornane diamine, and the like.

  Examples of the aromatic diamine include 1,4-phenylenediamine, 1,3-phenylenediamine, 2,4-toluenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'- Diaminodiphenylmethane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, α, α'-bis (4 -Aminophenyl) -1,4-diisopropylbenzene, α, α'-bis (3-aminophenyl) -1,4-diisopropylbenzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4,4'-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- 3-aminophenoxy) phenyl] sulfone, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene and the like.

  Examples of the diamine having a functional group include 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2,4-diaminophenol, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, in particular, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane (MBAA), 3,5 -Diaminobenzoic acid (DBA), 3,3'-dihydroxy-4,4'-diaminobiphenyl (HAB), 4,4'-diaminobenzophenone (4,4'-DBP) are preferred.

  It is preferable to use MXDA and BAPP as the diamine component (Z2).

  The polyimide P contains the tetracarboxylic acid component (Y) with respect to 1 mol of the diamine component (Z) (diamine component (Z1) or diamine component (Z1) + diamine component (Z2)), preferably 0.00. It is produced by reacting 66 to 1.5 mol, more preferably 0.9 to 1.1 mol, and still more preferably 0.97 to 1.03 mol.

  For example, a polyimide P having a logarithmic viscosity η within the above range is produced by adjusting at least one of the conditions such as the use ratio of raw materials, reaction temperature and time, presence / absence and use of a terminal terminator, and the amount of catalyst. can do. Those skilled in the art can easily adjust the conditions by performing a preliminary reaction or the like. For example, when the logarithmic viscosity η is adjusted by the molar ratio of the tetracarboxylic acid component (Y) and the diamine component (Z) and the reaction time, the closer the molar ratio is to 1, the longer the reaction time, The logarithmic viscosity η increases within the above range. As the molar ratio is far from 1 in the range of 0.66 to 1.5 and the reaction time is shorter, the logarithmic viscosity η is smaller in the range. In the solution polymerization method, the relationship between the viscosity of the reaction solution, the reaction time, and other reaction conditions, and the logarithmic viscosity corresponding thereto is obtained in advance, and the end point of the reaction is determined based on this relationship. A polyimide P having a logarithmic viscosity η can be produced. The reaction time is preferably 2 to 12 hours, and the reaction temperature is preferably 180 to 205 ° C.

  The polyimide P is usually produced as an organic solvent solution.

  The organic solvent is not particularly limited. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methyl Caprolactam, hexamethylphosphoramide, tetramethylenesulfone, dimethylsulfoxide, m-cresol, phenol, p-chlorophenol, 2-chloro-4-hydroxytoluene, diglyme, triglyme, tetraglyme, dioxane, γ-butyrolactone, dioxolane, Cyclohexanone, cyclopentanone and the like can be used, and two or more kinds may be used in combination. However, considering the performance of polyimide varnish composed of polyimide P and a solvent, N-methyl-2-pyrrolidone (NMP), N, N-dimethylacetamide (DMAC), and γ-butyrolactone (GBL) may be used alone or in combination. preferable. The organic solvent is used in such an amount that the polyimide P concentration in the obtained organic solvent solution is preferably 1 to 50% by mass, more preferably 5 to 40% by mass. In addition, in the case of production by solution polymerization, a poor solvent such as hexane, heptane, benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene and the like can be used together with the above solvent to such an extent that the polymer does not precipitate.

  Polyimide P is obtained by (1) solution polymerization method, (2) preparing a polyamic acid solution, forming a film and imidizing it, and (3) obtaining a salt or imide oligomer such as HPMDA half ester salt, It can be produced by a method of performing phase polymerization, (4) a method of reacting tetracarboxylic dianhydride and diisocyanate, or other conventionally known methods. You may use each method together. The reaction between the tetracarboxylic acid component (Y) and the diamine component (Z) may be carried out in the presence of a conventionally known catalyst such as an acid, a tertiary amine or an anhydride.

Among these methods, since an organic solvent solution of polyimide P is obtained directly, the following solution polymerization methods (1) to (3) are preferable.
(1) A mixture containing a diamine component (Z), an organic solvent, and, if necessary, a catalyst is stirred at 10 to 600 rpm to form a homogeneous solution, which is maintained at a temperature of 30 to 90 ° C., and the tetracarboxylic acid component (Y) And if necessary, a catalyst is added.
(2) A mixture containing a tetracarboxylic acid component (Y), an organic solvent, and, if necessary, a catalyst is stirred at 10 to 600 rpm to form a homogeneous solution, which is maintained at a temperature of 30 to 90 ° C., and a diamine component (Z) And if necessary, a catalyst is added.
(3) After the method (1) or (2), the temperature is raised to 160 to 230 ° C, preferably 180 to 205 ° C over 0.1 to 6 hours. This temperature depends on the boiling point of the organic solvent used. While collecting the components to be removed outside the reaction system, the temperature is kept substantially constant for 0.5 to 24 hours, preferably 2 to 12 hours. Thereafter, if necessary, an organic solvent is further added and cooled to an appropriate temperature.

  Solution polymerization for producing polyimide P includes trimethylamine, triethylamine (TEA), tripropylamine, tributylamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N- The reaction may be performed in the presence of at least one catalyst selected from tertiary amine compounds such as methylpyrrolidine, N-ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline and isoquinoline. When used, the amount of the catalyst used is preferably from 0.1 to 100 mol%, more preferably from 1 to 10 mol% of the tetracarboxylic acid component (Y).

(1.3) Polyamideimide Polyamideimide used in the present invention is an acid component,
a) tricarboxylic acid; diphenyl ether-3,3 ', 4'-tricarboxylic acid, diphenylsulfone-3,3', 4'-tricarboxylic acid, benzophenone-3,3 ', 4'-tricarboxylic acid, naphthalene-1,2 , 4-tricarboxylic acid, monoanhydrides such as tricarboxylic acid such as butane-1,2,4-tricarboxylic acid, esterified compounds, or a mixture of two or more.

  b) Tetracarboxylic acid; diphenylsulfone-3,3 ', 4,4'-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid , Naphthalene-1,4,5,8-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid monoanhydride, dianhydride , Esterified compounds alone, or a mixture of two or more.

  c) Dicarboxylic acid; adipic acid, azelaic acid, sebacic acid, dicarboxylic acid of cyclohexane-4,4'-dicarboxylic acid, and monoanhydrides and esterified products thereof.

As an amine component,
d) Amine component 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-diethoxy-4,4'-diaminobiphenyl, p-phenylenediamine, m -Phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminobiphenyl, 3,3 ' -Diaminobiphenyl, 3,3'-diaminobenzanilide, 4,4'-diaminobenzanilide, 4,4'-diaminobenzene Nzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 2,6-tolylenediamine, 2,4-tolylenediamine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl Sulfide, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, p-xylenediamine, m-xylenediamine, 2,2 ' -Bis (4-aminophenyl) propane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2 , 2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4 Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] propane, 4,4′-bis (4-aminophenoxy) biphenyl, 4 , 4'-bis (3-aminophenoxy) biphenyl, tetramethylenediamine, hexamethylenediamine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, cyclohexane-1,4-diamine, diaminosiloxane, or their corresponding diisocyanates These may be used alone or in combination of two or more.

  In particular, trimellitic anhydride (TMA), 3,3,4 ', 4'-benzophenonetetracarboxylic dianhydride (BTDA), and 3,3,4', 4'-biphenyltetracarboxylic acid as acid components Polyamideimide resin polymerized with a raw material containing dianhydride (BPDA) and 1,5-naphthalene diisocyanate (NDI) as an isocyanate component is preferable.

  The molar ratio between the imide bond and the amide bond of the polyamideimide is preferably 99/1 to 60/40, more preferably 99/1 to 75/25, and even more preferably 90/10 to 80/20. is there. When the molar ratio of the imide bond to the amide bond is 60/40 or more, the heat resistance, moisture resistance reliability, and heat resistance reliability are improved. On the other hand, if it is 99/1 or less, the elastic modulus tends to be low, and the folding resistance and bending characteristics tend to be improved.

  In one preferred embodiment, the unit represented by the formula (6) is an essential component, and at least one selected from the group represented by the formula (7), the formula (8), and the formula (9). Is a polyamidoimide resin containing as a repeating unit in the molecular chain.

（Ｘは、酸素原子、ＣＯ、ＳＯ_２、又は、結合を表し、ｎは０又は１を表す。）

（Ｙは、酸素原子、ＣＯ、又はＯＯＣ−Ｒ−ＣＯＯを表し、ｎは０又は１を、Ｒは二価の有機基を表す。）

(X represents an oxygen atom, CO, SO ₂ , or a bond, and n represents 0 or 1.)

(Y represents an oxygen atom, CO, or OOC-R-COO, n represents 0 or 1, and R represents a divalent organic group.)

Here, in the formula (7), X is SO ₂ or a bond (biphenyl bond) or n = 0 is preferable, and a bond (biphenyl bond) or n = 0 is more preferable. In formula (8), Y is preferably a benzophenone type (CO) or a bond type (biphenyl bond).

  One preferred embodiment is that formula (6) is a repeating unit from trimellitic anhydride and 1,5-naphthalene diisocyanate, formula (7) is a repeating unit from terephthalic acid and 1,5-naphthalene diisocyanate, formula (8) Is a repeating unit from biphenyltetracarboxylic dianhydride and / or benzophenonetetracarboxylic dianhydride and 1,5-naphthalene diisocyanate, the content ratio of which is the formula (6) / {formula (7) + formula ( 8) + Formula (9)} = 1/99 to 40/60 molar ratio, and Formula (7) / Formula (8) = 10/90 to 90/10 molar ratio is preferable.

  The polyamideimide resin can be synthesized by a usual method. For example, the isocyanate method, the amine method (acid chloride method, low temperature solution polymerization method, room temperature solution polymerization method, etc.), etc., but the polyamideimide resin used in the present invention is preferably soluble in an organic solvent. For reasons such as ensuring the reliability of strength (adhesive strength), production by the isocyanate method is preferred. Also, industrially, it is preferable because the solution at the time of polymerization can be applied as it is.

The molecular weight of the polyamide-imide resin used in the present invention is 0.3 to 2.5 cm ³ / g in N-methyl-2-pyrrolidone (polymer concentration 0.5 g / cm ³ ) and logarithmic viscosity at 30 ° C. Those having a corresponding molecular weight are preferred, more preferably those having a molecular weight corresponding to 0.5 to 2.0 cm ³ / g. When the logarithmic viscosity is 0.3 cm ³ / g or more, mechanical properties are sufficient when formed into a molded product such as a film. On the other hand, if it is 2.0 cm ³ / g or less, the solution viscosity does not become too high and the molding process becomes easy.

(1.4) Polyetherimide The polyetherimide used in the present invention is a thermoplastic resin containing an aromatic nucleus bond and an imide bond in its structural unit, and is not particularly limited. It is a polyetherimide having a repeating unit represented by the formula (10) or the following formula (11).

  The polyetherimide having the repeating unit represented by the above formula (10) is trade names “Ultem 1000” (glass transition temperature: 216 ° C.) and “Ultem 1010” (glass transition temperature: 216 ° C.) manufactured by General Electric Co., Ltd. Examples of the polyetherimide having a repeating unit represented by the above formula (11) include “Ultem CRS5001” (glass transition temperature Tg 226 ° C.), and other specific examples include trade names “Mitsui Chemicals, Inc.” Aurum PL500AM ”(glass transition temperature 258 ° C.).

  The method for producing the polyetherimide is not particularly limited. Usually, the amorphous polyetherimide having the above formula (10) is 4,4 ′-[isopropylidenebis (p-phenyleneoxy)]. As a polycondensate of diphthalic dianhydride and m-phenylenediamine, and polyetherimide having the above structural formula (11), 4,4 ′-[isopropylidenebis (p-phenyleneoxy)] diphthalic acid It is synthesized by a known method as a polycondensate of anhydride and p-phenylenediamine.

  Further, the polyetherimide used in the present invention may contain other copolymerizable monomer units such as an amide group, an ester group, and a sulfonyl group within the range not exceeding the gist of the present invention. In addition, polyetherimide can be used individually by 1 type or in combination of 2 or more types.

(1.5) Additives When the polyimide resin according to the present invention is formed by a solution casting film forming method, various additives can be added to the dope containing the polyimide resin. Additives that can be used are described below.

  A thermally conductive filler may be added to the dope containing a polyimide resin as long as the effects of the present invention are not impaired. Thereby, the thermal conductivity of a polyimide film can be raised.

  The thermally conductive filler is preferably a highly thermally conductive filler, and specifically includes aluminum, copper, nickel, silica, diamond, alumina, magnesia, beryllia, boron nitride, aluminum nitride, silicon nitride, and silicon carbide. The filler shape is not particularly limited to a spherical or plate-like material, or a needle shape. Among these, at least one filler selected from silica, alumina, aluminum nitride, boron nitride, silicon nitride, and magnesia is preferable.

  Further, a dehydrating agent may be added to the dope containing the polyimide resin according to the present invention. Specific examples of the dehydrating agent include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride, but acetic anhydride and / or anhydrous Benzoic acid is preferred. The content of the dehydrating agent relative to the polyamic acid or polyimide is preferably in the range where the content of dehydrating agent (mole) / polyamic acid or polyimide content (mole) is 0.1 to 5.0. In this case, a gelation retarder such as acetylacetone may be used in combination.

  Moreover, you may add surfactant, such as a fluorine type and a polysiloxane type, to dope containing the polyimide resin which concerns on this invention, for example. When a surfactant is added, a film with good surface smoothness can be easily obtained. A commercially available product may be used as the surfactant, and examples of the fluorosurfactant include a mega-fac (registered trademark) series manufactured by DIC Corporation and a footer such as Neos Corporation's Footgent (registered trademark) series. Gent (registered trademark) 251, 212MH, 250, 222F, 212D, FTX-218, and the like. Examples of the polysiloxane surfactant include BYK-307, BYK-315, BYK-320, BYK-325, BYK-330, BYK-331, BYK-332, BYK-333, BYK manufactured by BYK-Chemie Japan Co., Ltd. -344 and the like.

  Moreover, you may add antioxidant, such as a phenol type, sulfur type, phosphoric acid type, phosphorous acid type, to dope containing the transparent heat resistant resin which concerns on this invention.

In addition, various other functional materials may be added to the dope containing the polyimide resin according to the present invention. Various functional materials include, for example, conductive materials such as carbon nanotubes and nano metal materials, ferroelectric materials such as barium titanate, and phosphors such as ZnS: Ag, ZnS: Cu, and Y ₂ O ₂ S: Eu. UV absorbers and the like.

  Further, a phosphorus flame retardant may be added to the dope containing the polyimide resin according to the present invention. Thereby, a flame retardance can be provided to a polyimide-type optical film. Examples of the phosphorus-based flame retardant include ammonium polyphosphate, phosphate ester, condensed phosphate ester, phenoxyphosphazene compound, phosphate ester amide, and the like. Among these phosphorus flame retardants, it is preferable to use a phenoxyphosphazene compound. As the phenoxyphosphazene compound, for example, SPS-100 manufactured by Otsuka Chemical Co., Ltd. can be used. Although a flame retardant can be imparted by mixing a halogen type flame retardant, it is preferable to use a phosphorus-based flame retardant.

(1.6) Imidization treatment of film When a cast film is formed using polyamic acid, a polyimide film can be produced by applying an imidization treatment to the obtained film.

When the film is subjected to appropriate heat treatment, imidization in the polymer chain molecules and between the polymer chain molecules proceeds to improve the mechanical properties. However, as the heat treatment is performed, the optical film using polyimide changes in the absorption wavelength. The color changes with color. In particular, in a film using a thin polyimide of 4.0 to 15.0 μm, the higher the L ^* value, the thinner the color, so the horizontal unevenness due to thickness unevenness is difficult to see, but the appearance is good. Since the progress of imidization is not sufficient, mechanical properties such as flex resistance and breaking strength of the polyimide film are deteriorated. On the other hand, if the L ^* value is too low, the color contrast due to the thickness unevenness becomes clear and the horizontal unevenness deteriorates, and the optical film using polyimide partially carbonizes and becomes brittle. Characteristics are significantly regressed. For the above reasons, in the method for producing a transparent base material (B) using the polyimide used in the present invention, it is good to maintain good mechanical properties with an L ^* value of 30 to 55, more preferably, The L ^* value is preferably 38 to 54.

The L ^* value of the film was measured using SM-7-CH manufactured by Suga Test Instruments. About each sample divided into 5 in the film width direction, the range of 30 mm x 30 mm centering on the center position of the width direction was cut out and measured, and it was set as the 5-point average value. In addition, since the sensitivity of a detector becomes dull and the appropriate evaluation cannot be performed when the film thickness is thin, the L ^* value is one for a film having a thickness of 50 μm or more, and 50 μm or more for a film having a thickness of less than 50 μm. It is a value measured by overlapping the minimum number of sheets.

Regarding a heat treatment method for obtaining a film having an L ^* value of 30 to 55, for example, a method of adjusting the heat treatment amount using a known means such as hot air or an electric heater (for example, an infrared heater). Can be mentioned.

  In the method for producing a film using the polyimide according to the present invention, a solution of a polyamic acid not containing a ring-closing catalyst and a dehydrating agent is cast, formed into a film, heated and dried on the support, and then the film from the support. Can be used, and a thermal ring closure method in which imidization is performed by further drying and heat treatment at a high temperature can be used. In addition, a solution of a polyamic acid containing a ring-closing catalyst and a dehydrating agent is cast to form a film, and after partially imidizing on the support to form a film, the film is peeled off from the support. Alternatively, a chemical ring closure method in which heat drying / imidization and heat treatment are performed can also be used. As the ring-closing catalyst, the above-mentioned tertiary amine or the like can be used.

  In the thermal ring closure method, heat treatment can be performed by using, for example, an infrared heater.

  As the infrared heater, for example, a heater main body formed so that a filament is surrounded by an inner tube is covered with an outer tube, and a cooling fluid can be circulated between the heater main body and the outer tube. The filament is energized and heated to 700 to 1200 ° C., and emits infrared rays having a peak at a wavelength near 3 μm. The inner tube and the outer tube are made of quartz glass, borosilicate crown glass, or the like, and function as a filter that passes infrared rays having a wavelength of 3.5 μm or less and absorbs infrared rays having a wavelength exceeding 3.5 μm. Such infrared heaters irradiate the film with infrared light having a wavelength of 3.5 μm or less through an inner tube or an outer tube when infrared light having a peak near 3 μm is emitted from the filament. By irradiating with infrared rays having this wavelength, the mixed solvent in the film can be efficiently evaporated and the polyamic acid in the film can be imidized. The inner tube and the outer tube absorb infrared rays having a wavelength exceeding 3.5 μm, but are cooled by the cooling fluid flowing through the flow path, so that the temperature can be maintained below the ignition point of the mixed solvent evaporating from the film. Is possible.

  In the method for producing a film using the polyimide according to the present invention, any of the above ring closure methods may be adopted, but the chemical ring closure method requires equipment for containing a ring closure catalyst and a dehydrating agent in the polyamic acid solution. However, it can be said to be a more preferable method in that a film having self-supporting properties can be obtained in a short time.

(1.7) Method for Producing Film Using Transparent Heat Resistant Resin Having Imide Structure A specific example of the method for producing the transparent substrate (B) according to the present invention (hereinafter also referred to as polyimide film) will be described below.

  A step of preparing a dope by dissolving the transparent heat resistant resin having an imide structure according to the present invention in a mixed solvent preferably containing 50% by mass or more of dichloromethane (dope preparation step), and flowing the dope on a support. Extending the casting film to form a casting film (casting process), evaporating the solvent from the casting film on the support (solvent evaporation process), and peeling the casting film from the support (peeling process) A step of drying the obtained film (first drying step), a step of stretching the film (stretching step), a step of performing a bending treatment while further drying the stretched film (second drying step), and It is preferably performed by a step of winding a polyimide film (winding step), a step of heating the film to imidize (heating step), or the like.

  Hereinafter, each step will be specifically described.

[A] Dope preparation step In the dope preparation step, it is preferable to prepare a dope in which the polyimide resin according to the present invention is dissolved in dichloromethane as a main solvent, preferably a mixed solvent containing dichloromethane at 50% by mass or more of the solvent. .

  Thereafter, the prepared dope is guided to a filter by a liquid feed pump or the like and filtered.

  That is, the foreign substance in the dope is removed by filtering the dope at a temperature of boiling point at 1 atm of dichloromethane, which is the main solvent of the dope, at a temperature of 5 ° C. or higher. A preferred temperature range is 45 to 120 ° C, more preferably 45 to 70 ° C, and still more preferably 45 to 55 ° C.

  Here, it is preferable to use a solvent containing 50% by mass or more of dichloromethane from the viewpoint of improving the smoothness of the polyimide film.

  The solvent contained together with dichloromethane may be any solvent that can dissolve the transparent heat-resistant resin having an imide structure according to the present invention, such as ethanol, butanol, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylcaprolactam, hexamethylphosphoramide, tetramethylenesulfone, dimethylsulfoxide, m-cresol, Phenol, p-chlorophenol, 2-chloro-4-hydroxytoluene, diglyme, triglyme, tetraglyme, dioxane, γ-butyrolactone, dioxolane, cyclohexanone, cyclopentanone, 1,4-dioxane, epsilon caprolact Beam, chloroform and the like can be used, and may be used in combination of two or more. In addition to these solvents, a poor solvent such as hexane, heptane, benzene, toluene, xylene, chlorobenzene, or o-dichlorobenzene may be used to the extent that polyamic acid or polyimide does not precipitate.

  Moreover, as a solvent contained in a mixed solvent with the said dichloromethane, it is preferable that it is a solvent whose boiling point is higher than a dichloromethane. Thereby, the curling of the cast film after peeling from the support can be effectively suppressed.

[B] Casting film forming step An endless support such as a stainless steel belt or a rotating metal drum that feeds the prepared dope to a die through a feed pump (for example, a pressurized metering gear pump) The dope is cast from the die at the casting position on the metal support.

  The metal support in casting (cast) is preferably a mirror-finished surface, and the support is a stainless steel belt or a drum whose surface is plated with a casting, or a metal support such as a stainless steel belt or a stainless steel belt. Is preferably used. The width of the cast can be in the range of 1 to 4 m, preferably in the range of 1.5 to 3 m, more preferably in the range of 2 to 2.8 m. Note that the support may not be made of metal.

  The running speed of the metal support is not particularly limited, but is usually 5 m / min or more, preferably 10 to 180 m / min, particularly preferably 80 to 150 m / min. As the traveling speed of the metal support increases, entrained gas is more likely to be generated, and the occurrence of film thickness unevenness due to disturbance is more pronounced.

  The traveling speed of the metal support is the moving speed of the outer surface of the metal support.

  Although the surface temperature of a metal support body is not restrict | limited in particular, Usually, it is 0 degreeC or more, Preferably it is 20-60 degreeC, More preferably, it is 20-25 degreeC.

  The die has a shape that becomes gradually narrower toward the discharge port in a vertical cross section with respect to the width direction. In general, the die usually has tapered surfaces on the downstream side and the upstream side in the lower traveling direction, and a discharge port is formed in a slit shape between the tapered surfaces. A die made of metal is preferably used, and specific examples include stainless steel, titanium, and the like. In the present invention, when manufacturing films having different thicknesses, it is not necessary to change to dies having different slit gaps.

  It is preferable to use a pressure die that can adjust the slit shape of the die portion of the die and easily make the film thickness uniform. Examples of the pressure die include a coat hanger die and a T die, and any of them is preferably used. Even when films with different thicknesses are continuously manufactured, the discharge rate of the dies is maintained at a substantially constant value. Therefore, when a pressure die is used, conditions such as extrusion pressure and shear rate are also substantially reduced. Maintained at a constant value. In order to increase the film forming speed, two or more pressure dies may be provided on the metal support, and the dope amount may be divided and laminated.

The discharge amount of the dope from the die is preferably 20 to 1000 g / m ² , more preferably 40 to 800 g / m ² . In the present invention, even when films having different thicknesses are continuously produced, it is preferable that the dope discharge amount from the die is maintained at a substantially constant value within the above range. When the discharge amount is 40 g / m ² or more, the cast film is not easily affected by disturbances such as vibration and wind, and thus film thickness unevenness can be sufficiently prevented. When the discharge amount is 800 g / m ² or less, the shrinkage does not occur excessively, and the film thickness unevenness due to the contraction does not occur, so that the film thickness unevenness can be sufficiently prevented.

[C] Solvent evaporation step The solvent evaporation step is a preliminary drying step in which the casting film (also referred to as web) is heated on the metal support to evaporate the solvent.

  In order to evaporate the solvent, for example, a method of blowing heated air from the casting membrane side and the back side of the metal support by a dryer, a method of transferring heat from the back side of the metal support by a heating liquid, a method of transferring heat from the front and back by radiant heat Etc. A method of appropriately selecting and combining them is also preferable. The surface temperature of the metal support may be the same as a whole or may vary depending on the position. The temperature of the heating air is preferably 10-80 ° C.

  In the method of heating the metal support, a higher temperature is preferable because the drying speed of the cast film can be increased. However, if the temperature is too high, the cast film may foam or the planarity may deteriorate. Therefore, it is preferable to carry out at 10-30 degreeC.

  In the solvent evaporation step, it is preferable to dry the cast film until the residual solvent amount is 10 to 150% by mass from the viewpoint of peelability of the cast film and transportability after peeling.

  In the present invention, the residual solvent amount can be expressed by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is the mass at a predetermined point of the casting membrane (film), and N is the mass when M is dried at 200 ° C. for 3 hours. In particular, M when calculating the amount of residual solvent achieved in the solvent evaporation step is the mass of the cast film immediately before the peeling step.

[D] Peeling process The casting film from which the solvent has evaporated on the metal support is peeled off at the peeling position.

  The peeling tension at the time of peeling the metal support and the cast film is usually in the range of 60 to 400 N / m. However, if wrinkles easily occur at the time of peeling, the peeling is carried out with a tension of 190 N / m or less. It is preferable.

  In the present invention, the temperature at the peeling position on the metal support is preferably in the range of −50 to 60 ° C., more preferably in the range of 10 to 40 ° C., and in the range of 15 to 40 ° C. Most preferred.

  The peeled film may be sent directly to the stretching step, or may be sent to the stretching step after being sent to the first drying step so as to achieve a desired residual solvent amount. In the present invention, from the viewpoint of stable conveyance in the stretching step, it is preferable that the film is sequentially sent to the first drying step and the stretching step after the peeling step.

[E] First drying step The first drying step is a drying step in which the film is heated and the solvent is further evaporated. The drying means is not particularly limited, and for example, hot air, infrared rays, a heating roller, microwaves and the like can be used. From the viewpoint of simplicity, it is preferable to dry with hot air or the like while transporting the film with rollers arranged in a staggered manner. The drying temperature is preferably in the range of 30 to 200 ° C. in consideration of the residual solvent amount and the stretching ratio in transportation.

[F] Stretching Step By stretching the film peeled from the metal support, the film thickness, flatness, orientation, etc. of the film can be controlled.

  In the manufacturing method of the polyimide film which concerns on this invention, it is preferable to extend | stretch in a longitudinal direction and / or a lateral direction.

  The stretching operation may be performed in multiple stages. Moreover, when performing biaxial stretching, simultaneous biaxial stretching may be performed and you may implement in steps. In this case, stepwise means that, for example, stretching in different stretching directions can be sequentially performed, stretching in the same direction is divided into multiple stages, and stretching in different directions is added to any one of the stages. Is also possible.

Thus, for example, the following stretching steps are possible:
-Stretch in the longitudinal direction-> Stretch in the width direction-> Stretch in the longitudinal direction-> Stretch in the longitudinal direction-Stretch in the width direction-> Stretch in the width direction-> Stretch in the longitudinal direction-> Stretch in the longitudinal direction Includes stretching in one direction and contracting the other while relaxing the tension.

  The amount of residual solvent at the start of stretching is preferably in the range of 0.5 to 100% by mass.

  If the amount of the residual solvent is 2% by mass or more, the film thickness deviation is small and is preferable from the viewpoint of flatness, and if it is within 10% by mass, the surface unevenness is reduced, and the flatness is improved.

  In the method for producing a polyimide film according to the present invention, the film may be stretched in the longitudinal direction and / or the width direction, preferably in the width direction so that the film thickness after stretching is in a desired range. The film is preferably stretched in a temperature range of (TgL−200) to (TgH + 50) ° C., where TgL is the lowest Tg and TgH is the highest Tg of the glass transition point (Tg) of the film. If it extends in the said temperature range, since a extending | stretching stress can be reduced, a haze will become low. Moreover, generation | occurrence | production of a fracture | rupture is suppressed and the polyimide film excellent in planarity and the coloring property of the film itself is obtained. The stretching temperature is more preferably in the range of (TgL−150) to (TgH + 40) ° C.

  In the manufacturing method of the polyimide film which concerns on this invention, the film which has the self-supporting property peeled from the support body can be extended | stretched to a longitudinal direction by restrict | limiting a running speed with an extending | stretching roller. The draw ratio in the longitudinal direction is preferably 1.05 to 2.50 times, more preferably 1.10 to 2.0 times, still more preferably 1.10 to 1.80 times in a temperature range of 30 to 350 ° C. is there.

  In order to stretch the film in the width direction, for example, the entire width of the film is held with clips or pins in the width direction for the entire drying process or a part of the process as disclosed in JP-A-62-46625. A method of drying while drying (referred to as a tenter method), among which a tenter method using a clip is preferably used.

  The film stretched in the longitudinal direction is preferably introduced into the tenter in a state where both ends in the width direction are gripped by the clip, and stretched in the width direction while running with the tenter clip. Although the draw ratio of the width direction is not specifically limited, 1.05-1.90 times are preferable in the temperature range of 30-300 degreeC, More preferably, it is 1.10-1.60 times, More preferably, it is 1.10. 1.50 times.

  From the viewpoint of improving the flatness of the film, it is preferable to stretch the film in the width direction at a stretching speed of 50 to 1000% / min.

  If the stretching speed is 50% / min or more, the planarity is improved and the film can be processed at high speed, which is preferable from the viewpoint of production aptitude, and if it is within 1000% / min, the film is broken. Can be processed without any problem.

  A more preferable stretching speed is in the range of 100 to 500% / min. The stretching speed is defined by the following formula.

Stretching speed (% / min) = [(d ₁ / d ₂ ) −1] × 100 (%) / t
(In the above formula, d ₁ is the width dimension in the stretching direction of the resin film after stretching, d ₂ is the width dimension in the stretching direction of the resin film before stretching, and t is the time (min) required for stretching. .)
In the stretching step, usually, after stretching, holding and relaxation are performed. That is, in this step, it is preferable to perform a stretching step for stretching the film, a holding step for holding the film in a stretched state, and a relaxation step for relaxing the film in the stretched direction in this order. In the holding step, the drawing at the draw ratio achieved in the drawing step is held at the drawing temperature in the drawing step. In the relaxation stage, the stretching in the stretching stage is held in the holding stage, and then the stretching is relaxed by releasing the tension for stretching. The relaxation step may be performed at a temperature lower than the stretching temperature in the stretching step.

[G] Second drying step Next, the stretched film is heated and dried. When the film is heated with hot air or the like, a means for preventing the mixing of used hot air by installing a nozzle that can exhaust used hot air (air containing solvent or wet air) is also preferably used. The hot air temperature is more preferably in the range of 40 to 350 ° C. The drying time is preferably about 5 seconds to 30 minutes, and more preferably 10 seconds to 15 minutes.

  Further, the heating and drying means is not limited to hot air, and for example, infrared rays, heating rollers, microwaves, and the like can be used. The drying temperature is more preferably in the range of 40 to 350 ° C. in consideration of the residual solvent amount, the expansion / contraction rate in conveyance, and the like.

  In the second drying step, it is preferable to dry the film until the residual solvent amount is 0.5% by mass or less.

  The transparent base material (B) according to the present invention has a gray value standard deviation σ within a range of 0.50 to 1.10 in a predetermined rectangular area cut out from the projected image of the transparent base material (B). And that the area occupied by the black portion in the binarized image of the rectangular area is 50% or less and is smooth to some extent, the effect of making the surface of the hydrophilic resin layer of the polarizer (A) smoother is high. From the viewpoint of improving depolarization, it is preferable.

  For example, if the surface is a transparent base material (B) having a lot of unevenness and horizontal steps, the projected image is cut into a predetermined rectangular area, and when the standard deviation σ of the gray value of the area is taken, the σ value is large, and The area of the black part when the image of the area is binarized becomes large. Therefore, the smoothness of the surface of the transparent substrate (B) can be represented by the standard deviation σ and the area occupied by the black portion in the binarized image of the rectangular area.

  FIG. 3 is a schematic diagram for analyzing a film projection image according to the present invention.

  Adjust the distance between the transparent substrate (B) 11 and the white light source 12 to 60 cm from the direction of 45 ° obliquely with respect to the transparent substrate (B) 11 with the white light source 12 (Japan Technology Center Co., Ltd. S-light) Irradiate and project the distance from the transparent substrate (B) 11 to the projection surface 13 as 70 cm. Camera 14 (for example, EOS KISS50 manufactured by Canon, lens EF-S 18 = 55 mm, ISO sensitivity 100, aperture 5.6, shutter speed 1/10 second, white balance at a distance of 80 cm in the direction of 90 ° from the projection plane 3 The projection image is photographed by manual setting) to obtain a photographed image.

  Next, the captured image is analyzed according to the following procedure.

[Mura numerical procedure for smoothness]
1. The captured image is read into a personal computer using the free software ImageJ.

  2. A rectangular evaluation area that is 1 cm × 5 cm in an actual captured image is set. At that time, the long side of the rectangle is set to be in the transport direction of the film sample.

  3. Using free software ImageJ, 8-bit conversion (gray scale) is performed.

  4). Background correction is performed by the free software ImageJ.

  5. The standard deviation σ and the average value m of the gray value in the gray scale are calculated.

  6). The rectangular evaluation area is binarized using the average value m as a threshold.

  7). The black portion area ratio K (%) is calculated by dividing the area of the black portion (dark portion) obtained by the binarization by the entire area.

  Here, free software ImageJ refers to ImageJ1.32S created by Wayne Rasband.

  In addition, the background correction is output as different brightness even when the right half area and the left half area of the image have the same brightness, or as the image moves from the left side to the right side of the image. When it is output as a result of gradually brightening, background correction is performed, histogram calculation, average gradation calculation, and binarization processing are performed to obtain the area ratio K (%) of the black part (dark part) Is preferred.

  The standard deviation σ of the gray value in the gray scale is calculated by the method shown below.

Gray data N pieces of data x ₁ , x ₂ ,... XN is a population, and an arithmetic mean (population average) m of the population is obtained by the following formula 2.

  Next, using the population average m obtained above, the variance is obtained by the following Equation 3.

The positive square root σ of this variance (σ ² ) is taken as the standard deviation σ.

  The standard deviation σ of the gray value in the gray scale of the transparent base material (B) according to the present invention is preferably in the range of 0.50 to 1.10. In consideration, it is more preferably in the range of 0.70 to 1.05.

  In addition, the area occupied by the black portion in the binarized image of the rectangular area of the polyimide film according to the present invention is preferably adjusted to 50% or less, but considering the range and productivity that are not visually recognized as unevenness, A range of 40 to 50% is more preferable, and a range of 40 to 45% is more preferable.

  Means for adjusting the standard deviation σ of the gray value and the area occupied by the black portion in the binarized image within the range are not particularly limited, and the selection of the type of polyimide and the type and amount of additive are not limited. Further, this can be achieved by adding a bending process during film formation, which will be described later. Among these, it is preferable to select a polyimide type and perform a bending process.

[Bending process]
In the second drying step in which the polyimide film according to the present invention is dried in the dryer zone, the dryer zone has a drying temperature in the range of (glass transition temperature Tg-150) to (glass transition temperature Tg-30) ° C. of the film. In this case, the bending process is performed 150 times or more while transporting the roller, the standard deviation σ of the gray value is adjusted within a predetermined range, and the area occupied by the black portion in the binarized image is in the range of 10 to 50%. From the viewpoint of improving the smoothness of the film.

The bending process refers to a B surface (for example, a casting support) that faces the A surface (for example, the air surface side of the web on the casting support) of the film by a transport roller while being maintained at a predetermined drying temperature. This is a process in which the belt is bent by a roller in the conveying process so that the belt surface side of the upper web is alternately inside. The bending process, when the radius when bending the film was a (mm), the value of 1 / a is in the range of 0.035mm ^-1 ~0.050mm ^-1, and 150 times the bending It is preferable that the drying is carried out by repeating the steps less than 500 times. Preferably, it is preferably in the range of 200 to 400 times in order to satisfy the effect of improving smoothness and productivity. The film folding interval is preferably in the range of 1 second to 1 minute, and more preferably in the range of 2 to 30 seconds.

  The bending process preferable for the present invention will be described with reference to the drawings. However, it is not limited to this.

  FIG. 4 is a schematic diagram of a bending processing apparatus that can be preferably applied to the present invention.

  A dope solution is cast from a die 101 onto a metal support 102 and continuously dried on the metal support by a driving roller 103 to obtain a web (referred to as a dope film after casting on the metal support. Form). The web is dried so that the residual solvent amount becomes a desired value, peeled into a film at the peeling point 104, subjected to preliminary drying and stretching treatment (not shown), conveyed to the bending zone 106, The transfer roller 105 causes the A side (the air surface side of the web on the casting support) and the B side (the belt side of the web on the casting support) to alternately be inside the transport roller 105. It is conveyed and the bending process is repeated continuously. The bending process is performed in a bending zone 106 having an intake port 107 and an exhaust port 108, and is adjusted so that the film is bent at a desired atmospheric temperature. A cooling zone 109 for cooling the film to a predetermined temperature may be provided after the bending zone 106.

The diameter of the conveying roller is preferably in the range of 90 to 108 mm, and the distance between the rollers is preferably about 1800 mm. What is necessary is just to determine a roller diameter so that the value of 1 / a may become the range of 0.035-0.050mm- ¹ when the radius when a film is bent is set to a (mm).

  In the bending zone 106, hot air whose temperature has been adjusted is introduced from the intake port 107, and the inside of the bending zone 106 is maintained at a constant atmospheric temperature and is exhausted from the exhaust port 108. In order to adjust the atmospheric temperature in the bending zone 106, it may be performed by infrared rays, a heating roller, or the like, but it is preferably performed by hot air in terms of simplicity. The atmosphere in the drying apparatus may be air, but may be performed in an inert gas atmosphere such as nitrogen gas, carbon dioxide gas, or argon.

  The atmospheric temperature during the bending treatment of the polyimide film according to the present invention is preferably performed at a drying temperature within the range of (glass transition temperature Tg-150 ° C.) to (glass transition temperature Tg-30 ° C.) of the film. The range of 180 to 250 ° C. is more preferable for obtaining the effects of the present invention.

  The conveyance speed of the polyimide film according to the present invention in the bending zone is preferably 10 to 250 m / min, and more preferably 15 to 200 m / min in terms of productivity and breaking.

[H] Winding step The winding step is a step of winding the obtained film and cooling it to room temperature. The winding machine may be a commonly used one, and can be wound by a winding method such as a constant tension method, a constant torque method, a taper tension method, a program tension control method with a constant internal stress, or the like.

  The thickness in particular of a film is not restrict | limited, For example, it is preferable that it is 1-200 micrometers, especially 2-100 micrometers.

  In the winding process, both ends of the film sandwiched between tenter clips when stretched and conveyed may be slit. The slit end is preferably reused as a return material. Here, the recycled material refers to a portion that is formed into a film and is reused as a raw material for some reason, and the slit end (also referred to as an ear), or the feeding / termination of production. In addition, a film that is not suitable as a product due to an appearance problem such as a scratch or a streak is exemplified. The slit film edge is finely cut to a width of 1 to 30 mm, and then dissolved in a solvent and reused.

  The ratio of the portion of the formed film that is reused as a recycled material is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass.

  The input amount is slightly changed depending on the amount of return material generated in the middle of the film forming process or finally, but usually the mixing ratio of the returned material with respect to the total solid content in the dope is about 10 to 50% by mass, preferably, It is about 15-40 mass%. The mixing ratio of the recycled materials is preferably as constant as possible for production stability.

  Each step from the solvent evaporation step to the winding step described above may be performed in an air atmosphere or an inert gas atmosphere such as nitrogen gas. Moreover, each process, especially a drying process and a extending process, are performed in consideration of the explosion limit concentration of the solvent in the atmosphere.

[I] Heating step After the winding step, heating to further heat-treat the film dried in the second drying step in order to improve imidization in the polymer chain molecules and between the polymer chain molecules to improve the mechanical properties. It is preferable to perform a process.

  Moreover, even when the dope is prepared using polyimide (imidation rate 100%) or when the imidation rate of the film becomes 100% by performing the second drying step, the residual stress of the film For the purpose of relaxing, it is preferable to perform a heating step.

  In addition, the said 2nd drying process may serve as a heating process.

  A heating means is performed using well-known means, such as a hot air, an electric heater, and a microwave, for example. As the electric heater, the above-described infrared heater can be used.

  The heat treatment conditions are such that the heater output and hot air temperature are adjusted so that the film L value is 30 to 55, and the final treatment condition is in the temperature range of 200 to 450 ° C., and in the range of 30 seconds to 1 hour. It is preferable to perform appropriately. Thereby, the dimensional stability of a polyimide film can be improved. In the heating step, if the film is heated rapidly, defects such as an increase in surface defects occur, and therefore it is preferable to select the heating method as appropriate. The heating step is preferably performed in a low oxygen atmosphere.

  When the heating temperature in the second drying step and the heating step exceeds 450 ° C., the energy required for heating becomes very large, resulting in an increase in manufacturing cost and an increase in environmental load. The following is preferable.

  In addition, after the winding process, before or after the heating process, a process of slitting the width direction end of the polyimide film, or a process of neutralizing the polyimide film if charged, etc. It is also good.

[2] Liquid Crystal Display Device By using the polarizing plate of the present invention for a liquid crystal display device, various liquid crystal display devices having excellent visibility can be produced. By peeling the base material of the polarizer (A) according to the present invention and bonding the hydrophilic polymer layer side to the liquid crystal cell, a liquid crystal display device having a thin film polarizing plate can be produced.

  The polarizing plate of the present invention can be used for liquid crystal display devices of various drive systems such as STN, TN, OCB, HAN, VA (MVA, PVA), IPS, OCB.

  A VA (MVA, PVA) type or IPS type liquid crystal display device is preferable.

  In particular, even a large-screen liquid crystal display device having a screen size of 30 or more can provide a liquid crystal display device with excellent visibility such as color unevenness and front contrast with little environmental fluctuation and reduced light leakage.

[3] Organic electroluminescence display The organic EL display of the present invention preferably comprises the polarizing plate of the present invention. The polarizer (A) of the polarizing plate of the present invention has improved planarity, and when used on the surface of the organic EL display, the unevenness of the film when viewed through polarized sunglasses is not noticeable, and the organic EL has excellent visibility. A display can be provided.

  Regarding the outline of the organic EL element applicable to the organic EL display of the present invention, for example, JP2013-157634A, JP2013-168552A, JP2013-177361A, JP2013-187221A. JP, 2013-191644, JP 2013-191804, JP 2013-225678, JP 2013-235994, JP 2013-243234, JP 2013-243236, JP 2013-242366 A, JP 2013-243371 A, JP 2013-245179 A, JP 2014-003249 A, JP 2014-003299 A, JP 2014-013910 A, JP Japanese Patent Laid-Open No. 2014-017493, Japanese Patent Laid-Open No. 201 It can be mentioned arrangement described in -017494 Patent Publication.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "mass part" or "mass%" is represented.

Example 1
<Production of Stretched Laminate 1 Having Polarizer (A)>
<Production of laminate>
(Substrate A)
The following PET film was prepared and used as the base material A.

  As the crystalline ester thermoplastic resin, an amorphous polyethylene terephthalate film (A-PET) (Mitsubishi Resin Nova Clear SG-007, glass transition temperature 80 ° C.) having a film thickness of 200 μm and a length of 1000 m was used.

(Hydrophilic polymer layer)
Polyvinyl alcohol powder (manufactured by Nippon Vinegar Poval Co., Ltd., average polymerization degree 2500, saponification degree 99.0 mol% or more, product name: J40) as a hydrophilic polymer is dissolved in hot water at 95 ° C. An 8% by mass aqueous polyvinyl alcohol solution was prepared. The obtained polyvinyl alcohol aqueous solution is applied onto the substrate A for lamination using a lip coater and dried at 70 ° C. for 5 minutes to produce a laminate 1 comprising the substrate A and a hydrophilic polymer layer. did. The hydrophilic polymer layer had a thickness of 12.0 μm.

(Stretching process)
The laminate was subjected to 4.5-fold free end uniaxial stretching in the air at 100 ° C. in the transport direction (MD direction). The thickness of the hydrophilic polymer layer after stretching was 5.6 μm.

(Dyeing process)
Next, the stretched laminate was immersed in a 60 ° C. bath for 60 seconds, and immersed in an aqueous solution containing 0.05 parts by mass of iodine and 5 parts by mass of potassium iodide per 100 parts by mass of water at a temperature of 28 ° C. for 60 seconds. . Next, while maintaining the tension state, it was immersed in a boric acid aqueous solution containing 7.5 parts by mass of boric acid and 6 parts by mass of potassium iodide per 100 parts by mass of water at a temperature of 73 ° C. for 300 seconds. Then, it wash | cleaned for 10 second with 15 degreeC pure water. The film washed with water was dried at 70 ° C. for 300 seconds while keeping the tension state, and a dyed stretched laminate 1 composed of the substrate A and the hydrophilic polymer layer was obtained.

<Preparation of transparent substrate (B)>
<Polyimide resin>
A polyimide resin used in the examples was prepared by the following procedure.

<Polyimide A>
In a 500 mL separable four-necked flask equipped with a stainless steel vertical stirrer, nitrogen inlet tube, and Dean-Stark apparatus, 56.11 g (0.18 mol) of 4,4′-oxydiphthalic anhydride (ODPA), diethyl Methylbenzenediamine (DETDA) 32.09 g (0.18 mol), gamma butyrolactone (GBL) 326.87 g, pyridine 2.85 g, and toluene 33 g were charged, and the inside of the reaction system was purged with nitrogen. ODPA was dissolved by stirring at 80 ° C. for 30 minutes under a nitrogen stream, and then heated to 180 ° C. and stirred for 6 hours.

  Water generated during the reaction was removed from the reaction system as an azeotrope with toluene and pyridine. After completion of the reaction, the mixture was cooled to room temperature to obtain a 20% by mass polyimide solution. The structure of the obtained polyimide is as shown in the following formula. Isopropanol was added to this polyimide solution and cooled after stirring to obtain a polyimide A solid. Polyimide A had a weight average molecular weight of 80000 and an imidization ratio of 98%. This solid was washed and dried, and then dissolved in dichloromethane. Dioxolane was added with 1% by mass of dichloromethane to prepare a polyimide solution for film formation.

(In the formula, ^one of R ^{1 to} R ³ is a methyl group, and two are ethyl groups.)
<Polyimide B>
In the same apparatus as for the preparation of polyimide A, ODPA 46.80 g (0.15 mol), 4,4′-diamino-3,3 ′, 5,5′-tetramethyldiphenylmethane 38.16 g (0.15 mol), GBL147 .67 g, pyridine 2.39 g, and toluene 50 g were charged, and the reaction system was purged with nitrogen. ODPA was dissolved by stirring at 80 ° C. for 30 minutes under a nitrogen stream, and then heated to 180 ° C. and heated and stirred for 7 hours.

  Water generated during the reaction was removed from the reaction system as an azeotrope with toluene and pyridine. After completion of the reaction, when cooled to 120 ° C., 100 g of GBL was added to obtain a polyimide solution having a concentration of 25% by mass. The structure of the obtained polyimide is as shown in the following formula. Isopropanol was added to this polyimide solution, and the mixture was stirred and cooled to obtain a polyimide B solid. Polyimide B had a weight average molecular weight of 94000 and an imidization ratio of 99%. This solid was washed and dried, and then dissolved in dichloromethane. Dioxolane was added with 1% by mass of dichloromethane to prepare a polyimide solution for film formation.

<Polyimide C>
(Polymerization of polyimide precursor)
A stainless steel separable flask was provided as a reaction vessel, two paddle blades were provided as a stirring device in the separable flask, and a polyamic acid was produced using a reaction device provided with a cooling device. During the polymerization reaction, a nitrogen gas dehydrated by passing through a calcium chloride tube was flowed at 0.05 L / min in order to prevent moisture from mixing.

  The separable flask is charged with 223.5 g of N, N-dimethylacetamide (DMAC) as a polymerization solvent, and 40.0 g (0.125 mol) of diamine 1 which is the following exemplary compound as a diamine is dissolved therein. To this solution, 55.5 g (0.125 mol) of acid anhydride 1, which is an exemplary compound, was added as an acid anhydride and stirred to completely dissolve it. The charged concentration of diamine 1 and acid anhydride 1 in this reaction solution is 30% by mass with respect to the total reaction solution.

(Chemical imidation to polyimide)
DMAC was added to the above solution to adjust the solid concentration to 15% by mass, and 60 g of pyridine (pkBH +; 5.17) as an imidization accelerator (molar ratio of imidization accelerator / amide group in polyamic acid = 3) was added. Disperse completely. To the dispersed solution, 30.6 g (molar ratio of dehydrating agent / amide group in polyamic acid = 1.2) of acetic anhydride was added at a rate of 1 g per minute and stirred for another 30 minutes. After stirring, the internal temperature was raised to 50 ° C., and superheated stirring was performed for 5 hours.

(Extraction of polyimide)
The obtained solution was added to methanol to precipitate the target polyimide powder. The obtained white precipitate was sufficiently washed with methanol, dried by heating to 50 ° C. using a drying apparatus, and taken out as polyimide C. Polyimide C had a weight average molecular weight of 203,000 and an imidization ratio of 100%.

<Polyimide D>
To a 4-necked flask equipped with a dry nitrogen gas inlet tube, a condenser, a Dean-Stark aggregator filled with toluene, and a stirrer, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1, 25,59 g (57.6 mmol) of 3,3,3-hexafluoropropane dianhydride (acid anhydride 2) (manufactured by Daikin Industries, Ltd.) was added to N, N-dimethylacetamide (134 g) at room temperature under a nitrogen stream. Stir with.

  To this was added 19.2 g (60 mmol) of 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl (diamine 2) (manufactured by Daikin Industries), and the mixture was stirred with heating at 80 ° C for 6 hours. Thereafter, the external temperature was heated to 190 ° C., and water generated along with imidization was distilled off azeotropically with toluene. When heating, refluxing, and stirring were continued for 6 hours, generation of water was not observed. Subsequently, the mixture was heated for 7 hours while distilling off toluene. Further, after distilling off toluene, methanol was added for reprecipitation, and after drying the solid content, a dichloromethane solution was prepared to prepare a polyimide D solution. Polyimide D had a weight average molecular weight of 110,000 and an imidization ratio of 98%.

<Polyimide E>
In a 3 L four-necked flask, component (A): 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile (hereinafter also referred to as “DFBN”), component (B): 9,9-bis (4- Hydroxyphenyl) fluorene (hereinafter also referred to as “BPFL”) 70.08 g (0.200 mol), resorcinol (hereinafter also referred to as “RES”) 5.51 g (0.050 mol), potassium carbonate 41.46 g (0.300 mol) ), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.
Next, after the atmosphere in the flask was replaced with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours. After the reaction, the reaction mixture was cooled to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer). Polyimide E had a weight average molecular weight of 78000 and an imidization ratio of 100%.

  20 g of the obtained white powder was dissolved in 80 g of dichloromethane to prepare a polyimide E solution.

  Using the above polyimide resin, a transparent substrate (B): polyimide film was produced by the following method.

<Preparation of transparent substrate (B) 101>
<Preparation of dope>
A main dope having the following composition was prepared. First, dichloromethane and ethanol were added to the pressure dissolution tank. The prepared polyimide resin A was charged into a pressure dissolution tank containing a solvent while stirring. While this was heated and stirred, it was completely dissolved, and this was dissolved in Azumi Filter Paper No. After filtration using 244, the remaining components were added and stirred to dissolve to prepare the main dope.

<Composition of main dope>
Dichloromethane 340 parts by mass Ethanol 10 parts by mass Polyimide A 100 parts by mass <Casting process>
Next, using an endless belt casting apparatus, the dope was cast uniformly on a stainless steel belt support at a temperature of 30 ° C. and a width of 1500 mm. The temperature of the stainless steel belt was controlled at 30 ° C.

<Peeling process>
On the stainless steel belt support held at 40 ° C., the solvent was evaporated until the amount of residual solvent in the cast (cast) film reached 75%, and then from the stainless steel belt support at a peeling tension of 180 N / m. It peeled.

<Extension process>
The peeled polyimide film is 1.1 times in the MD direction (longitudinal direction) using the peripheral speed difference of the transport roller while applying heat at 200 ° C., and 1 in the TD direction (width direction) using a clip type tenter. The film was stretched 1 time. The residual solvent amount at the start of stretching was 20% by mass.

<Drying step a>
The stretched film was subjected to 10 bending processes using a conveying roller in a bending zone 106 shown in FIG. The film was dried at a transport tension of 100 N / m and a drying time of 20 minutes so that the amount of residual solvent was less than 0.1% by mass to obtain a film having a dry film thickness of 25 μm.

<Preparation of Transparent Substrate (B) 102-105>
In the production of the polyimide film 101, transparent substrates (B) 102 to 105 were produced in the same manner except that polyimides B to E were used instead of polyimide A.

<Preparation of transparent substrate (B) 106>
A transparent substrate (B) 106 was produced in the same manner as in the production of the transparent substrate (B) 105 except that the drying step a was changed to the following drying step b.

<Drying step b>
The stretched film was subjected to 300 times of bending treatment with a large number of conveying rollers at a drying temperature of 200 ° C. in the bending zone 106 shown in FIG. The film was dried at a transport tension of 100 N / m and a drying time of 20 minutes so that the amount of residual solvent was less than 0.1% by mass to obtain a film having a dry film thickness of 25 μm.

<Preparation of Transparent Substrate (B) 107, 108>
In the production of the transparent substrate (B) 106, the dope flow rate is further changed, the transport tension is adjusted to 20 N / m by the drying step a, the transparent substrate (B) 107 having a film thickness of 5 μm, and the film thickness A 3 μm transparent substrate (B) 108 was produced.

<Production of Comparative Transparent Base Material (B) 109>
A cellulose acylate film was prepared as a comparative transparent substrate (B) by the following procedure.

<Dope composition>
Dichloromethane 365 parts by mass Ethanol 50 parts by mass Cellulose acylate (triacetyl cellulose: TAC, acetyl group substitution degree 2.85, MW 250,000) 100 parts by mass The following polycondensation ester P5 7 parts by mass And dissolved with stirring to prepare a dope.

  On the stainless steel belt support, the solvent was evaporated until the residual solvent amount in the cast (cast) film was 75%, and then peeled off from the stainless steel belt support with a peeling tension of 130 N / m. The peeled cellulose acylate film was stretched 1.3 times in the width direction using a tenter while applying heat at 150 ° C. The residual solvent at the start of stretching was 15%.

  Next, drying was terminated while the drying zone was conveyed by a roller. The drying temperature was 130 ° C. and the transport tension was 100 N / m. As described above, a transparent base material (B) 109 mainly composed of cellulose acylate having a dry film thickness of 25 μm was obtained.

<Preparation of polycondensation ester P5>
251 g of 1,2-propylene glycol, 354 g of terephthalic acid, 680 g of p-troyl acid and 0.191 g of tetraisopropyl titanate as an esterification catalyst are charged into a 2 L four-necked flask equipped with a thermometer, a stirrer and a slow cooling tube. The temperature is gradually raised with stirring until it reaches 230 ° C. in a nitrogen stream. The dehydration condensation reaction was carried out while observing the degree of polymerization. After completion of the reaction, unreacted 1,2-propylene glycol was distilled off at 200 ° C. under reduced pressure to obtain the following polycondensed ester P5. The acid value was 0.30 and the number average molecular weight was 400.

<Preparation of Comparative Transparent Base Material (B) 110>
As polycarbonate (PC) resin, Tei DeDupont Film Co., Ltd. product name Panlite AD-5503 was used, and 150 g was put into 800 g of dichloromethane and dissolved by stirring at room temperature to prepare a dope.

  The dope was formed on a stainless steel plate using a doctor blade, and the web was peeled off. The amount of residual solvent at the time of peeling was 15 to 30%. This web is fixed to a metal frame, hot air of 100 ° C. is applied, the residual solvent amount is dried to about 10%, and then stretched by 1.2 times in both the vertical and horizontal directions. A transparent substrate (B) 110 having a thickness of 25 μm was obtained.

<Preparation of Comparative Transparent Substrate (B) 111>
A group of rolls heated to 78 ° C. after casting a resin in which polyethylene terephthalate (PET) is melted on a cooling drum having a surface temperature of 30 ° C. and bringing it into close contact with the surface of the cooling drum using an electrostatic application method. After raising the film temperature to 75 ° C., the film was heated to 105 ° C. with an infrared heater and stretched 2.8 times in the longitudinal direction with a group of rolls having a difference in peripheral speed. The obtained uniaxially stretched film was held with a clip and stretched 4.5 times at 120 ° C. in the width direction with a tenter. Next, heat treatment is performed at 210 ° C. for 15 seconds, slits are made at the ends of the 0-15% region and 85-100% region in the mill roll width direction, and a transparent base mainly composed of biaxially stretched polyethylene terephthalate having a thickness of 25 μm. Material (B) 111 was obtained.

<Preparation of polarizing plate>
<Preparation of polarizing plates 101-111>
The surface of the transparent substrate (B) 101 to 111 subjected to the corona discharge treatment on the hydrophilic polymer layer side of the produced stretched laminate 1 having the polarizer (A) is respectively shown in FIG. As shown in the figure, the nip roller was applied with a load of 30 kg / 30 cm and bonded together. Next, the excess PVA aqueous solution was removed, the substrate A was peeled off, two sides were fixed with a clip, and dried at 60 ° C. for 5 minutes to prepare polarizing plates 101 to 111.

  The corona discharge treatment was performed at a corona output intensity of 2.0 kW and a speed of 18 m / min.

≪Evaluation≫
(1) Evaluation of transparent substrate (B) [Martens hardness]
The Martens hardness was measured according to the procedure of the indentation test specified by ISO14577-1 Annex A. An ultra-micro hardness tester (DUH-211S test force: set to 12 mN, manufactured by Shimadzu Corporation) is used as a testing machine, and a pyramid-type diamond indenter having a square base and a facing angle of 136 ° is used as an indenter. The value was obtained by dividing by the surface area of the indenter that entered beyond the point.

[Total light transmittance]
The total light transmittance of the transparent substrate (B) according to the present invention was calculated using the method described in JIS K 7105: 1981. As a measuring device, a haze meter NDH5000 manufactured by Tokyo Denshoku Co., Ltd. was used.

[Flatness evaluation]
The film projection image was analyzed using the apparatus and layout shown in FIG.

  Irradiate the white light source 2 with respect to the film sample 1 from an angle of 45 °, adjusting the distance between the transparent base material (B) sample and the white light source to 60 cm. Is projected as 70 cm. Camera 4 (Canon EOS KISS50, lens EF-S 18 = 55 mm, ISO sensitivity 100, aperture 5.6, shutter speed 1/10 sec, white balance manual setting) at a distance of 80 cm in the direction of 90 ° from the projection plane A projected image was taken at 1 to obtain a taken image.

  Next, the standard deviation σ of the gray value and the area ratio K (%) of the black part (dark part) of the binarized image were obtained for the photographed image by the following procedure.

  1. The photographed image was read into a personal computer using free software ImageJ.

  2. A rectangular evaluation area was set to be 1 cm × 5 cm in the actual captured image. At that time, the long side of the rectangle was set to be the film sample transport direction.

  3. 8-bit conversion (gray scale conversion) was performed using free software ImageJ.

  4). Background correction was performed with the free software ImageJ.

  5. The standard deviation σ and the average value m of the gray value in the gray scale were calculated.

  6). The rectangular evaluation area was binarized using the average value m as a threshold.

  7). The area of the black part (dark part) obtained by the binarization was divided by the total area to calculate the black part area ratio K (%).

  Here, the free software ImageJ is ImageJ1.32S created by Wayne Rasband.

  For the transparent substrate (B) 102 of the present invention, the projection image (A), the binarized image (B), and the standard deviation (C) of the gray value are shown in FIG.

(2) Evaluation of polarizing plate [Measurement of degree of polarization]
The degree of polarization was determined according to the following method.

  A polarizing plate sample was subjected to a humidity conditioning treatment for 24 hours in an environment of 23 ° C. and 55% RH, then cut into a size of 30 cm × 30 cm, and the parallel transmittance of light having a light wavelength of 550 nm was obtained at the center point of the diagonal line. The orthogonal transmittance was measured using an automatic polarizing film measuring apparatus (VAP-7070, manufactured by JASCO Corporation). Subsequently, based on each obtained measurement value, polarization degree (%) was calculated | required based on the following formula (B2). The degree of polarization is preferably 99.995% or more because there is no light leakage.

表１の結果から、本発明の偏光板１０２〜１０８は、偏光解消が減り偏光度に優れていることが分かる、特に、本発明の偏光板１０６において、透明基材（Ｂ）にベンディング処理を行い平滑性を向上することによって、より偏光度に優れることが分かった。

From the results in Table 1, it can be seen that the polarizing plates 102 to 108 of the present invention have reduced depolarization and are excellent in polarization degree. In particular, in the polarizing plate 106 of the present invention, the transparent substrate (B) is subjected to bending treatment. It was found that by improving the smoothness, the degree of polarization was further improved.

Example 2
<Production of liquid crystal display device>
The 40-side display BRAVIA X1 made by SONY is peeled off from both sides of the previously bonded polarizing plate, and the hydrophilic resin layer is exposed by peeling off the substrate A for each of the above-described polarizing plates 101-111. Was bonded to the glass surface of the liquid crystal cell using an acrylic adhesive. At that time, the polarizers on both sides were bonded so that the absorption axes thereof were orthogonal to each other.

  Liquid crystal display devices 101 to 111 corresponding to the polarizing plates 101 to 111 were produced.

≪Evaluation≫
[Visual evaluation of contrast]
Images were displayed on the liquid crystal display device produced above, and the contrast was visually evaluated.

A: The image contrast is high and the image is clear. ○: The image contrast is high. Δ: The image is slightly blurred and the contrast is slightly low.

  As a result of Table 2, the liquid crystal display device using the polarizing plates 102 to 108 of the present invention had clear images and excellent contrast. On the other hand, in the liquid crystal display device using the polarizing plates 101 and 109 to 111 of the comparative example, the image was slightly unclear and the contrast was low. That is, when a film having high Martens hardness and good flatness was used, both the contrast and visibility were good.

Example 3
<Production of organic EL display>
Using the polarizing plates 101 to 111 produced as described above, organic EL displays 101 to 111 were produced with the following configuration.

(Production of organic EL display)
An organic EL display A having the configuration shown in FIG. 6 was produced.

[Production of organic EL display]
In the configuration shown in FIG. 6, a PET film is used as the transparent substrate 211, a reflective electrode made of chromium is formed on the transparent substrate 211, a metal electrode 212 is formed on the reflective electrode using ITO as a metal electrode (anode), and the organic light emitting layer 213 is formed. As a hole transport layer, poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT: PSS) is formed to a thickness of 80 nm on the anode by a sputtering method, and then a shadow mask is formed on the hole transport layer. In this way, RGB light emitting layers 213R, 213G, and 213B (both not shown) were formed to a thickness of 100 nm. As the red light-emitting layer 213R, tris (8-hydroxyquinolinate) aluminum (Alq ₃ ) and a light-emitting compound [4- (dicyanomethylene) -2-methyl-6 (p-dimethylaminostyryl) -4H-pyran] ( DCM) were co-evaporated (mass ratio 99: 1) to form a thickness of 100 nm. As the green light emitting layer 213G, Alq ₃ as a host and the light emitting compound coumarin 6 (3- (2-benzothiazolyl) -7- (diethylamino) coumarin) are co-evaporated (mass ratio 99: 1) to a thickness of 100 nm. Formed. The blue light-emitting layer 213B was formed with a thickness of 100 nm by co-evaporating BAlq and a light-emitting compound Perylene as a host (mass ratio 90:10).

  Further, calcium is deposited in a thickness of 4 nm by vacuum deposition as a first cathode having a low work function so that electrons can be efficiently injected onto the organic light emitting layer, and a second cathode is formed on the first cathode. As a result, aluminum was formed to a thickness of 2 nm. Here, the aluminum used as the second cathode has a role to prevent calcium as the first cathode from being chemically altered when the transparent conductive film formed thereon is formed by sputtering. . As described above, an organic light emitting layer was obtained. Next, a transparent conductive film having a thickness of 80 nm was formed on the cathode by a sputtering method to form a transparent electrode 214. Here, ITO was used as the transparent conductive film. Furthermore, 200 nm of silicon nitride was deposited on the transparent electrode 214 by a CVD method to form the insulating film 215, thereby fabricating an organic EL element unit.

  Next, a polyethylene terephthalate film with a gas barrier layer having a thickness of 20 μm is used as the gas barrier film 217, and a thermosetting liquid adhesive (epoxy resin) is formed as a sealing layer 216 on one side of the gas barrier film 217. A sealing unit having a thickness of 25 μm was produced.

  Next, the organic EL element unit formed from the transparent substrate 211 to the insulating layer 215 and the sealing unit were pressed and held for 5 minutes under reduced pressure conditions of 90 MPa at 0.1 MPa. Subsequently, the laminate was returned to the atmospheric pressure environment, and further heated at 90 ° C. for 30 minutes to cure the adhesive, whereby an organic EL display device B was produced.

The light-emitting area of the produced organic EL display device B was 1296 mm × 784 mm. Further, the front luminance when a DC voltage of 6 V was applied to the organic EL display device B was 1200 cd / m ² . The front luminance is measured using a spectral radiance meter CS-1000 manufactured by Konica Minolta, with the 2 ° viewing angle front luminance being set so that the optical axis of the spectral radiance meter matches the normal from the light emitting surface. The range of visible light wavelength of 430 to 480 nm was measured, and the integrated intensity was taken.

[Preparation of organic EL displays 101-111]
Polarizer (A) 2 in which a commercially available λ / 4 retardation film 218 and the base material A of the prepared polarizing plates 101 to 111 are peeled off to the prepared organic EL display device B to expose a hydrophilic resin layer, and The circularly polarizing plate C provided with the protective film 4 which is the transparent base material (B) according to the present invention in this order is fixed through an adhesive layer so as to have the configuration shown in FIG. Display 101-111 was produced. The slow axis of the commercially available λ / 4 retardation film 218 and the absorption axis of the polarizer (A) 2 were bonded so that the direction was 45 ° to prepare a circularly polarizing plate.

<Visibility evaluation>
Electricity is supplied to the produced organic EL displays 101 to 111 to display an image, which is visually observed. The visibility at that time was evaluated.
◎: The image is clear with almost no reflection from the outside. ○: The reflection from the outside is small. △: The reflection from the outside is slightly seen and the image is slightly unclear.

  The organic EL displays 102 to 108 using the polarizing plate of the present invention had little external reflection and good visibility. Also in the case of an organic EL display, when a film having high Martens hardness and good flatness was used, both the contrast and visibility were good.

  The polarizing plate of the present invention is a thin polarizing plate and has a reduced depolarization and an improved degree of polarization, and is therefore suitable for a thin liquid crystal display device and an organic electroluminescence display.

1 Base Material 2 Polymer Layer 3 Polarizer (A)
4 Transparent substrate (B)
DESCRIPTION OF SYMBOLS 5 Nip roller 10 Polarizing plate 11 Transparent base material (B): Polyimide film 12 White light source 13 Projection surface 14 Camera 101 Die 102 Metal support 103 Driving roller 104 Peeling point 105 Conveyance roller 106 Bending zone 107 Intake port 108 Exhaust port 109 Cooling Zone A Organic EL display B Organic EL display device C Circular polarizing plate 211 Substrate, transparent substrate 212 Metal electrode 213 Organic light emitting layer 214 Transparent electrode 215 Insulating layer 216 Sealing layer 217 Gas barrier film 218 λ / 4 retardation film

Claims (8)

  A polarizer (A) having a hydrophilic polymer layer dyed with a dichroic material, and an indentation elastic modulus of 4.5 GPa or more and a total light transmittance of 80 on at least one surface of the polarizer (A). % Of the transparent substrate (B) which is at least%.   The polarizing plate according to claim 1, wherein the transparent substrate (B) contains a transparent heat-resistant resin having an imide structure.   In the predetermined rectangular area where the transparent base material (B) is cut out from the projected image of the transparent base material (B), the standard deviation σ of the gray value is in the range of 0.50 to 1.10. The polarizing plate according to claim 1 or 2, wherein an area occupied by a black portion in the binarized image of the rectangular area is 50% or less.   The said polarizer (A) is a coating type polarizer, The polarizing plate as described in any one of Claim 1- Claim 3 characterized by the above-mentioned. A method for producing a polarizing plate comprising a polarizer (A) having a hydrophilic polymer layer and a transparent substrate (B) having an indentation elastic modulus of 4.5 GPa or more and a total light transmittance of 80% or more,
A step of casting a coating solution containing a hydrophilic polymer on a substrate to form a hydrophilic polymer layer;
Stretching the hydrophilic polymer layer and dyeing with a dichroic material;
A process of forming a polarizing plate by laminating the transparent base material (B) with a nip roller on the air interface side surface of the hydrophilic polymer layer,
The manufacturing method of the polarizing plate characterized by having.   The said transparent base material (B) contains the transparent heat resistant resin which has an imide structure, The manufacturing method of the polarizing plate of Claim 5 characterized by the above-mentioned.   A liquid crystal display device comprising the polarizing plate according to any one of claims 1 to 4.   An organic electroluminescence display device comprising the polarizing plate according to any one of claims 1 to 4.

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