JP2021144247A - Liquid crystal display device and polarizer - Google Patents

Abstract

To provide a liquid crystal display device in which even if using a light source having a steep light emission spectrum in a red area such as a KSF phosphor and the like as a backlight source, an irregular color is not conspicuous, and a reproduction color band is broad.SOLUTION: A liquid crystal display device has: a backlight source; two polarization plates; and a liquid crystal cell that is arranged between the two polarization plates. The backlight source is a white light source that has a peak top of a light emission spectrum in each wavelength area equal to or more than 400nm and less than 495nm, equal to or more than 495nm and less than 600nm, and equal to or more than 600nm and less than 780nm, respectively, and has a light emission spectrum in which a half value width of the highest intensity peak top is less tha 5nm in a wavelength area equal to or more than 600nm and less than 780nm. At least one polarization plate of the polarization plates has a polyester film with 1500 to 30000 nm retardation laminated on at least one surface of the polarizer, and a refractive index of the polyester film is 1.53 to 1.62 that is in a direction parallel with a transmission axis of the polarizer.SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal display device and a polarizing plate. More specifically, the present invention relates to a liquid crystal display device and a polarizing plate in which the occurrence of iridescent color spots is reduced.

The polarizing plate used in the liquid crystal display (LCD) usually has a structure in which a polarizing element obtained by dyeing iodine on polyvinyl alcohol (PVA) or the like is sandwiched between two polarizing element protective films, and is used as a polarizing element protective film. Usually, a triacetyl cellulose (TAC) film is used. In recent years, as LCDs have become thinner, there has been a demand for thinner polarizing plates. However, if the thickness of the TAC film used as the protective film is reduced for this purpose, sufficient mechanical strength cannot be obtained, and there arises a problem that the moisture permeability is deteriorated. Further, the TAC film is very expensive, and a polyester film has been proposed as an inexpensive alternative material (Patent Documents 1 to 3), but there is a problem that iridescent color spots are observed.

When an oriented polyester film having birefringence is arranged on one side of the polarizer, the polarization state of the linearly polarized light emitted from the backlight unit or the polarizer changes when passing through the polyester film. The transmitted light exhibits an interference color peculiar to retardation, which is the product of birefringence and thickness of the oriented polyester film. Therefore, if a discontinuous emission spectrum such as a cold-cathode tube or a hot-cathode tube is used as the light source, the transmitted light intensity differs depending on the wavelength, resulting in iridescent color spots (see: Proceedings of the 15th Microoptical Conference, No. 30-31).

As a means for solving the above problems, a white light source having a continuous and wide emission spectrum such as a white light emitting diode is used as the backlight light source, and an oriented polyester film having a certain retardation is used as the polarizer protective film. It has been proposed (Patent Document 4). White light emitting diodes have a continuous and wide emission spectrum in the visible light region. Therefore, focusing on the envelope shape of the interference color spectrum due to the transmitted light transmitted through the compound refracting body, by controlling the retardation of the oriented polyester film, a spectrum similar to the emission spectrum of the light source can be obtained, and rainbow spots can be suppressed. It has been proposed that it is possible.

By making the orientation direction of the oriented polyester film perpendicular to or parallel to the polarization direction of the polarizing plate, the linearly polarized light emitted from the polarizer passes through the oriented polyester film while maintaining the polarized state. Further, by controlling the birefringence of the oriented polyester film to enhance the uniaxial orientation, light incident from an oblique direction can also pass while maintaining the polarized state. When the oriented polyester film is viewed from an angle, a deviation occurs in the orientation spindle direction as compared with a case where it is viewed from directly above, but when the uniaxial orientation is high, the deviation in the orientation spindle direction when viewed from an angle becomes small. Therefore, it is considered that the deviation between the direction of linearly polarized light and the direction of the main axis of orientation is small, and the change in the polarization state is less likely to occur. By controlling the emission spectrum of the light source, the orientation state of the compound refracting body, and the orientation main axis direction in this way, changes in the polarization state are suppressed, rainbow-shaped color spots do not occur, and visibility is significantly improved. Was thought to be.

Japanese Unexamined Patent Publication No. 2002-116320 Japanese Unexamined Patent Publication No. 2004-219620 Japanese Unexamined Patent Publication No. 2004-205773 WO2011 / 162198

Due to the increasing demand for expanding the color gamut of liquid crystal display devices in recent years, the peaks of the light emission spectrum are in each wavelength region of the blue region (400 nm or more and less than 495 nm), the green region (495 nm or more and less than 600 nm), and the red region (600 nm or more and 780 nm or less). A white light emitting diode having a top and a light emission spectrum having a relatively narrow peak half-value width (less than 5 nm) in the red region (600 nm or more and 780 nm or less) (for example, a blue light emitting diode and at least K ₂ SiF ₆ : as a phosphor): A liquid crystal display device using a backlight light source made of a white light emitting diode having a fluoride phosphor such as Mn ^{4+) has been developed.}

When a liquid crystal display device is industrially produced using a polarizing plate using a polyester film as a polarizer protective film, the directions of the transmission axis of the polarizer and the phase advance axis of the polyester film are usually arranged to be perpendicular to each other. Will be done. This is because the polyvinyl alcohol film, which is a polarizer, is produced by longitudinally uniaxially stretching, and the polyester film, which is the protective film thereof, is produced by longitudinally stretching and then laterally stretching. This is because the main axis direction is the lateral direction, and when a polarizing plate is manufactured by laminating these long objects, the phase advance axis of the polyester film and the transmission axis of the polarizer are usually in the vertical direction. In this case, an oriented polyester film having a specific retardation is used as the polyester film, and the backlight source is represented by, for example, a white LED composed of a light emitting element in which a blue light emitting diode and an yttrium aluminum garnet yellow phosphor are combined. By using a light source having a continuous and wide emission spectrum, the iridescent color spots are significantly improved, but the half-value width of the peak in the red region (600 nm or more and 780 nm or less) is relatively narrow (less than 5 nm). We have found that there is still a new problem of rainbow spots when using a backlit light source consisting of a white light emitting diode with a spectrum.

That is, the subject of the present invention is to have a peak top of the emission spectrum in each wavelength region of the blue region (400 nm or more and less than 495 nm), the green region (495 nm or more and less than 600 nm), and the red region (600 nm or more and 780 nm or less), and red. When a polyester film is used as the polarizer protective film in a liquid crystal display device having a backlight source composed of a white light emitting diode having an emission spectrum having a relatively narrow half-value width (less than 5 nm) of a peak in a region (600 nm or more and 780 nm or less). Another object of the present invention is to provide a liquid crystal display device and a polarizing plate in which rainbow spots are suppressed.

A typical invention is as follows.
Item 1.
A liquid crystal display device having a backlight light source, two polarizing plates, and a liquid crystal cell arranged between the two polarizing plates.
The backlight source has a peak top of the emission spectrum in each wavelength region of 400 nm or more and less than 495 nm, 495 nm or more and less than 600 nm, and 600 nm or more and 780 nm or less, and has the highest peak intensity in the wavelength region of 600 nm or more and 780 nm or less. A white light emitting diode having an emission spectrum with a peak width of less than 5 nm.
At least one of the polarizing plates is obtained by laminating a polyester film having a retardation of 1500 to 30,000 nm on at least one surface of the polarizing element, and is in a direction parallel to the transmission axis of the polarizing element. The refractive index of the polyester film is 1.53 to 1.62.
Liquid crystal display device.
Item 2.
The emission spectrum of the backlight source is
The half width of the peak with the highest peak intensity in the wavelength region of 400 nm or more and less than 495 nm is 5 nm or more.
The half width of the peak with the highest peak intensity in the wavelength region of 495 nm or more and less than 600 nm is 5 nm or more.
Item 2. The liquid crystal display device according to Item 1.
Item 3.
Item 2. The liquid crystal display device according to Item 1 or 2, wherein the difference between the refractive index of the polarizer in the transmission axis direction and the refractive index of the polyester film in the direction parallel to the transmission axis of the polarizer is 0.12 or less. ..
Item 4.
A polarizing plate in which a polyester film having a retardation of 1500 to 30000 nm is laminated on at least one surface of a polarizing element.
The polyester film has a refractive index of 1.53 to 1.62 in a direction parallel to the transmission axis of the polarizer.
It has a peak top of the emission spectrum in each wavelength region of 400 nm or more and less than 495 nm, 495 nm or more and less than 600 nm, and 600 nm or more and 780 nm or less, and the half width of the peak with the highest peak intensity in the wavelength region of 600 nm or more and 780 nm or less is 5 nm. A polarizing plate for a liquid crystal display device having a backlight source composed of a white light emitting diode having an emission spectrum of less than.

The liquid crystal display device and the polarizing plate of the present invention can ensure good visibility in which the occurrence of rainbow-shaped color spots is significantly suppressed at any observation angle.

Generally, a liquid crystal display device is composed of a rear surface module, a liquid crystal cell, and a front surface module in the order from the side facing the backlight source to the side displaying an image (visual recognition side). The rear module and the front module are generally composed of a transparent substrate, a transparent conductive film formed on the surface of the liquid crystal cell side thereof, and a polarizing plate arranged on the opposite side thereof. Here, the polarizing plate is arranged on the side facing the backlight light source in the rear module, and is arranged on the image display side (visual recognition side) in the front module.

The liquid crystal display device of the present invention comprises at least a backlight source, two polarizing plates, and a liquid crystal cell arranged between the two polarizing plates as constituent members.

In addition to the backlight source, the polarizing plate, and the liquid crystal cell, the liquid crystal display device may appropriately have other configurations such as a color filter, a lens film, a diffusion sheet, and an antireflection film. A brightness improving film may be provided between the light source side polarizing plate and the backlight light source. Examples of the brightness improving film include a reflective polarizing plate that transmits one linearly polarized light and reflects the linearly polarized light orthogonal to the linearly polarized light. As the reflective polarizing plate, for example, a brightness improving film of the DBEF (registered trademark) (Dual Brightness Enhancement Film) series manufactured by Sumitomo 3M Ltd. is preferably used. The reflective polarizing plate is usually arranged so that the absorption axis of the reflective polarizing plate and the absorption axis of the light source side polarizing plate are parallel to each other.

Of the two polarizing plates arranged in the liquid crystal display device, at least one polarizing plate is one in which a polyester film is laminated on at least one surface of a polarizing element obtained by dyeing iodine with polyvinyl alcohol (PVA) or the like. Is. The refractive index of the polyester film in the direction parallel to the transmission axis of the polarizer is preferably 1.53 to 1.62. It is preferable that a film having no double refraction such as a TAC film, an acrylic film, or a norbornene-based film is laminated on the other surface of the polarizing element (three-layered polarizing plate), but it is not always the same as the polarizing element. It is not necessary for the film to be laminated on the other surface (two-layer polarizing plate). When a polyester film is used as the protective film on both sides of the polarizer, it is preferable that the slow axes of both polyester films are substantially parallel to each other.

As the polarizing element, any polarizing element (polarizing film) used in the art can be appropriately selected and used. As a typical polarizer, a polyvinyl alcohol film or the like dyed with a dichroic material such as iodine can be mentioned, but the present invention is not limited to this, and a known and can be developed in the future. Can be appropriately selected and used.

Commercially available PVA films can be used, for example, "Kuraray Vinylon (manufactured by Kuraray Co., Ltd.)", "Tosero Vinylon (manufactured by Tohcello Co., Ltd.)", "Nigo Vinylon (manufactured by Nippon Synthetic Chemical Co., Ltd.)". (Manufactured)] and the like. Examples of the bicolor material include iodine, a diazo compound, a polymethine dye and the like.

The polarizer can be obtained by any method. For example, a PVA film dyed with a dichroic material is uniaxially stretched in an aqueous boric acid solution, and washed and dried while maintaining the stretched state. Can be obtained by The draw ratio of uniaxial stretching is usually about 4 to 8 times, but is not particularly limited. Other manufacturing conditions and the like can be appropriately set according to a known method.

The backlight may be configured by an edge light system having a light guide plate, a reflector, or the like as a constituent member, or a direct system, but in the present invention, the backlight source of the liquid crystal display device is used. The peak top of the emission spectrum is in each wavelength region of 400 nm or more and less than 495 nm, 495 nm or more and less than 600 nm, and 600 nm or more and 780 nm or less, and the half-value width of the peak with the highest peak intensity in the wavelength region of 600 nm or more and 780 nm or less is A backlight source composed of a white light emitting diode having an emission spectrum of less than 5 nm is preferable. The upper limit of the half width of the peak having the highest peak intensity in the wavelength region of 600 nm or more and 780 nm or less is preferably less than 5 nm, more preferably less than 4 nm, and further preferably less than 3.5 nm. The lower limit is preferably 1 nm or more, more preferably 1.5 nm or more. When the half width of the peak is less than 5 nm, the color gamut of the liquid crystal display device is widened, which is preferable. Further, if the half width of the peak is less than 1 nm, the luminous efficiency may deteriorate, which is not preferable. The shape of the emission spectrum is designed from the balance between the required color gamut and luminous efficiency. Here, the full width at half maximum is the peak width (nm) at half the intensity of the peak intensity at the wavelength of the peak top.

The application of a backlight source having an emission spectrum having the above-mentioned characteristics to an LCD is a technique that has attracted attention due to the increasing demand for color gamut expansion in recent years. An LED that uses a conventionally used white LED (for example, a light emitting element that combines a blue light emitting diode and an yttrium aluminum garnet yellow phosphor) as a backlight source has a spectrum that can be recognized by the human eye. Only about 20% of the colors can be reproduced. On the other hand, when a backlight source having an emission spectrum having the above-mentioned characteristics is used, it is said that 60% or more of colors can be reproduced.

The wavelength region of 400 nm or more and less than 495 nm is more preferably 430 nm or more and 470 nm or less. The wavelength region of 495 nm or more and less than 600 nm is more preferably 510 nm or more and 560 nm or less. The wavelength region of 600 nm or more and 780 nm or less is more preferably 600 nm or more and 700 nm or less, and even more preferably 610 nm or more and 680 mn or less.

The peak half width at the peak top of each wavelength region of 400 nm or more and less than 495 nm (half width of the peak having the highest peak intensity in each wavelength region) of the emission spectrum is not particularly limited, but is 400 nm or more and less than 495 nm. The half width of the peak having the highest peak intensity in the wavelength region of 495 nm or more is preferably 5 nm or more, and the half width of the peak having the highest peak intensity in the wavelength region of 495 nm or more and less than 600 nm is preferably 5 nm or more. From the viewpoint of ensuring an appropriate color gamut, the upper limit of the peak half width (half width of the peak having the highest peak intensity in each wavelength region) at the peak top of each wavelength region of 400 nm or more and less than 495 nm and 495 nm or more and less than 600 nm is set. It is preferably 140 nm or less, preferably 120 nm or less, preferably 100 nm or less, more preferably 80 nm or less, still more preferably 60 nm or less, and even more preferably 50 nm or less.

Specific examples of the white light source having the emission spectrum having the above-mentioned characteristics include a phosphor-type white light emitting diode in which a blue light emitting diode and a phosphor are combined. Examples of the red fluorescent substance among the fluorescent substances include, for example _{, a fluoride fluorescent substance having a composition formula of K 2} SiF ₆ : Mn ⁴⁺ (also referred to as “KSF”), and others. The Mn4 + activated fluoride complex phosphor is a phosphor having Mn ⁴⁺ as an activator and a fluoride complex salt of an alkali metal, an amine or an alkaline earth metal as a parent crystal. The fluoride complex forming the parent crystal has a coordination center of a trivalent metal (B, Al, Ga, In, Y, Sc, lanthanoid) and a tetravalent metal (Si, Ge, Sn, Ti, Zr, There are those of Re, Hf) and those of pentavalent metals (V, P, Nb, Ta), and the number of fluorine atoms coordinated around them is 5 to 7.

Preferable examples of the Mn ⁴⁺ activated fluoride complex phosphor are A ₂ [MF ₆ ]: Mn (A is one or more selected from Li, Na, K, Rb, Cs, NH ₄ ; M is Ge, Si, One or more selected from Sn, Ti, Zr), E [MF ₆ ]: Mn (E is one or more selected from Mg, Ca, Sr, Ba, Zn; M is selected from Ge, Si, Sn, Ti, Zr. (A is one or more selected from Li, Na, K, Rb, Cs, NH ₄ ), Ba _0.65 , Zr _0.35 F _2.70 : Mn, A ₃ [ZrF _{7]: Mn (A is one or more selected from Li, Na, K, Rb, Cs, NH 4)} , A ₂ [MF ₅ ]: Mn (A is one or more selected from Li, Na, K, Rb, Cs, NH ₄ ; M is one or more selected from Al, Ga, In), A ₃ [MF ₆ ] : Mn (A is one or more selected from Li, Na, K, Rb, Cs, NH4; M is one or more selected from Al, Ga, In), Zn ₂ [MF ₇ ]: Mn (M is Al, Ga) , One or more selected from In), A [In ₂ F ₇ ]: Mn (A is one or more selected from Li, Na, K, Rb, Cs, NH _{4) and the like.}

One of the preferred Mn ⁴⁺ activated fluoride complex phosphors is selected from _{A 2} MF ₆ : Mn (A is Li, Na, K, Rb, Cs, NH ₄₎ having a hexafluoro complex salt of an alkali metal as a parent crystal. One or more; M is one or more selected from Ge, Si, Sn, Ti, and Zr). Of these, A is one or more selected from K (potassium) or Na (sodium), and M is Si (silicon) or Ti (titanium). Among them, it is particularly preferable that A is K (the ratio of K to the total amount of A is 99 mol% or more) and M is Si. The activating element is preferably Mn (manganese) of 100%, but Ti, Zr, Ge, Sn, Al, Ga, B, In, Cr, in the range of less than 10 mol% with respect to the total amount of the activating element. Fe, Co, Ni, Cu, Nb, Mo, Ru, Ag, Zn, Mg and the like may be contained. When M is Si, the ratio of Mn in the total of Si and Mn is preferably in the range of 0.5 mol% to 10 mol%. Other preferred Mn4 + -activated fluoride complex phosphor, the formula _{A 2 + x M y Mn z} F n (A is Na and K; M is Si and Al; -1 ≦ x ≦ 1 and 0.9 ≦ y + z ≦ 1. 1 and 0.001 ≦ z ≦ 0.4 and 5 ≦ n ≦ 7) can be mentioned.

As the backlight source, a white light emitting diode having a blue light emitting diode and at least a fluoride phosphor as a phosphor is preferable, and a fluoride having at least K ₂ SiF ₆ : Mn ^{4+ as a blue light emitting diode and a phosphor is particularly preferable.} It is a white light emitting diode having a phosphor. For example, a commercially available product such as NSSW306FT, which is a white LED manufactured by Nichia Corporation, can be used.

Among the fluorescent substances, the green fluorescent substance includes, for example, a sialone-based fluorescent substance having a basic composition of β-SiAlON: Eu or the like, or a silicate-based fluorescent substance having a basic composition of _{(Ba, Sr) 2} SiO _{4: Eu or the like.} , Others are exemplified.

When a plurality of peaks are present in any of the wavelength region of 400 nm or more and less than 495 nm, the wavelength region of 495 nm or more and less than 600 nm, or the wavelength region of 600 nm or more and 780 nm or less, it is considered as follows.
When the plurality of peaks are independent peaks, it is preferable that the half width of the peak having the highest peak intensity is in the above range. Further, for other peaks having an intensity of 70% or more of the highest peak intensity, it is more preferable that the half width is similarly in the above range.
For one independent peak having a shape in which a plurality of peaks overlap, the half width of the peak having the highest peak intensity among the plurality of peaks can be measured as it is, and the half width is used. Here, the independent peak has an intensity region that is halved of the peak intensity on both the short wavelength side and the long wavelength side of the peak. That is, when a plurality of peaks overlap and each peak does not have an intensity region on both sides of which is 1/2 of the peak intensity, the plurality of peaks are regarded as one peak as a whole. For one peak having such a shape in which a plurality of peaks overlap, the width of the peak (nm) at half the intensity of the highest peak intensity among them is set as the half width.
Of the plurality of peaks, the peak with the highest peak intensity is set as the peak top.
The peak having the highest peak intensity in each wavelength region of 400 nm or more and less than 495 nm, 495 nm or more and less than 600 nm, or 600 nm or more and 780 nm or less is independent of the peaks of other wavelength regions. It is preferable to have a relationship with each other. In particular, in the wavelength region between the peak having the highest peak intensity in the wavelength region of 495 nm or more and less than 600 nm and the peak having the highest peak intensity in the region of 600 nm or more and 780 nm or less, the wavelength having an intensity of 600 nm or more and 780 nm or less It is preferable from the viewpoint of color clarity that there is a region having the highest peak intensity of the region and which is 1/3 of the peak intensity of the peak.

The emission spectrum of the backlight source can be measured by using a spectroscope such as the Hamamatsu Photonics multi-channel spectroscope PMA-12.

As a result of diligent studies by the present inventions, as a result of diligent studies, each wavelength region of a blue region (400 nm or more and less than 495 nm), a green region (495 nm or more and less than 600 nm), and a red region (600 nm or more and 780 nm or less) is formed, respectively. Polyester as a polarizer protective film in a liquid crystal display device having a backlit light source consisting of a white light emitting diode having a peak top of an emission spectrum and a relatively narrow peak half-value width of less than 5 nm in the red region (600 nm or more and 780 nm or less). Even when a polarizing plate using a film is used, it is significant if the refractive index of the polyester film is in the range of 1.53 or more and 1.62 or less in the direction parallel to the transmission axis of the polarizer constituting the polarizing plate. It was found that rainbow spots can be suppressed. The mechanism by which the occurrence of iridescent color spots is suppressed by the above aspect is considered as follows.

When an oriented polyester film is arranged on one side of the polarizer, the polarization state of the linearly polarized light emitted from the backlight unit or the polarizer changes when passing through the polyester film. It is possible that one of the factors that change the polarization state is the difference in refractive index at the interface between the air layer and the oriented polyester film, or the difference in refractive index at the interface between the polarizer and the oriented polyester film. When the linearly polarized light incident on the oriented polyester film passes through each interface, a part of the light is reflected due to the difference in refractive index at the interface. At this time, the polarization state of both the emitted light and the reflected light changes, which is considered to be one of the factors that cause rainbow-shaped color spots. Therefore, by reducing the difference in refractive index between the air layer and the oriented polyester film and the difference in refractive index between the polarizer and the oriented polyester film in the polarization direction (transmission axis direction) of the incident linearly polarized light, at each interface. It is considered that the reflection of the light is suppressed and the iridescent color spots are suppressed. In order to reduce the difference in refractive index between the air layer and the oriented polyester film and the difference in refractive index between the polarizer and the oriented polyester film in the polarization direction (transmission axis direction) of the incident linearly polarized light, it is parallel to the transmission axis. This can be achieved by adjusting the refractive index of the polyester film in the above direction as low as about 1.53 to 1.62.

As described above, in the present invention, each wavelength region of the blue region (400 nm or more and less than 495 nm), the green region (495 nm or more and less than 600 nm), and the red region (600 nm or more and 780 nm or less) has a peak top of the emission spectrum. In a liquid crystal display device having a backlight light source composed of a white light emitting diode having a peak half-value width of less than 5 nm in the red region (600 nm or more and 780 nm or less), a polarizing plate using a polyester film as a polarizer protective film is used. However, it is possible to have good visibility without the occurrence of iridescent color spots.

In the polarizing plate of the present invention, a polarizing element protective film made of a polyester film is laminated on at least one surface of the polarizing element. The refractive index of the polyester film in the direction parallel to the transmission axis direction of the polarizer is preferably adjusted to be low so as to be in the range of 1.53 or more and 1.62 or less. This makes it possible to suppress reflection at the interface between the air layer and the polyester film and the interface between the polarizer and the polyester film, and suppress iridescent color spots. If the refractive index exceeds 1.62, iridescent color spots may occur when observed from an oblique direction. It is preferably 1.61 or less, more preferably 1.60 or less, still more preferably 1.59 or less, and even more preferably 1.58 or less.

On the other hand, the lower limit of the refractive index is 1.53. If the refractive index is less than 1.53, the crystallization of the polyester film becomes insufficient, and the properties obtained by stretching such as dimensional stability, mechanical strength, and chemical resistance become insufficient, which is not preferable. It is preferably 1.54 or more, more preferably 1.55 or more, still more preferably 1.56 or more, still more preferably 1.57 or more.

In order to set the refractive index of the polyester film in the range parallel to the transmission axis direction of the polarizer in the range of 1.53 or more and 1.62 or less, the polarizing plate of the present invention can be used for the transmission axis of the polarizer and the polyester film. It is preferable that the phase-advancing axis (the method perpendicular to the slow-phase axis) is substantially parallel. The refractive index of the polyester film in the phase-advancing axis direction (direction perpendicular to the slow-phase axis) can be adjusted in the range of 1.53 to 1.62 by the stretching treatment in the film-forming step described later. By making the phase-advancing axis direction of the polyester film substantially parallel to the transmission axis direction of the polarizer, the refractive index of the polyester film in the direction parallel to the transmission axis direction of the polarizer is 1.53 to 1.62. A polarizing plate can be manufactured. Here, substantially parallel means that the angle formed by the transmission axis of the polarizer and the phase advance axis of the polarizer protective film is preferably -15 ° to 15 °, more preferably -10 ° to 10 °, and even more preferably. It means that it is −5 ° to 5 °, more preferably -3 ° to 3 °, still more preferably -2 ° to 2 °, and particularly preferably -1 ° to 1 °. In one preferred embodiment, substantially parallel is substantially parallel. Here, substantially parallel means that the transmission axis and the phase advance axis are parallel to the extent that the deviation that inevitably occurs when the polarizer and the protective film are bonded to each other is allowed. The direction of the slow-phase axis can be determined by measuring with a molecular orientation meter (for example, MOA-6004 type molecular orientation meter manufactured by Oji Measuring Instruments Co., Ltd.).

That is, the refractive index of the polyester film used in the present invention in the phase-advancing axis direction is preferably 1.53 or more and 1.62 or less, and the transmission axis of the polarizer and the phase-advancing axis of the polyester film are laminated so as to be substantially parallel to each other. By doing so, it is possible to manufacture a polarizing plate having a refractive index of 1.53 or more and 1.62 or less of the polyester film in the direction parallel to the transmission axis of the polarizer.

The difference between the refractive index of the polarizer constituting the polarizing plate in the transmission axis direction and the refractive index of the polyester film in the direction parallel to the transmission axis of the polarizer is preferably 0.12 or less, preferably 0.10. Hereinafter, it is preferably 0.09 or less, preferably 0.08 or less, preferably 0.07 or less, preferably 0.06 or less, and preferably 0.05 or less. The smaller the difference in refractive index, the more preferable it is because the reflection at the polyester film interface can be suppressed and the rainbow spots can be suppressed. The lower limit is 0.

The polarizer is not particularly limited, but conventionally known polarizers such as those obtained by dyeing polyvinyl alcohol (PVA) or the like with iodine can be used. The refractive index of the polarizer in the transmission axis direction is preferably 1.41 to 1.56, more preferably 1.44 to 1.55, and even more preferably 1.47 to 1.54.

Further, the polyester film used for the polarizer protective film preferably has a retardation of 1500 to 30000 nm. If the retardation is within the above range, rainbow spots tend to be more easily reduced, which is preferable. The lower limit of the preferred retardation is 3000 nm, the next preferred lower limit is 3500 nm, the more preferred lower limit is 4000 nm, the more preferred lower limit is 6000 nm, and the further preferred lower limit is 8000 nm. The preferable upper limit is 30,000 nm, and a polyester film having a retardation of more than this tends to have a considerably large thickness and a decrease in handleability as an industrial material.

The retardation can be obtained by measuring the refractive index and thickness in the orthogonal biaxial directions on the film, or can be obtained by using a commercially available automatic birefringence measuring device such as KOBRA-21ADH (Oji Measuring Instruments Co., Ltd.). You can also do it. The refractive index can be determined by an Abbe refractive index meter (measurement wavelength 589 nm).

The ratio (Re / Rth) of the polyester film retardation (Re: in-plane retardation) to the thickness direction retardation (Rth) is preferably 0.2 or more, more preferably 0.5 or more, still more preferably 0. 6 or more. The larger the ratio (Re / Rth) of the above retardation to the thickness direction retardation, the more isotropic the action of birefringence, and the less likely it is that iridescent color spots will occur depending on the observation angle. Since the ratio of the above retardation to the thickness direction retardation (Re / Rth) is 2.0 in a completely uniaxial (uniaxially symmetric) film, the ratio of the above retardation to the thickness direction retardation (Re / Rth) The upper limit is preferably 2.0. The thickness direction phase difference means the average of the phase differences obtained by multiplying the two birefringence ΔNxz and ΔNyz when the film is viewed from the cross section in the thickness direction by the film thickness d, respectively.

The polarizing element protective film made of the polyester film can be used for both the incident light side (light source side) and the emitted light side (visual recognition side). In the polarizing plate arranged on the incident light side, the polarizer protective film made of the polyester film is arranged on both sides regardless of whether the polarizing element is arranged on the incident light side or the liquid crystal cell side as a starting point. It may be arranged, but it is preferable that it is arranged at least on the incident light side. Regarding the polarizing plate arranged on the emitting light side, the polarizing element protective film made of the polyester film is arranged on both sides regardless of whether it is arranged on the liquid crystal side or the emitting light side with the polarizing element as the starting point. However, it is preferable that the film is arranged at least on the emitted light side.

As the polyester used for the polyester film, polyethylene terephthalate or polyethylene naphthalate can be used, but other copolymerization components may be contained. These resins are excellent in transparency as well as thermal and mechanical properties, and retardation can be easily controlled by stretching. In particular, polyethylene terephthalate has a large intrinsic birefringence, and by stretching the film, the refractive index in the phase-advancing axis (perpendicular to the slow-phase axis direction) can be suppressed to a low level, and it is relatively easy even if the film is thin. It is the most suitable material because it can obtain a large amount of retardation.

Further, for the purpose of suppressing deterioration of optical functional dyes such as iodine dyes, it is desirable that the polyester film has a light transmittance of 20% or less at a wavelength of 380 nm. The light transmittance at 380 nm is more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less. When the light transmittance is 20% or less, deterioration of the optical functional dye due to ultraviolet rays can be suppressed. The transmittance is measured in the direction perpendicular to the plane of the film, and can be measured using a spectrophotometer (for example, Hitachi U-3500 type).

In order to reduce the transmittance of the polyester film at a wavelength of 380 nm to 20% or less, it is desirable to appropriately adjust the type and concentration of the ultraviolet absorber and the thickness of the film. The UV absorber used in the present invention is a known substance. Examples of the ultraviolet absorber include an organic ultraviolet absorber and an inorganic ultraviolet absorber, but an organic ultraviolet absorber is preferable from the viewpoint of transparency. Examples of the organic ultraviolet absorber include benzotriazole-based, benzophenone-based, cyclic iminoester-based, and combinations thereof, but are not particularly limited as long as they are within the above-mentioned absorbance range. However, from the viewpoint of durability, benzotriazole-based and cyclic iminoester-based are particularly preferable. When two or more kinds of ultraviolet absorbers are used in combination, ultraviolet rays having different wavelengths can be absorbed at the same time, so that the ultraviolet absorption effect can be further improved.

Examples of benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and acrylonitrile-based ultraviolet absorbers include 2- [2'-hydroxy-5'-(methacryloyloxymethyl) phenyl] -2H-benzotriazole, 2- [2'. -Hydroxy-5'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2,2'-dihydroxy- 4,4'-Dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,4-di-tert-butyl-6- (5-chlorobenzotriazole-2-yl) phenol, 2- ( 2'-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (5-chloro (2H) -benzotriazole-2-yl) -4-methyl-6- ( Examples thereof include tert-butyl) phenol and 2,2′-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazole-2-yl) phenol). Examples of the ultraviolet absorbers include 2,2'-(1,4-phenylene) bis (4H-3,1-benzoxadinone-4-one) and 2-methyl-3,1-benzoxazine-4-one. , 2-Butyl-3,1-benzoxazine-4-one, 2-phenyl-3,1-benzoxazine-4-one and the like, but are not particularly limited thereto.

In addition to the ultraviolet absorber, it is also preferable to contain various additives other than the catalyst as long as the effects of the present invention are not impaired. As additives, for example, inorganic particles, heat-resistant polymer particles, alkali metal compounds, alkaline earth metal compounds, phosphorus compounds, antistatic agents, light retardants, flame retardants, heat stabilizers, antioxidants, antigelling agents. , Surfactants and the like. Further, in order to obtain high transparency, it is also preferable that the polyester film contains substantially no particles. "Substantially free of particles" means, for example, in the case of inorganic particles, the content of 50 ppm or less, preferably 10 ppm or less, particularly preferably the detection limit or less when the inorganic element is quantified by Keiko X-ray analysis. means.

On the surface of the polyester film, which is a polarizing element protective film used in the present invention, various functional layers, that is, a hard coat layer, an antiglare layer, an antireflection layer, etc., are used for the purpose of preventing reflection, glare, and scratches. It is also a preferable mode to provide. When providing various functional layers, it is preferable that the polyester film has an easy-adhesion layer on its surface. At that time, from the viewpoint of suppressing interference due to reflected light, it is preferable to adjust the refractive index of the easy-adhesion layer so as to be close to the synergistic average of the refractive index of the functional layer and the refractive index of the polyester film. A known method can be adopted for adjusting the refractive index of the easy-adhesion layer. For example, the refractive index can be easily adjusted by adding titanium, germanium, or other metal species to the binder resin.

The polyester film can also be subjected to a corona treatment, a coating treatment, a flame treatment, or the like in order to improve the adhesiveness with the polarizer.

In the present invention, in order to improve the adhesiveness to the polarizer, an easy-adhesion layer containing at least one of polyester resin, polyurethane resin or polyacrylic resin as a main component is provided on at least one side of the film of the present invention. Is preferable. Here, the "main component" refers to a component that is 50% by mass or more of the solid components constituting the easy-adhesion layer. The coating liquid used for forming the easy-adhesion layer of the present invention is preferably an aqueous coating liquid containing at least one of a water-soluble or water-dispersible copolymerized polyester resin, an acrylic resin and a polyurethane resin. Examples of these coating solutions include water-soluble or water-dispersible copolymers disclosed in Japanese Patent No. 3567927, Japanese Patent No. 3589232, Japanese Patent No. 3589233, Japanese Patent No. 3900191, Japanese Patent No. 4150982, and the like. Examples thereof include a polymerized polyester resin solution, an acrylic resin solution, and a polyurethane resin solution.

The easy-adhesion layer can be obtained by applying the coating liquid to one or both sides of a uniaxially stretched film in the vertical direction, drying at 100 to 150 ° C., and further stretching in the horizontal direction. The final coating amount of the easy-adhesion layer is preferably controlled to 0.05 to 0.20 g / m2. If the coating amount is ^{less than 0.05 g / m 2} , the adhesiveness with the obtained polarizer may be insufficient. On the other hand, if the coating amount ^{exceeds 0.20 g / m 2} , the blocking resistance may decrease. When the easy-adhesion layers are provided on both sides of the polyester film, the coating amounts of the easy-adhesion layers on both sides may be the same or different, and can be independently set within the above ranges.

It is preferable to add particles to the easy-adhesion layer in order to impart slipperiness. It is preferable to use particles having an average particle size of 2 μm or less. When the average particle size of the particles exceeds 2 μm, the particles are likely to fall off from the coating layer. The particles contained in the easy-adhesion layer include, for example, titanium oxide, barium sulfate, calcium carbonate, calcium sulfate, silica, alumina, talc, kaolin, clay, calcium phosphate, mica, hectrite, zirconia, tungsten oxide, lithium fluoride, etc. Examples thereof include inorganic particles such as calcium fluoride and organic polymer particles such as styrene-based, acrylic-based, melamine-based, benzoguanamine-based, and silicone-based particles. These may be added to the easy-adhesion layer alone, or may be added in combination of two or more.

Further, as a method of applying the coating liquid, a known method can be used. For example, the reverse roll coating method, the gravure coating method, the kiss coating method, the roll brush method, the spray coating method, the air knife coating method, the wire bar coating method, the pipe doctor method, etc. can be mentioned, and these methods can be used alone. Alternatively, it can be performed in combination.

The average particle size of the above particles is measured by the following method. The particles are photographed with a scanning electron microscope (SEM), and the maximum diameter of 300 to 500 particles (between the two most distant points) is magnified so that the size of one of the smallest particles is 2 to 5 mm. Distance) is measured, and the average value is taken as the average particle size.

The polyester film used as the polarizer protective film can be manufactured according to a general polyester film manufacturing method. For example, a non-oriented polyester obtained by melting a polyester resin and extruding it into a sheet is stretched in the vertical direction by utilizing the speed difference of rolls at a temperature equal to or higher than the glass transition temperature, and then stretched in the horizontal direction by a tenter. A method of applying heat treatment can be mentioned.

The polyester film used in the present invention may be a uniaxially stretched film or a biaxially stretched film, but when the biaxially stretched film is used as a polarizer protective film, it is observed from directly above the film surface. However, rainbow-shaped color spots are not seen, but it should be noted that rainbow-shaped color spots may be observed when observed from an oblique direction.

Specifically, the film forming conditions of the polyester film are preferably 80 to 135 ° C., more preferably 80 to 130 ° C., and particularly preferably 90 to 120 ° C. for the longitudinal stretching temperature and the transverse stretching temperature. In order to orient the film so that the slow axis is in the TD direction, the longitudinal stretching ratio is preferably 1.0 to 3.5 times, particularly preferably 1.0 to 3.0 times. The lateral stretching ratio is preferably 2.5 to 6.0 times, particularly preferably 3.0 to 5.5 times. In order to orient the film so that the slow axis is in the MD direction, the longitudinal stretching ratio is preferably 2.5 to 6.0 times, particularly preferably 3.0 to 5.5 times. The transverse stretching ratio is preferably 1.0 to 3.5 times, and particularly preferably 1.0 to 3.0 times.
In order to control the refractive index or retardation of the polyester film in the phase-advancing axis direction within the above range, it is preferable to control the ratio of the longitudinal stretching ratio to the transverse stretching ratio. If the difference between the vertical and horizontal stretching ratios is too small, the refractive index of the polyester film in the phase-advancing axis direction tends to exceed 1.62, and it becomes difficult to increase the retardation, which is not preferable. Further, setting the stretching temperature low is a preferable measure for increasing the retardation. In the subsequent heat treatment, the treatment temperature is preferably 100 to 250 ° C, particularly preferably 180 to 245 ° C.
In order to suppress the fluctuation of retardation, it is preferable that the thickness unevenness of the film is small. Since the stretching temperature and the stretching ratio have a great influence on the thickness unevenness of the film, it is necessary to optimize the film forming conditions from the viewpoint of the thickness unevenness. In particular, if the longitudinal stretching ratio is lowered in order to increase the retardation, the vertical thickness unevenness may worsen. Since there is a region where the vertical thickness unevenness becomes very poor in a specific range of the draw ratio, it is desirable to set the film forming conditions outside this range.
The thickness unevenness of the polyester film is preferably 5.0% or less, more preferably 4.5% or less, still more preferably 4.0% or less, and more preferably 3.0% or less. Is particularly preferable.

As described above, in order to control the retardation of the polyester film within a specific range, it can be performed by appropriately setting the draw ratio, the draw temperature, and the thickness of the film. For example, the higher the stretching ratio, the lower the stretching temperature, and the thicker the film, the easier it is to obtain high retardation. On the contrary, the lower the stretching ratio, the higher the stretching temperature, and the thinner the film, the easier it is to obtain low retardation. However, when the thickness of the film is increased, the phase difference in the thickness direction tends to increase. Therefore, it is desirable to appropriately set the film thickness within the range described later. Further, in addition to the control of retardation, it is necessary to set the final film forming conditions in consideration of the physical characteristics required for processing.

The thickness of the polyester film is arbitrary, but is preferably in the range of 15 to 300 μm, more preferably in the range of 15 to 200 μm. In principle, it is possible to obtain retardation of 1500 nm or more even with a film having a thickness of less than 15 μm. However, in that case, the anisotropy of the mechanical properties of the film becomes remarkable, and tearing, tearing, etc. are likely to occur, and the practicality as an industrial material is remarkably lowered. A particularly preferable lower limit of the thickness is 25 μm. On the other hand, if the upper limit of the thickness of the polarizing element protective film exceeds 300 μm, the thickness of the polarizing plate becomes too thick, which is not preferable. From the viewpoint of practicality as a polarizer protective film, the upper limit of the thickness is preferably 200 μm. A particularly preferable upper limit of the thickness is 100 μm, which is equivalent to that of a general TAC film. In order to control the retardation within the range of the present invention even in the above thickness range, polyethylene sauce phthalate is preferable as the polyester used as the film base material.

Further, as a method of blending the ultraviolet absorber into the polyester film, a known method can be used in combination. For example, a master batch is prepared by blending the dried ultraviolet absorber and the polymer raw material using a kneading extruder in advance. It can be prepared and blended by a method of mixing the predetermined masterbatch with the polymer raw material at the time of film formation.

At this time, the concentration of the ultraviolet absorber in the masterbatch is preferably 5 to 30% by mass in order to uniformly disperse the ultraviolet absorber and to blend it economically. As a condition for producing the masterbatch, it is preferable to use a kneading extruder and extrude the polyester raw material at a temperature equal to or higher than the melting point of the polyester raw material and not higher than 290 ° C. for 1 to 15 minutes. If the temperature exceeds 290 ° C., the amount of the ultraviolet absorber is greatly reduced, and the viscosity of the masterbatch is significantly reduced. If the extrusion time is 1 minute or less, it becomes difficult to uniformly mix the ultraviolet absorber. At this time, a stabilizer, a color tone adjusting agent, and an antistatic agent may be added as needed.

Further, it is preferable that the polyester film has a multilayer structure of at least three layers or more, and an ultraviolet absorber is added to the intermediate layer of the film. Specifically, a film having a three-layer structure containing an ultraviolet absorber in the intermediate layer can be produced as follows. A polyester pellet alone for the outer layer, and a masterbatch containing an ultraviolet absorber for the intermediate layer and polyester pellets are mixed at a predetermined ratio, dried, and then supplied to a known fused deposition model extruder to form a slit. It is extruded from a die into a sheet and cooled and solidified on a casting roll to form an unstretched film. That is, using two or more extruders, a three-layer manifold or a merging block (for example, a merging block having a square merging portion), the film layers constituting both outer layers and the film layers constituting the intermediate layer are laminated. A three-layer sheet is extruded from the base and cooled with a casting roll to make an unstretched film. In addition, in order to remove foreign substances contained in the raw material polyester, which causes optical defects, it is preferable to perform high-precision filtration at the time of melt extrusion. The filter particle size (initial filtration efficiency 95%) of the filter medium used for high-precision filtration of the molten resin is preferably 15 μm or less. If the size of the filtered particles of the filter medium exceeds 15 μm, the removal of foreign matter of 20 μm or more tends to be insufficient.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples, and is carried out with appropriate modifications to the extent that it can be adapted to the gist of the present invention. It is also possible, all of which are within the technical scope of the invention. The method for evaluating the physical properties in the following examples is as follows.

(1) Refraction of polyester film Using a molecular orientation meter (MOA-6004 type molecular orientation meter manufactured by Oji Measuring Instruments Co., Ltd.), determine the slow axis direction of the film, and the slow axis direction is the long side of the sample for measurement. A rectangle of 4 cm × 2 cm was cut out so as to be parallel to the above, and used as a measurement sample. For this sample, the refractive indexes of the two orthogonal axes (refractive index in the slow axis direction: Ny, refractive index in the phase advance axis (refractive index in the direction orthogonal to the slow axis direction): Nx), and the refractive index in the thickness direction ( Nz) was determined by an Abbe refractive index meter (manufactured by Atago Co., Ltd., NAR-4T, measurement wavelength 589 nm).

(2) Reference (Re)
The retardation is a parameter defined by the product (ΔNxy × d) of the anisotropy of the refractive indexes of the two orthogonal axes on the film (ΔNxy = | Nx−Ny |) and the film thickness d (nm). Yes, it is a scale showing optical isotropic and anisotropy. The biaxial refractive index anisotropy (ΔNxy) was determined by the following method. Using a molecular orientation meter (MOA-6004 type molecular orientation meter manufactured by Oji Measuring Instruments Co., Ltd.), determine the slow-phase axial direction of the film, and make the slow-phase axial direction parallel to the long side of the measurement sample, 4 cm. A rectangle of × 2 cm was cut out and used as a measurement sample. For this sample, the refractive index of two orthogonal axes (refractive index in the slow axis direction: Ny, refractive index in the direction orthogonal to the slow axis direction: Nx), and the refractive index in the thickness direction (Nz) are abbe refraction. It was determined by a rate meter (manufactured by Atago Co., Ltd., NAR-4T, measurement wavelength 589 nm), and the absolute value (| Nx-Ny |) of the difference in refractive index between the two axes was defined as the anisotropy of the refractive index (ΔNxy). The film thickness d (nm) was measured using an electric micrometer (Millitron 1245D, manufactured by Fine Wolf Co., Ltd.), and the unit was converted to nm. The retardation (Re) was determined from the product (ΔNxy × d) of the anisotropy of the refractive index (ΔNxy) and the thickness d (nm) of the film.

(3) Thickness direction retardation (Rth)
The thickness direction retardation is obtained by multiplying two birefringences ΔNxz (= | Nx−Nz |) and ΔNyz (= | Ny−Nz |) when viewed from a cross section in the film thickness direction by the film thickness d, respectively. It is a parameter indicating the average of the refraction obtained. Nx, Ny, Nz and the film thickness d (nm) are obtained by the same method as the measurement of retardation, and the average value of (ΔNxz × d) and (ΔNyz × d) is calculated to calculate the thickness direction retardation (Rth). ) Was asked.

(4) Measurement of Emission Spectrum of Backlight Light Source REGZA 43J10X manufactured by Toshiba Corporation was used as the liquid crystal display device used in each example. When the emission spectrum of the backlight source (white light emitting diode) of this liquid crystal display device was measured using a multi-channel spectroscope PMA-12 manufactured by Hamamatsu Photonics, an emission spectrum having peak tops near 450 nm, 535 nm, and 630 nm was observed. Was done. The half width of each peak top (half width of the peak having the highest peak intensity in each wavelength region) was 17 nm for the peak at 450 nm and 45 nm for the peak at 535 nm and 2 nm for the peak at 630 nm, respectively. This light source had a plurality of peaks in the wavelength region of 600 nm or more and 780 nm or less, and the half width was evaluated at the peak near 630 nm, which has the highest peak intensity in this region. The exposure time for spectrum measurement was 20 msec.

(5) Observation of rainbow spots
The liquid crystal display device obtained in each example was visually observed in a dark place from the front and from an oblique direction, and the presence or absence of rainbow spots was determined as follows.

◯: No rainbow spots are observed △: Slight rainbow spots are observed ×: Rainbow spots are observed × ×: Rainbow spots are significantly observed

(6) Refractive index of polarizer
The refractive index of the polarizer in the transmission axis direction was measured with an Abbe refractometer (manufactured by Atago, NAR-4T SOLID, measurement wavelength 589 nm).

(Production Example 1-Polyester A)
When the temperature of the esterification reaction can was raised to 200 ° C., 86.4 parts by mass of terephthalic acid and 64.6 parts by mass of ethylene glycol were charged, and 0.017 parts by mass of antimony trioxide was used as a catalyst while stirring. 0.064 parts by mass of magnesium acetate tetrahydrate and 0.16 parts by mass of triethylamine were charged. Then, the pressure was raised and the pressure esterification reaction was carried out under the conditions of a gauge pressure of 0.34 MPa and 240 ° C., the esterification reaction can was returned to normal pressure, and 0.014 parts by mass of phosphoric acid was added. Further, the temperature was raised to 260 ° C. over 15 minutes, and 0.012 parts by mass of trimethyl phosphate was added. Then, after 15 minutes, dispersion treatment was carried out with a high-pressure disperser, and after 15 minutes, the obtained esterification reaction product was transferred to a polycondensation reaction can, and a polycondensation reaction was carried out under reduced pressure at 280 ° C.

After completion of the polycondensation reaction, filtration is performed with a Naslon filter having a 95% cut diameter of 5 μm, extruded into a strand shape from a nozzle, and cooled and solidified using cooling water that has been previously filtered (pore diameter: 1 μm or less). , Cut into pellets. The intrinsic viscosity of the obtained polyethylene terephthalate resin (A) was 0.62 dl / g, and it contained substantially no inert particles and internally precipitated particles. (Hereafter, it is abbreviated as PET (A).)

(Production Example 2-Polyester B)
10 parts by mass of dried UV absorber (2,2'-(1,4-phenylene) bis (4H-3,1-benzoxadinone-4-one), particle-free PET (A) (intrinsic viscosity) 0.62 dl / g) 90 parts by mass was mixed, and a polyethylene terephthalate resin (B) containing an ultraviolet absorber was obtained using a kneading extruder (hereinafter abbreviated as PET (B)).

(Manufacturing Example 3-Adhesive Modification Coating Liquid Adjustment)
Transesterification and polycondensation reactions were carried out by a conventional method to obtain 46 mol% of terephthalic acid, 46 mol% of isophthalic acid and 8 mol% of sodium 5-sulfonatoisophthalate as dicarboxylic acid components (relative to the entire dicarboxylic acid component). A water-dispersible metal sulfonate metal base-containing copolymer resin having a composition of 50 mol% of ethylene glycol and 50 mol% of neopentyl glycol as the glycol component was prepared. Next, 51.4 parts by mass of water, 38 parts by mass of isopropyl alcohol, 5 parts by mass of n-butyl cell solution, and 0.06 parts by mass of a nonionic surfactant were mixed, and then heated and stirred. After adding 5 parts by mass of a water-dispersible metal sulfonate metal-based copolymer resin and continuing to stir until the resin is no longer clumped, the resin aqueous dispersion is cooled to room temperature to have a solid content concentration of 5.0% by mass. A uniform water-dispersible copolymerized polyester resin liquid was obtained. Further, after 3 parts by mass of aggregate silica particles (Syricia 310 manufactured by Fuji Silicia Co., Ltd.) were dispersed in 50 parts by mass of water, 99.46 parts by mass of the water-dispersible copolymerized polyester resin liquid was added to Syricia 310. 0.54 parts by mass of an aqueous dispersion was added, and 20 parts by mass of water was added with stirring to obtain an adhesive modification coating liquid.

(Polarizer)
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm, which was continuously dyed in an aqueous iodine solution, was stretched 5 times in the transport direction and dried to obtain a long polarizer. The refractive index of the produced polarizer in the transmission axis direction was 1.51.

(Polarizer protective film 1)
After 90 parts by mass of PET (A) resin pellets containing no particles and 10 parts by mass of PET (B) resin pellets containing an ultraviolet absorber are dried under reduced pressure (1 Torr) at 135 ° C. for 6 hours as raw materials for the base film intermediate layer. , It was supplied to the extruder 2 (for the intermediate layer II layer), and the PET (A) was dried by a conventional method and supplied to the extruder 1 (for the outer layer I layer and the outer layer III), respectively, and melted at 285 ° C. .. These two types of polymers are filtered through a stainless steel sintered filter medium (nominal filtration accuracy of 10 μm particles 95% cut), laminated in a two-type three-layer confluence block, extruded into a sheet from the base, and then extruded. Using the electrostatic application casting method, the film was wound around a casting drum having a surface temperature of 30 ° C. and cooled and solidified to prepare an unstretched film. At this time, the discharge amount of each extruder was adjusted so that the ratio of the thicknesses of the I layer, the II layer, and the III layer was 10:80:10.

Next, the adhesive modification coating liquid was applied to both sides of the unstretched PET film by the reverse roll method ^{so that the coating amount after drying was 0.08 g / m 2} , and then dried at 80 ° C. for 20 seconds. ..

The unstretched film on which the coating layer was formed was guided to a tenter stretching machine, and while gripping the edge of the film with a clip, it was guided to a hot air zone having a temperature of 125 ° C. and stretched 4.0 times in the width direction. Next, while maintaining the width stretched in the width direction, the film was treated at a temperature of 225 ° C. for 10 seconds, and further subjected to a relaxation treatment of 3.0% in the width direction to obtain a uniaxially stretched PET film having a film thickness of about 100 μm. rice field. The Re of the obtained film was 10300 nm, the Rth was 12350 nm, the Re / Rth was 0.83, Nx = 1.588, and Ny = 1.691.

(Polarizer protective film 2)
A film was formed in the same manner as the polarizer protective film 1 except that the line speed was changed to change the thickness of the unstretched film, and a uniaxially stretched PET film having a film thickness of about 80 μm was obtained. The Re of the obtained film was 8080 nm, Rth was 9960 nm, Re / Rth was 0.81, Nx = 1.589, and Ny = 1.690.

(Polarizer protective film 3)
A film was formed in the same manner as the polarizer protective film 1 except that the line speed was changed to change the thickness of the unstretched film, and a uniaxially stretched PET film having a film thickness of about 60 μm was obtained. The Re of the obtained film was 6060 nm, Rth was 7470 nm, Re / Rth was 0.81, Nx = 1.589, and Ny = 1.690.

(Polarizer protective film 4)
A film was formed in the same manner as the polarizer protective film 1 except that the line speed was changed to change the thickness of the unstretched film, and a uniaxially stretched PET film having a film thickness of about 40 μm was obtained. The Re of the obtained film was 4160 nm, the Rth was 4920 nm, the Re / Rth was 0.85, Nx = 1.587, and Ny = 1.691.

(Polarizer protective film 5)
The unstretched film produced by the same method as the polarizer protective film 1 is heated to 105 ° C. using a heated roll group and an infrared heater, and then 1.5 in the traveling direction in the roll group having a peripheral speed difference. After double-stretching, the film was guided to a hot air zone at a temperature of 130 ° C. and stretched 4.0 times in the width direction to obtain a biaxially stretched PET film having a film thickness of about 100 μm in the same manner as in the polarizer protective film 1. The Re of the obtained film was 7820 nm, the Rth was 13890 nm, the Re / Rth was 0.56, Nx = 1.608, and Ny = 1.686.

(Polarizer protective film 6)
The unstretched film produced by the same method as the polarizer protective film 1 is heated to 105 ° C. using a heated roll group and an infrared heater, and then 2.0 in the traveling direction in the roll group having a peripheral speed difference. After double stretching, the film was guided to a hot air zone at a temperature of 135 ° C. and stretched 4.0 times in the width direction to obtain a biaxially stretched PET film having a film thickness of about 100 μm in the same manner as the polarizer protective film 1. The Re of the obtained film was 6400 nm, the Rth was 14600 nm, the Re / Rth was 0.44, Nx = 1.617, and Ny = 1.681.

(Polarizer protective film 7)
The unstretched film produced by the same method as the polarizer protective film 1 is heated to 105 ° C. using a heated roll group and an infrared heater, and then 2.8 in the traveling direction in the roll group having a peripheral speed difference. After double-stretching, the film was guided to a hot air zone at a temperature of 140 ° C. and stretched 4.0 times in the width direction to obtain a biaxially stretched PET film having a film thickness of about 100 μm in the same manner as in the polarizer protective film 1. The Re of the obtained film was 5400 nm, the Rth was 15900 nm, the Re / Rth was 0.34, Nx = 1.631, and Ny = 1.685.

(Polarizer protective film 8)
The unstretched film produced by the same method as the polarizer protective film 1 is heated to 105 ° C. using a heated roll group and an infrared heater, and then 3.3 in the traveling direction in the roll group having a peripheral speed difference. After double-stretching, the film was guided to a hot air zone at a temperature of 140 ° C. and stretched 4.0 times in the width direction to obtain a biaxially stretched PET film having a film thickness of about 100 μm in the same manner as in the polarizer protective film 1. The Re of the obtained film was 4800 nm, Rth was 16700 nm, Re / Rth was 0.29, Nx = 1.640, and Ny = 1.688.
A liquid crystal display device was created using the polarizer protective films 1 to 8 as described later.

(Example 1)
A polarizing element protective film 1 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are parallel to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. The polarizing plate 1 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was created by replacing the polarizing plate on the visible side of REGZA 43J10X manufactured by Toshiba Corporation with the above polarizing plate 1 so that the polyester film was on the opposite side (distal) to the liquid crystal. The direction of the transmission axis of the polarizing plate 1 was replaced so as to be the same as the direction of the transmission axis of the polarizing plate before the replacement.

(Example 2)
A polarizing element protective film 2 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are parallel to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. The polarizing plate 2 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was produced in the same manner as in Example 1 except that the polarizing plate 1 was changed to the polarizing plate 2.

(Example 3)
A polarizing element protective film 3 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are parallel to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. The polarizing plate 3 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was produced in the same manner as in Example 1 except that the polarizing plate 1 was changed to the polarizing plate 3.

(Example 4)
A polarizing element protective film 3 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are parallel to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. The polarizing plate 3 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was created by replacing the polarizing plate on the light source side of REGZA 43J10X manufactured by Toshiba with the above polarizing plate 3 so that the polyester film is on the opposite side (distal) to the liquid crystal. The direction of the transmission axis of the polarizing plate 3 was replaced so as to be the same as the direction of the transmission axis of the polarizing plate before the replacement.

(Example 5)
A polarizing element protective film 3 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are parallel to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. The polarizing plate 3 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was created by replacing the polarizing plates on the visual side and the light source side of REGZA 43J10X manufactured by Toshiba with the above polarizing plate 3 so that the polyester film was on the opposite side (distal) to the liquid crystal. The direction of the transmission axis of the polarizing plate 3 was replaced so as to be the same as the direction of the transmission axis of the polarizing plate before the replacement.

(Example 6)
A polarizing element protective film 4 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are parallel to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. The polarizing plate 4 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was produced in the same manner as in Example 1 except that the polarizing plate 1 was changed to the polarizing plate 4.

(Example 7)
A polarizing element protective film 5 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are parallel to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. A polarizing plate 5 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was produced in the same manner as in Example 1 except that the polarizing plate 1 was changed to the polarizing plate 5.

(Example 8)
A polarizing element protective film 6 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are parallel to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. A polarizing plate 6 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was produced in the same manner as in Example 1 except that the polarizing plate 1 was changed to the polarizing plate 6.

(Comparative Example 1)
A polarizing element protective film 1 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are perpendicular to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. A polarizing plate 7 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was created by replacing the polarizing plate on the visible side of REGZA 43J10X manufactured by Toshiba with the above polarizing plate 7 so that the polyester film was on the opposite side (distal) to the liquid crystal. The direction of the transmission axis of the polarizing plate 7 was replaced so as to be the same as the direction of the transmission axis of the polarizing plate before the replacement.

(Comparative Example 2)
A polarizing element protective film 2 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are perpendicular to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. A polarizing plate 8 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was produced in the same manner as in Comparative Example 1 except that the polarizing plate 7 was changed to the polarizing plate 8.

(Comparative Example 3)
A polarizing element protective film 3 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are perpendicular to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. A polarizing plate 9 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was produced in the same manner as in Comparative Example 1 except that the polarizing plate 7 was changed to the polarizing plate 9.

(Comparative Example 4)
A polarizing element protective film 3 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are perpendicular to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. A polarizing plate 9 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was created by replacing the polarizing plate on the light source side of REGZA 43J10X manufactured by Toshiba with the above polarizing plate 9 so that the polyester film is on the opposite side (distal) to the liquid crystal. The direction of the transmission axis of the polarizing plate 9 was replaced so as to be the same as the direction of the transmission axis of the polarizing plate before replacement.

(Comparative Example 5)
A polarizing element protective film 3 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are perpendicular to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. A polarizing plate 9 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was created by replacing the visible plate and the light source side polarizing plate manufactured by Toshiba REGZA 43J10X with the above polarizing plate 9 so that the polyester film was on the opposite side (distal) to the liquid crystal. The direction of the transmission axis of the polarizing plate 9 was replaced so as to be the same as the direction of the transmission axis of the polarizing plate before replacement.

(Comparative Example 6)
A polarizing element protective film 4 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are perpendicular to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. The polarizing plate 10 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was produced in the same manner as in Comparative Example 1 except that the polarizing plate 7 was changed to the polarizing plate 10.

(Comparative Example 7)
A polarizing element protective film 7 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are parallel to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. The polarizing plate 11 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was produced in the same manner as in Comparative Example 1 except that the polarizing plate 7 was changed to the polarizing plate 11.

(Comparative Example 8)
A polarizing element protective film 8 is attached to one side of a polarizer composed of PVA and iodine so that the transmission axis of the polarizer and the phase advance axis of the film are parallel to each other, and TAC film (Fuji Film Co., Ltd.) is attached to the opposite surface. The polarizing plate 12 was prepared by pasting (manufactured by 80 μm in thickness). A liquid crystal display device was produced in the same manner as in Comparative Example 1 except that the polarizing plate 7 was changed to the polarizing plate 12.

The results of measuring the rainbow spot observation for the liquid crystal display device obtained in each example are shown in Table 1 below.

The liquid crystal display device and the polarizing plate of the present invention can ensure good visibility in which the occurrence of rainbow-shaped color spots is significantly suppressed at any observation angle, and have extremely high industrial applicability. ..

Claims (14)

A liquid crystal display device having a backlight light source, two polarizing plates, and a liquid crystal cell arranged between the two polarizing plates.
The backlight source has a peak top of the emission spectrum in each wavelength region of 400 nm or more and less than 495 nm, 495 nm or more and less than 600 nm, and 600 nm or more and 780 nm or less, and has the highest peak intensity in the wavelength region of 600 nm or more and 780 nm or less. A white light source having an emission spectrum with a peak width of less than 5 nm.
At least one of the polarizing plates is obtained by laminating a polyester film having a retardation of 1500 to 30,000 nm on at least one surface of the polarizing element, and is in a direction parallel to the transmission axis of the polarizing element. The refractive index of the polyester film is 1.53 to 1.62.
Liquid crystal display device. The liquid crystal display device according to claim 1, wherein the polyester film has a thickness of 25 to 80 μm (excluding those having a thickness of 80 μm). The retardation of the polyester film is 8000 nm or more.
The liquid crystal display device according to claim 1. The polyester film has a refractive index of 1.53 to 1.61 in a direction parallel to the transmission axis of the polarizer.
The Re / Rth of the polyester film is 0.2 to 0.85.
The liquid crystal display device according to claim 1. The refractive index of the polyester film in the direction parallel to the transmission axis of the polarizer is 1.53 to 1.60.
The retardation of the polyester film is 4160 nm or more.
The liquid crystal display device according to claim 1. The retardation of the polyester film is 4160-7820 nm.
The liquid crystal display device according to claim 1. The emission spectrum of the backlight source is
The half width of the peak with the highest peak intensity in the wavelength region of 400 nm or more and less than 495 nm is 5 nm or more.
The half width of the peak with the highest peak intensity in the wavelength region of 495 nm or more and less than 600 nm is 5 nm or more.
The liquid crystal display device according to any one of claims 1 to 6. 7. LCD display device. A polarizing plate in which a polyester film having a retardation of 1500 to 30000 nm is laminated on at least one surface of a polarizing element.
The polyester film has a refractive index of 1.53 to 1.62 in a direction parallel to the transmission axis of the polarizer.
It has a peak top of the emission spectrum in each wavelength region of 400 nm or more and less than 495 nm, 495 nm or more and less than 600 nm, and 600 nm or more and 780 nm or less, and the half width of the peak with the highest peak intensity in the wavelength region of 600 nm or more and 780 nm or less is 5 nm. A polarizing plate for a liquid crystal display device having a backlight light source composed of a white light source having an emission spectrum of less than. The polarizing plate for a liquid crystal display device according to claim 9, wherein the polyester film has a thickness of 25 to 80 μm (excluding those having a thickness of 80 μm). The retardation of the polyester film is 8000 nm or more.
The polarizing plate for a liquid crystal display device according to claim 9. The polyester film has a refractive index of 1.53 to 1.61 in a direction parallel to the transmission axis of the polarizer.
The Re / Rth of the polyester film is 0.2 to 0.85.
The polarizing plate for a liquid crystal display device according to claim 9. The refractive index of the polyester film in the direction parallel to the transmission axis of the polarizer is 1.53 to 1.60.
The retardation of the polyester film is 4160 nm or more.
The polarizing plate for a liquid crystal display device according to claim 9. The retardation of the polyester film is 4160-7820 nm.
The polarizing plate for a liquid crystal display device according to claim 9.