JP2016021000A - Polarizer protective film, polarizing plate, and liquid crystal display device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polarizer protective film that ensures good visibility of a liquid crystal display device while preventing iridescent speckles in observation of the device in a direction oblique to the normal direction on a display screen of the device, even when the film is made thin, and to provide a polarizing plate and a liquid crystal display device using the above film.SOLUTION: The polarizer protective film is composed of a polyester film having a retardation of 3000 to 30000 nm. The polyester constituting the above polyester film is a mixture of a polyester (A) and a polyester (B). The polyester (A) comprises an aromatic dicarboxylic acid component and ethylene glycol as a glycol component; and the polyester (B) comprises an aromatic dicarboxylic acid component and a glycol component comprising at least an alkylene glycol having 3 or more carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to a polarizer protective film having good visibility and suitable for thinning, a polarizing plate using the same, and a liquid crystal display device.

  A liquid crystal display device has polarizing plates on both sides of a liquid crystal cell, and has a light source such as a cold cathode fluorescent lamp (hereinafter referred to as CCFL) or a light emitting diode (hereinafter referred to as LED) disposed on one surface. It is a device that displays an image or the like by a backlight.

  The polarizing plate is composed of a film called a polarizer mainly composed of polyvinyl alcohol (PVA) and adsorbed and oriented with iodine compound molecules, and a polarizer protective film disposed on both sides thereof. In general, the polarizer protective film is composed of a triacetyl cellulose (hereinafter referred to as TAC) film.

  In recent years, with the thinning of liquid crystal display devices, there has been a demand for thinner polarizing plates. Thereby, it was desired to reduce the thickness of the polarizer protective film, but when the polarizer protective film is a TAC film, sufficient mechanical strength cannot be obtained, and there are problems such as easy moisture permeability, Due to its high price, an inexpensive alternative material has been strongly desired.

  It is proposed to use a polyester film as an alternative material for the above problems (Patent Documents 1 to 4).

  Polyester film is promising as an alternative material because it has high mechanical strength and low moisture permeability compared to TAC film, but the effect of optical anisotropy is likely to be manifested by thinning the film. When observed from an oblique direction with respect to the vertical direction of the display surface, there is a problem that rainbow spots (color spots) and the like are easily recognized.

  In order to solve the above problem, in Patent Documents 1 to 3, a countermeasure is taken to reduce optical anisotropy by using a copolyester as a polyester, but to eliminate rainbow spots (color spots). Not reached.

  Patent Document 4 focuses on the birefringence of the polyester film and the emission spectrum of the backlight. By using a combination of a specific backlight light source and a polyester film having a specific retardation, the above rainbow spots (color spots) can be obtained. It is disclosed that the problem can be solved.

JP 2002-116320 A JP 2004-219620 A JP 2004-205773 A Japanese Patent No. 4926661

However, even with the polarizer protective film disclosed in Patent Document 4, rainbow spots may occur in response to a request for further thinning of the polyester film.
That is, the present invention provides a polarizer capable of ensuring good visibility with no rainbow when observed from an oblique direction with respect to the vertical direction on the display surface of the liquid crystal display device even when the film thickness is reduced. It is an object to provide a protective film, a polarizing plate using the protective film, and a liquid crystal display device.

  As a result of intensive studies, the present inventor has found that a polyester (A) obtained by polymerizing an aromatic dicarboxylic acid component and ethylene glycol, a glycol containing at least an aromatic dicarboxylic acid component and an alkylene glycol having 3 or more carbon atoms. If it is a polarizer protective film using polyester obtained by mixing polyester (B) obtained by polymerizing components, the above problems can be solved, and a film that can be adapted to further thinning can be obtained. I found.

Item 1.
A polarizer protective film comprising a polyester film having a retardation of 3000 to 30000 nm,
The polyester constituting the polyester film is a mixture of polyester (A) and polyester (B),
The polyester (A) is a polyester composed of an aromatic dicarboxylic acid component and ethylene glycol as a glycol component,
The polyester (B) is a polyester composed of an aromatic dicarboxylic acid component and a glycol component containing at least an alkylene glycol having 3 or more carbon atoms.
Polarizer protective film.
Item 2.
When the refractive index in the slow axis direction in the plane of the polyester film is Ny, the refractive index in the direction perpendicular to the slow axis in the plane is Nx, and the refractive index in the thickness direction is Nz, The polarizer protective film of claim | item 1 whose NZ coefficient represented by (Nz-Ny) / (Nx-Ny) is 1.55 or less.
Item 3.
Item 1 or 2 characterized in that the polyester has 85 to 97 mol% ethylene glycol and 3 to 15 mol% alkylene glycol having 3 or more carbon atoms when the total glycol component is 100 mol%. The polarizer protective film of description.
Item 4.
Item 4. The polarizer protective film according to any one of Items 1 to 3, wherein the polyester (A) is polyethylene terephthalate and / or polyethylene naphthalate, and the polyester (B) is polytrimethylene terephthalate and / or polybutylene terephthalate. .
Item 5.
Item 5. The polarizer protective film according to any one of Items 1 to 4, wherein the polyester film has a thickness of 20 μm to 100 μm.
Item 6.
The polarizing plate by which the polarizer protective film in any one of claim | item 1 -5 was laminated | stacked on the at least one surface of the polarizer.
Item 7.
7. A liquid crystal display device having a backlight, a liquid crystal cell, and polarizing plates disposed on both sides of the liquid crystal cell, wherein at least one polarizing plate is the polarizing plate according to item 6.

In the case of the polarizer protective film of the present invention, even when the polarizer protective film is thinned, when observed from an oblique direction with respect to the vertical direction on the display surface of the liquid crystal display device, rainbow spots (color spots) And good visibility can be secured. Moreover, according to this invention, it is excellent in visibility and can provide a thinner polarizing plate and a liquid crystal display device.

Hereinafter, the present invention will be described in detail.

The polarizer protective film of the present invention is a polarizer protective film made of a polyester film having a retardation of 3000 to 30000 nm. The polyester constituting the polyester film is a mixture (blend) of polyester (A) and polyester (B). The polyester (A) is a polyester composed of an aromatic dicarboxylic acid component and ethylene glycol as a glycol component. The polyester (B) is a polyester composed of an aromatic dicarboxylic acid component and a glycol component containing at least an alkylene glycol having 3 or more carbon atoms.

The in-plane retardation of the polyester film is preferably 3000 nm or more and 30000 nm or less, and more preferably 3500 nm or more and 30000 nm or less. More preferably, it is 4000 nm or more and 30000 nm or less. If the in-plane retardation is less than 3000 nm, rainbow spots will occur. The in-plane retardation is proportional to the thickness and can be increased. However, since a thick polarizer protective film is not practically preferred, it is preferably 30000 nm or less.

The retardation value of the polyester film is obtained by multiplying the film thickness by the anisotropy (| Nx−Ny |) of the biaxial refractive index (Nx, Ny obtained at a measurement wavelength of 589 nm) perpendicular to the surface in accordance with a known method. It can ask for. For example, it can also measure using commercially available automatic birefringence measuring apparatuses, such as KOBRA-21ADH (Oji Scientific Instruments).

The present inventors have disclosed a polyester comprising an aromatic dicarboxylic acid component, a polyester (A) comprising ethylene glycol as a glycol component, an aromatic dicarboxylic acid component, and a glycol component containing at least an alkylene glycol having 3 or more carbon atoms. If it is a film made of polyester obtained by mixing (B), it is possible to lower the NZ coefficient relatively easily compared to a film made of polyethylene terephthalate homopolymer, etc. It has been found that rainbow spots observed from an oblique direction can be suppressed even when the film thickness is reduced.
The reason why the NZ coefficient can be lowered relatively easily in the case of a film made of polyester in which polyester (A) and polyester (B) are mixed is considered as follows. By containing an alkylene glycol having 3 or more carbon atoms in addition to ethylene glycol, the alkylene glycol having 3 or more carbon atoms can take a bulky structure in the polymer, and in the film traveling direction during stretching during the film production process. It is considered that the generated stress can be reduced. As a result, an increase in Nx (refractive index in the film traveling direction, refractive index in the direction perpendicular to the slow axis) can be reduced, and the NZ coefficient can be lowered.

Even if it is a film made of polyethylene terephthalate homopolymer, it is possible to obtain a film having a retardation of 3000 to 30000 nm and an NZ coefficient of 1.55 or less. There is a detrimental effect on the film physical properties, such as significantly worsening the properties. In addition, since the deformation of the film held in the TD stretching furnace becomes significant, there is a problem that it is difficult to obtain a continuous roll sample.

The polyester used for the polyester film is composed of an aromatic dicarboxylic acid component, a polyester (A) composed of ethylene glycol as a glycol component, an aromatic dicarboxylic acid component, and a glycol component containing at least an alkylene glycol having 3 or more carbon atoms. It is preferable to use a polyester (B) blended sufficiently uniformly.
When the total acid component of the polyester after blending is 100 mol% and the total glycol component is 100 mol%, the aromatic dicarboxylic acid is 100 mol%, the ethylene glycol is 85 to 97 mol%, and the alkylene glycol having 3 or more carbon atoms is It is preferable to blend polyester (A) and polyester (B) so that it may become 3-15 mol%. The mixing ratio of the polyester (A) and the polyester (B) depends on the molar ratio of the alkylene glycol having 3 or more carbon atoms of the polyester (B), but the polyester (A) is 50 to 97% by mass, the polyester (B ) Is preferably 3 to 50% by mass, more preferably 55 to 97% by mass of polyester (A), 3 to 45% by mass of polyester (B), and still more preferably 60 to 60% of polyester (A). -97 mass%, polyester (B) is 3-40 mass%, Most preferably, polyester (A) is 82-97 mass%, and polyester (B) is 3-18 mass%.

(Polyester (A))
The polyester (A) is a polyester obtained by polymerizing an aromatic dicarboxylic acid component and ethylene glycol. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and the like. However, a component containing a sulfonic acid is not preferable because moisture permeability at the time of film formation becomes high. When the total acid component of the polyester (A) is 100 mol% and the total glycol component is 100 mol%, the aromatic dicarboxylic acid is preferably contained in an amount of 95 mol% or more, more preferably 97 mol% or more, still more preferably 98 mol%. % Or more. Further, when the total acid component of the polyester (A) is 100 mol% and the total glycol component is 100 mol%, the ethylene glycol component is preferably contained in an amount of 95 mol% or more, more preferably 97 mol% or more, still more preferably It is 98 mol% or more. In particular, the polyester (A) is preferably polyethylene terephthalate or polyethylene naphthalate having a large intrinsic birefringence. Further, polyethylene terephthalate and polyethylene naphthalate may be used in combination as polyester (A).

The intrinsic viscosity of the polyester (A) is preferably 0.30 to 1.00 dl / g, more preferably 0.35 to 0.95 dl / g, and still more preferably 0.40 to 0.90 dl / g. . If it is less than 0.30 dl / g, it will be difficult to hold it as a film shape, and if it exceeds 1.00 dl / g, the pressure applied during extrusion increases with an increase in melt viscosity, which may damage the production line.

(Polyester (B))
The polyester (B) is a polyester obtained by polymerizing an aromatic dicarboxylic acid component and a glycol component containing at least an alkylene glycol having 3 or more carbon atoms. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and the like. However, a component containing a sulfonic acid is not preferable because moisture permeability at the time of film formation becomes high. The alkylene glycol having 3 or more carbon atoms may be linear, branched or cyclic. The number of carbons is counted by counting all the carbon numbers. The branched one counts all the carbons forming the ring, including the branched portion and the cyclic one. For example, propylene glycol has 3 carbon atoms, neopentyl glycol has 5 carbon atoms, cyclohexanedimethanol has 8 carbon atoms, and so on. . As the alkylene glycol component having 3 or more carbon atoms, propylene glycol, butylene glycol, neopentyl glycol, hexamethylene glycol and 1,4-cyclohexanedimethanol are preferable, among which propylene glycol and butylene glycol are more preferable, and butylene glycol is more preferable. . The number of carbon atoms is preferably 9 or less. A carbon number of 10 or more is not preferable because it is difficult to obtain practically. Further, “including at least an alkylene glycol having 3 or more carbon atoms” means that ethylene glycol may be included in addition to the alkylene glycol having 3 or more carbon atoms. That is, polyester (B) is a polyester obtained by polymerizing an aromatic dicarboxylic acid component and an alkylene glycol component having 3 or more carbon atoms, an aromatic dicarboxylic acid component and an alkylene glycol component having 3 or more carbon atoms, ethylene glycol, Is a copolyester obtained by polymerizing.

When the total acid component of the polyester (B) is 100 mol% and the total diol component is 100 mol%, the aromatic dicarboxylic acid is preferably contained in an amount of 95 mol% or more, more preferably 97 mol% or more, still more preferably It is 98 mol% or more. Further, when the total acid component of the polyester (B) is 100 mol% and the total diol component is 100 mol%, the alkylene glycol component having 3 or more carbon atoms is preferably contained in an amount of 5 mol% or more, more preferably 7.5 mol. % Or more, more preferably 10 mol% or more. Particularly, the polyester (B) includes polytrimethylene terephthalate, polybutylene terephthalate, trimethylene glycol copolymerized polyethylene terephthalate, butylene glycol copolymerized polyethylene terephthalate, neopentyl glycol copolymerized polyethylene terephthalate, hexamethylene glycol copolymerized polyethylene terephthalate, 1 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate is preferred, polytrimethylene terephthalate and polybutylene terephthalate are more preferred, and polybutylene terephthalate is even more preferred.

The intrinsic viscosity of the polyester (B) is preferably 0.05 to 1.00 dl / g, more preferably 0.10 to 0.95 dl / g, and still more preferably 0.10 to 0.90 dl / g. . If it is less than 0.10 dl / g, it will be difficult to finely mix and mix, and if it exceeds 1.00 dl / g, the pressure applied during extrusion will increase due to an increase in melt viscosity, which may damage the production line. It is.

The NZ coefficient of the polyester film is preferably 1.55 or less. Here, the NZ coefficient is Ny when the refractive index in the slow axis direction in the plane is Ny, Nx is the refractive index in the direction perpendicular to the slow axis in the plane, and Nz is the refractive index in the thickness direction. Nz−Ny) / (Nx−Ny). The NZ coefficient is more preferably 1.5 or less, still more preferably 1.48 or less, and particularly preferably 1.45 or less. As the NZ coefficient, 1 is an ideal value, and as the NZ coefficient becomes smaller, generation of rainbow spots from an oblique direction can be suppressed. When the NZ coefficient increases, rainbow spots from an oblique direction tend to occur.

The thickness of the polyester film is preferably 20 μm to 100 μm. Especially, 25 micrometers-95 micrometers are more preferable, and 30 micrometers-90 micrometers are still more preferable. When the thickness is less than 20 μm, there is a risk of breaking during film formation or process passability during post-processing. On the other hand, when it is thicker than 100 μm, the above problem is solved, but the handling property as an industrial material is deteriorated against the thinning of the polarizing plate.

  The liquid crystal display device of the present invention includes a backlight, a liquid crystal cell, and polarizing plates disposed on both sides of the liquid crystal cell. An image or the like is displayed by a backlight using a CCFL or LED arranged on one surface as a light source. The polarizing plate is composed of a film called a polarizer mainly composed of polyvinyl alcohol (PVA) and adsorbed and oriented with iodine compound molecules, and a polarizer protective film disposed on both sides thereof. In the polarizing plate of the present invention, at least one of the polarizer protective films is preferably the above-described polyester film. The liquid crystal display device may appropriately include, for example, a color filter, a lens film, a diffusion sheet, an antireflection film, and the like as other constituent members.

  The configuration of the backlight may be an edge light method using a light guide plate or a reflection plate as a constituent member, or may be a direct type, but in the present invention, it is a continuous light source for a liquid crystal display device. It is preferable to use a white light source having a broad emission spectrum.

“Continuous and broad emission spectrum” means an emission spectrum in which there is no wavelength region where the light intensity becomes zero in the wavelength region of at least 450 to 650 nm, preferably in the visible light region. The visible light region is, for example, a wavelength region of 400 to 760 nm, and may be 360 to 760 nm, 400 to 830 nm, or 360 to 830 nm.

  As a white light source having a continuous and broad emission spectrum, for example, a white light emitting diode (white LED) can be exemplified. A white LED is a phosphor type, that is, an element that emits white light by combining an LED emitting blue light or ultraviolet light using a compound semiconductor and a phosphor, an organic light-emitting diode (OLED), and the like. Can be mentioned. The phosphors include yttrium / aluminum / garnet yellow phosphors and terbium / aluminum / garnet yellow phosphors, among others, blue LEDs using compound semiconductors and yttrium / aluminum / garnet yellow phosphors. A white LED composed of a light-emitting element combined with a body has a continuous and broad emission spectrum and is excellent in luminous efficiency, and thus energy saving can be expected.

Hereinafter, the manufacturing method of the polarizer protective film of this invention is demonstrated.

It can be obtained in accordance with a general polymer film production method. For example, after melting polyester and obtaining a non-oriented sheet by extrusion, MD stretching (stretching in the film flow direction) utilizing the speed difference of the roll at a temperature equal to or higher than the glass transition temperature of the polyester, TD by the tenter Examples thereof include a method of performing heat treatment after stretching (stretching in the film width direction) alone or in combination.

  The production method of the polyester film is not limited to the above-described method, but in the case of a biaxially stretched film, when observed obliquely with respect to the direction perpendicular to the plane of the polarizer protective film, ) Tends to be recognized, and from the viewpoint of eliminating rainbow spots (color spots), simple uniaxial TD stretching is preferable, and it is more preferable to relax in the MD direction simultaneously with TD stretching. Although simple uniaxial MD stretching is possible, there are problems such as easy stretching unevenness, and attention is required.

  The retardation of the polyester film used in the present invention can be controlled by adjusting the stretching conditions during film production. Specifically, the adjustment is preferably made according to the molecular weight of the resin, additives, and monomers, but the stretching temperature is in the range of (Tg-10 ° C.) to (Tg + 50 ° C.) with the glass transition temperature (Tg) as a guide. Can be set. When the stretching temperature is low, breakage frequently occurs, and when the stretching temperature is high, uneven thickness or whitening may occur.

  The total stretching ratio of the film (= MD stretching ratio × TD stretching ratio) is preferably in the range of 3.0 times to 10.0 times. When stretching in multiple stages, it is preferable to increase the stretching ratio in the initial stage, so that the film tends to break, and the latter stretching ratio is preferably higher than the initial stretching ratio.

The MD draw ratio in MD drawing is preferably 1.0 to 2.5 times. In addition, when manufacturing the uniaxially stretched film extended | stretched only to MD direction without TD extending | stretching, it is preferable to make MD draw ratio into 3.5 times vicinity.

  The TD stretching ratio in TD stretching is preferably 3.0 to 6.0 times, more preferably 3.5 to 5.0 times. In addition, it is possible to relax in the MD direction simultaneously with TD stretching, and although depending on the TD stretching ratio, the relaxation ratio is preferably 0.5 to 0.9 times, more preferably 0.65 to 0.8 times. . It is preferable to control the film so that the film is free from rainbow spots by these methods. In addition, when heat treatment is performed in a post-processing step such as when manufacturing a polarizing plate by performing a relaxation treatment in the MD direction, or when a display is used at a high temperature for a long time, an optical generated due to heat shrinkage of the film It becomes possible to more effectively suppress distortion of characteristics, deterioration of flatness, wrinkles, curls, and the like.

  It can also be produced by simultaneous biaxial stretching. Specifically, in general, a facility called a simultaneous biaxial stretching machine is used, and a method of performing heat treatment after simultaneously performing TD stretching and MD stretching, or relaxing in the MD direction simultaneously with TD stretching. In the latter case, pay attention to the thickness unevenness, etc., and make the relaxation magnification in the MD direction 0.5 to 0.9 times, further 0.65 to 0.8 times. Is preferred. When the relaxation magnification in the MD direction is set in this way, heat treatment occurs in post-processing steps such as when manufacturing polarizing plates, or when the display is used at high temperatures for long periods of time, which occurs due to heat shrinkage of the film. It is possible to more effectively suppress distortion of optical characteristics, deterioration of flatness, wrinkles, curls, and the like.

  The heat treatment is preferably adjusted by the molecular weight and additives of the resin, the monomer, and the draw ratio, but the treatment temperature is Tg + 50 ° C. based on the glass transition temperature (Tg) and the melting point (Tm). The temperature is preferably set in the range of -Tm-30 ° C., and particularly preferably controlled so that the heat shrinkage rate of the film after film formation does not increase. Specifically, the thermal shrinkage ratio before and after heating at 150 ° C. for 30 minutes is preferably 3% or less in both the MD direction and the TD direction, more preferably 2% or less, and still more preferably 1.5%. Or less, more preferably 1.0% or less, and particularly preferably 0.5% or less. By performing relaxation in the MD direction during the heat treatment, it is possible to further reduce the thermal contraction rate efficiently.

  As for a polarizer protective film, it is desirable for the light transmittance of wavelength 380nm to be 20% or less. The light transmittance at 380 nm is more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less. For example, the light transmittance at a wavelength of 380 nm can be reduced to 20% or less by adding an ultraviolet absorber to polyester.

In addition to ultraviolet absorbers, additives include, for example, inorganic particles, heat-resistant polymer particles, alkali metal compounds, alkaline earth metal compounds, phosphorus compounds, antistatic agents, light-resistant agents, flame retardants, and heat stabilizers. Further, an antioxidant, an antigelling agent, and / or a surfactant can be added to the polyester as long as the effects of the present invention are not hindered and the transparency is not impaired.

  The polyester film used in the present invention is a known method such as a combining adapter method, a multi-slot method, a multi-manifold method, and the like, in which polyester and other additives and particles are mixed as long as the performance is not impaired. It is also possible to have a laminated structure such as a two-type two-layer configuration, a two-type three-layer configuration of B / A / B configuration, and a three-type three-layer configuration of C / A / B.

  Furthermore, the polarizer protective film has an easy-adhesion layer mainly composed of at least one of a polyester resin, a polyurethane resin, or a polyacrylic resin on at least one surface in order to improve the adhesion to the polarizer. Is preferred. 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 for the easy-adhesion layer formed on the polarizer protective film is preferably an aqueous coating liquid containing at least one of water-soluble or water-dispersible copolymer polyester resin, acrylic resin, and polyurethane resin. As these coating liquids, the water-soluble or water-dispersible properties disclosed in Japanese Patent No. 3567927, Japanese Patent No. 3589232, Japanese Patent No. 3589233, Japanese Patent No. 3900191, Japanese Patent No. 4150982, etc. Examples thereof include a copolymerized polyester resin solution, an acrylic resin solution, and a polyurethane resin solution.

  The easy adhesion layer formed on the polarizer protective film is a reverse roll coating method, a gravure coating method, a kiss coating method, a roll brush method, a spray coating method, an air knife coating method, a wire bar coating method, a pipe doctor method, The known methods such as these can be applied alone or in combination.

  Moreover, it is also preferable to use the polarizer protective film which apply | coated various functional layers on the surface for the purpose of prevention of a reflection, glare suppression, a crack suppression, etc. for the polarizing plate of this invention.

  Examples of the functional layer laminated at an arbitrary position on the viewing side of the polarizer protective film include, for example, a hard coat layer, an antiglare layer, an antireflection layer, a low reflection layer, a low reflection antiglare layer, an antireflection antiglare layer, and charging. One or more selected from the group consisting of a prevention layer, a silicone layer, an adhesive layer, an antifouling layer, a water repellent layer, a blue cut layer, and the like can be used.

  When providing various functional layers, it is preferable to have an easy-adhesion layer on the surface of the polarizer protective film. 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 that it is close to the geometric mean of the refractive index of the functional layer and the refractive index of the polyester film. The refractive index of the easy-adhesion layer can be adjusted by a known method. For example, the refractive index of the easy-adhesion layer can be easily adjusted by adding titanium, zirconium, or other metal species to the binder resin.

(Hard coat layer)
The hard coat layer only needs to be a layer having hardness and transparency. Usually, various curable properties such as an ionizing radiation curable resin typically cured by ultraviolet rays or an electron beam, and a thermosetting resin cured by heat. What was formed as a cured resin layer of resin is used. In order to appropriately add flexibility and other physical properties to these curable resins, thermoplastic resins and the like may be added as appropriate. Among the curable resins, ionizing radiation curable resins are preferable because they are representative and an excellent hard coating film can be obtained.

  As the ionizing radiation curable resin, a conventionally known resin may be appropriately employed. As the ionizing radiation curable resin, a radical polymerizable compound having an ethylenic double bond, a cationic polymerizable compound such as an epoxy compound, and the like are typically used. These compounds include monomers, oligomers, prepolymers, and the like. These can be used alone or in appropriate combination of two or more. Typical compounds are various (meth) acrylate compounds that are radical polymerizable compounds. Among the (meth) acrylate compounds, compounds used at a relatively low molecular weight include, for example, polyester (meth) acrylate, polyether (meth) acrylate, acrylic (meth) acrylate, epoxy (meth) acrylate, urethane (meth) ) Acrylate, etc.

  Examples of the monomer include monofunctional monomers such as ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone; or, for example, trimethylolpropane tri (meth) acrylate, tripropylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. These polyfunctional monomers are also used as appropriate. (Meth) acrylate means acrylate or methacrylate.

  When the ionizing radiation curable resin is cured with an electron beam, a photopolymerization initiator is unnecessary, but when it is cured with ultraviolet rays, a known photopolymerization initiator is used. For example, in the case of a radical polymerization system, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, or the like can be used alone or in combination as a photopolymerization initiator. In the case of a cationic polymerization system, an aromatic diazonium salt, aromatic sulfonium salt, aromatic iodonium salt, metatheron compound, benzoin sulfonate, or the like can be used alone or in combination as a photopolymerization initiator.

  The thickness of the hard coat layer may be an appropriate thickness, for example, 0.1 to 100 μm, but usually 1 to 30 μm. The hard coat layer can be formed by appropriately adopting various known coating methods.

  A thermoplastic resin, a thermosetting resin, or the like can be appropriately added to the ionizing radiation curable resin for the purpose of adjusting the physical properties as appropriate. Examples of the thermoplastic resin or thermosetting resin include an acrylic resin, a urethane resin, and a polyester resin, respectively.

  In order to impart light resistance to the hard coat layer and prevent discoloration, strength deterioration, cracking, and the like due to ultraviolet rays contained in sunlight, it is also preferable to add an ultraviolet absorber in the ionizing radiation curable resin. When an ultraviolet absorber is added, the ionizing radiation curable resin is preferably cured with an electron beam in order to reliably prevent the ultraviolet coater from inhibiting the curing of the hard coat layer. Examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole compounds and benzophenone compounds, or inorganic ultraviolet absorbers such as fine particles of zinc oxide, titanium oxide, and cerium oxide having a particle size of 0.2 μm or less, What is necessary is just to select and use from well-known things. The addition amount of the ultraviolet absorber is about 0.01 to 5% by mass in the ionizing radiation curable resin composition. In order to further improve the light resistance, it is preferable to add a radical scavenger such as a hindered amine radical scavenger in combination with an ultraviolet absorber. In addition, the electron beam irradiation has an acceleration voltage of 70 kV to 1 MV and an irradiation dose of about 5 to 100 kGy (0.5 to 10 Mrad).

(Anti-glare layer)
It is one of the preferred embodiments that an antiglare layer is provided on the most visible side of the image display device. As the antiglare layer, a conventionally known layer may be appropriately employed, and it is generally formed as a layer in which an antiglare agent is dispersed in a resin. As the antiglare agent, inorganic or organic fine particles are used. These fine particles have a spherical shape, an elliptical shape, or the like. The fine particles are preferably transparent. Examples of such fine particles include silica beads as inorganic fine particles and resin beads as organic fine particles. Examples of the resin beads include styrene beads, melamine beads, acrylic beads, acrylic-styrene beads, polycarbonate beads, polyethylene beads, and benzoguanamine-formaldehyde beads. The fine particles are usually added in an amount of 2 to 30 parts by mass, preferably about 10 to 25 parts by mass with respect to 100 parts by mass of the resin.

  The above resin for dispersing and holding the antiglare agent is preferably as hard as possible as in the hard coat layer. Therefore, as the resin, for example, a curable resin such as an ionizing radiation curable resin or a thermosetting resin described in the hard coat layer can be used.

  The thickness of the antiglare layer may be an appropriate thickness, and is usually about 1 to 20 μm. The antiglare layer can be formed by appropriately adopting various known coating methods. In addition, it is preferable to add well-known anti-settling agents such as silica to the coating liquid for forming the anti-glare layer in order to prevent precipitation of the anti-glare agent.

(Antireflection layer)
It is also one of preferable modes that an antireflection layer is provided on the outermost surface side of the image display device and the interface of each film with air.
As the antireflection layer, a conventionally known layer may be appropriately employed. In general, the antireflection layer is composed of at least a low refractive index layer, and a low refractive index layer and a high refractive index layer (having a higher refractive index than the low refractive index layer) are alternately stacked adjacent to each other and the surface side has a low refractive index. It consists of multiple layers as the rate layer. Each thickness of the low-refractive index layer and the high-refractive index layer may be an appropriate thickness according to the application, and is about 0.1 μm when adjacent layers are stacked, and about 0.1 to 1 μm when the low-refractive index layer is alone. It is preferable.

  As a low refractive index layer, a layer containing a low refractive index material such as silica or magnesium fluoride in a resin, a layer of a low refractive index resin such as a fluorine-based resin, or a low refractive index material in a low refractive index resin A thin film formed by a thin film forming method (for example, physical or chemical vapor deposition such as vapor deposition, sputtering, CVD, or the like), an oxidation layer, or a layer made of a low refractive index material such as silica or magnesium fluoride. Examples thereof include a film formed by a sol-gel method in which a silicon oxide gel film is formed from a silicon sol solution, or a layer in which void-containing fine particles are contained in a resin as a low refractive index substance.

  The void-containing fine particles are fine particles containing gas inside, fine particles having a porous structure containing gas, etc., and with respect to the original refractive index of the fine particle solid portion, It means fine particles whose refractive index is apparently lowered. Examples of such void-containing fine particles include silica fine particles disclosed in JP-A No. 2001-233611. Examples of the void-containing fine particles include hollow polymer fine particles disclosed in JP-A No. 2002-805031, in addition to inorganic substances such as silica. The particle diameter of the void-containing fine particles is, for example, about 5 to 300 nm.

  As the high refractive index layer, a layer containing a high refractive index material such as titanium oxide, zirconium oxide or zinc oxide in a resin, a layer of a high refractive index resin such as a fluorine-free resin, or a high refractive index material is highly refracted. A layer formed of a high-refractive-index material such as titanium oxide, zirconium oxide, or zinc oxide in a thin film forming method (for example, vapor deposition, sputtering, CVD, etc., physical or chemical vapor deposition) Method).

(Anti-fouling layer)
As the antifouling layer, a conventionally known layer may be appropriately employed. Generally, in the resin, a silicon compound such as silicone oil or silicone resin; a fluorine compound such as fluorine surfactant or fluorine resin. It can be formed by a known coating method using a paint containing a stain-proofing agent such as wax. The thickness of the antifouling layer may be set appropriately, and can usually be about 1 to 10 μm.

(Antistatic layer)
As the antistatic layer, a conventionally known layer may be employed as appropriate, and it is generally formed as a layer containing an antistatic layer in a resin. As the antistatic layer, an organic or inorganic compound is used. For example, examples of the antistatic layer of an organic compound include a cationic antistatic agent, an anionic antistatic agent, an amphoteric antistatic agent, a nonionic antistatic agent, and an organometallic antistatic agent. The inhibitor is used not only as a low molecular compound but also as a high molecular compound. As the antistatic agent, conductive polymers such as polythiophene and polyaniline are also used. Further, as the antistatic agent, for example, conductive fine particles made of a metal oxide are used. The particle diameter of the conductive fine particles is, for example, about 0.1 nm to 0.1 μm in average particle diameter in terms of transparency. Examples of the metal oxide include ZnO, CeO ₂ , Sb ₂ O ₂ , SnO ₂ , ITO (indium doped tin oxide), In ₂ O ₃ , Al ₂ O ₃ , ATO (antimony doped tin oxide), AZO (aluminum doped zinc oxide) etc. are mentioned. In addition, you may contain these antistatic agents in the easily bonding layer of the polyester film mentioned above.

  Examples of the resin containing the antistatic layer include curable resins such as ionizing radiation curable resins and thermosetting resins as described in the hard coat layer. When the layer is formed as a layer and the surface strength of the antistatic layer itself is unnecessary, a thermoplastic resin or the like is also used. The thickness of the antistatic layer may be set appropriately, and is usually about 0.01 to 5 μm. The antistatic layer can be formed by appropriately adopting various known coating methods.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by the following examples, and may be implemented with appropriate modifications within a scope that can meet the gist of the present invention. These are all included in the technical scope of the present invention.

Evaluation in Examples was performed according to the following method.
(1) Retardation (Re)
Retardation refers to the refractive index (Nx) in each axial direction of the film with respect to the thickness direction (z-axis) and the two axial directions (x-axis and y-axis) that are orthogonal to and perpendicular to the film surface. , Ny) is a phase difference represented by the product of birefringence and film thickness d. The evaluation method was performed as follows.
First, the direction of the slow axis of the film was calculated | required using the molecular orientation meter (Oji Keiki Co., Ltd. make, MOA-6004 type | mold molecular orientation meter). The slow axis direction was taken as the y-axis, and the direction perpendicular to it in the film plane was taken as the x-axis.
Next, the in-plane retardation that is the product of the birefringence index Nxy and the thickness d caused by the light incident on the film surface (xy plane) is defined as retardation (Re), and JIS K 7142 “Plastic refractive index measurement method” In accordance with (Method A), the refractive index (Nx) in the direction perpendicular to the slow axis, the refractive index (Ny) in the slow axis direction, and the refractive index (Nz) in the thickness direction are obtained, and Nx and Using the value of Ny, retardation was obtained from the following equation. The measurement of the refractive index is a value measured at a measurement wavelength of 589 nm. As usual, the unit of retardation is nm.
ΔNxy = | Nx−Ny |
Re = ΔNxy × d

(2) NZ coefficient NZ coefficient is an index indicating uniaxiality with respect to the y-axis direction, and in accordance with JIS K 7142 “Method for measuring refractive index of plastic (Method A)”, (1) In terms of retardation (Re) Using the obtained values of Nx, Ny, and Nz, the value was obtained from the following equation. In general, the unit of the NZ coefficient is dimensionless.
NZ coefficient = (Nz−Ny) / (Nx−Ny)

(3) Visibility (rainbow spot evaluation)
Examples prepared by the method described later on one side of a commercially available polarizer, and a film of a comparative example were pasted so that the absorption axis of the polarizer and the slow axis direction of the film were perpendicular to each other, and commercially available on the opposite side A TAC film (Fuji Film Co., Ltd., 80 μm) was attached to prepare a polarizing plate. The obtained polarizing plates were arranged one by one on both sides of the liquid crystal so that each polarizing plate was in a crossed Nicols condition to produce a liquid crystal display device. Each polarizing plate was arrange | positioned so that the film of an Example and a comparative example might be on the opposite side (distal) from a liquid crystal. White LED (manufactured by Nichia, NSPW500CS) was used as a backlight light source. Visual observation was performed from the front of the liquid crystal display device thus obtained and from an oblique direction, and the presence or absence of rainbow spots was determined as follows.
A: No rainbow spots are observed from any direction.
A ′: When observed from an oblique direction, very thin rainbow spots are observed depending on the angle.
B: When observed from an oblique direction, a thin iridescence is observed depending on the angle.
C: When observed from an oblique direction, rainbow spots are observed.
D: When observing from the front direction and the oblique direction, rainbow spots are observed.

(4) Resin composition The resin was dissolved in the following solvent, ¹ H-NMR analysis was performed using AVANCE500 manufactured by BRUKER, and the mol% ratio of each composition was determined from the integral ratio of the obtained spectrum.
Solvent: deuterated chloroform / trifluoroacetic acid = 85/15 (volume ratio)

(5) Film-forming property When stretching was performed in the film-forming process, the presence or absence of film breakage and stretching unevenness were visually observed and determined as follows.
○: No film breakage or stretching unevenness during film formation, and uniform film in the width direction ×: Film breakage occurred during film formation, sampling cannot be performed, or uneven filming due to stretching unevenness

(6) Thermal contraction rate (HS)
In accordance with JIS C 2318 “Electric polyethylene terephthalate film (dimensional change)”, the dimensional change rate before and after heating at 150 ° C. for 30 minutes was determined as the thermal shrinkage rate for MD and TD. In Tables 1 and 2, the thermal contraction rate in the MD direction is expressed as HS-MD, and the thermal contraction rate in the TD direction is expressed as HS-TD.

(7) Intrinsic viscosity (IV)
For the viscosity number obtained in accordance with JIS K 7367-5 "Plastics-Determination of viscosity of diluted solution using capillary viscometer-Part 5: Thermoplastic polyester (TP) homopolymer and copolymer" Under the following measurement conditions, the value when the mass concentration (c) = 0 was set as the intrinsic viscosity (IV) from the relationship of the viscosity number to the mass concentration (c) of the solution.
Solvent: Phenol / 1,1,2,2-tetrachloroethane = 60/40 (mass%)
Tube: Ubbelohde viscosity tube Temperature: 30 ± 0.1 (° C)

(Production Example 1-Adhesiveness Modification Solution)
With respect to all components of dicarboxylic acid, 46 mol% of terephthalic acid, 46 mol% of isophthalic acid, and 8 mol% of sodium 5-sulfonatoisophthalate and 50 mol% of neopentyl glycol with respect to all components of glycol A water-dispersible sulfonic acid metal base-containing copolymer polyester resin was obtained by a transesterification reaction and a polycondensation reaction by a conventional method. Next, an adhesive property modification liquid was obtained in which this and the agglomerated silica particles were dispersed in a solution in which water, isopropyl alcohol, n-butyl cellosolve, and nonionic surfactant were mixed.

(Production Example 2-Polyester resin)
Except for the commercially available product, a transesterification reaction and a polymerization reaction were performed by a conventional method to obtain a polyester resin. About a resin composition ratio, it is the value evaluated by < ¹ > H-NMR, and the value in () showed the value of intrinsic viscosity.
PET: Polyethylene terephthalate (0.74 dl / g)
PBT-a: Polybutylene terephthalate, NV5020 (0.52 dl / g) manufactured by Mitsubishi Engineering Plastics
PBT-b: Polybutylene terephthalate, DIC A-51 (0.17 dl / g)
PTT: Polytrimethylene terephthalate (0.98 dl / g)
PHT: Polyhexamethylene terephthalate (0.85 dl / g)
PEN: Polyethylene naphthalate (0.60 dl / g)
PNT: terephthalic acid // ethylene glycol / neopentyl glycol = 100 // 70/30 [mol ratio] (0.72 dl / g)
PCT: terephthalic acid // ethylene glycol / cyclohexanedimethanol = 100 // 60/40 [mol ratio] (0.68 dl / g)

<Example 1>
Using an extruder, 95% by mass of PET and 5% by mass of PBT-a were blended, melted at about 280 ° C., and melt extruded from the slit. An unstretched sheet cooled and solidified by electrostatic application on a chill roll having a surface temperature of about 25 ° C. is 0.08 g / m ² after the adhesive reforming liquid is dried on both sides by reverse roll coating. TD stretching was performed with a tenter having a set temperature of 100 ° C. and a stretching ratio of 4.0 times, followed by heat treatment at 180 ° C. to obtain a film having a thickness of about 45 μm. Table 1 shows a list of film forming conditions and evaluation results. Since the polyester film of this example contained both ethylene glycol and butylene glycol, no rainbow spots occurred even when observed from any direction.

<Example 2>
A film was formed in the same manner as in Example 1 except that 90% by mass of PET and 10% by mass of PBT-a were used. Since the polyester film of this example contained both ethylene glycol and butylene glycol, no rainbow spots occurred even when observed from any direction.

<Example 3>
A film was formed in the same manner as in Example 1 except that 85% by mass of PET and 15% by mass of PBT-a were used. Since the polyester film of this example contained both ethylene glycol and butylene glycol, no rainbow spots occurred even when observed from any direction.

<Example 4>
A film was formed in the same manner as in Example 1 except that PBT-b was used instead of PBT-a. Since the polyester film of this example contained both ethylene glycol and butylene glycol, no rainbow spots occurred even when observed from any direction.

<Example 5>
A film was formed in the same manner as in Example 1 except that 90% by mass of PET and 5% by mass of PNT were used. Since the polyester film of this example contained both ethylene glycol and neopentyl glycol, no rainbow spots were observed when observed from any direction.

<Example 6>
A film was formed in the same manner as in Example 1 except that 90% by mass of PET and 10% by mass of PTT were used. Since the polyester film of this example contained both ethylene glycol and trimethylene glycol, no rainbow spots were observed when observed from any direction.

<Example 7>
A film was formed in the same manner as in Example 1 except that 90% by mass of PET and 10% by mass of PHT were used. Since the polyester film of this example contains both ethylene glycol and hexamethylene glycol, no rainbow spots were observed from any direction.

<Example 8>
A film was formed in the same manner as in Example 1 except that 90% by mass of PET and 10% by mass of PCT were used. Since the polyester film of this example contained both ethylene glycol and cyclohexanedimethanol, no rainbow spots were observed when observed from any direction.

<Example 9>
A film was formed in the same manner as in Example 1 except that 65% by mass of PET, 30% by mass of PEN, 5% by mass of PBT were used, and the film formation conditions were changed as shown in Table 1. Since the polyester film of this example contained both ethylene glycol and butylene glycol, no rainbow spots occurred even when observed from any direction.

<Example 10>
A film was formed in the same manner as in Example 1 except that 60% by mass of PET, 30% by mass of PEN, 10% by mass of PBT were used, and the film formation conditions were changed as shown in Table 1. Since the polyester film of this example contained both ethylene glycol and butylene glycol, no rainbow spots occurred even when observed from any direction.

<Example 11>
A film was formed in the same manner as in Example 1 except that 55% by mass of PET, 30% by mass of PEN, and 15% by mass of PBT were used, and the film formation conditions were changed as shown in Table 2. Since the polyester film of this example contained both ethylene glycol and butylene glycol, no rainbow spots occurred even when observed from any direction.

<Example 12>
A film was formed in the same manner as in Example 1 except that 99% by mass of PET and 1% by mass of PBT-b were used. The polyester film of this example contains both ethylene glycol and butylene glycol, but since the amount of alkylene glycol having 3 or more carbon atoms is as low as 0.8 mol%, a partially thin rainbow is observed when observed from an oblique direction. Spots were confirmed.

<Example 13>
A film was formed in the same manner as in Example 1 except that 97.5% by mass of PET and 2.5% by mass of PBT-b were used. The polyester film of this example contains both ethylene glycol and butylene glycol. However, since the amount of alkylene glycol having 3 or more carbon atoms is as small as 2.3 mol%, the rainbow is partially thin when observed from an oblique direction. Spots were confirmed.

<Comparative Example 1>
A film was formed in the same manner as in Example 1 except that 100% by mass of PET was used. The polyester film of this comparative example has a retardation of 5000 nm or more, but only contains ethylene glycol and has a high NZ coefficient, so that when observed from an oblique direction, thin rainbow spots were observed depending on the angle.

<Comparative Example 2>
A film was formed in the same manner as in Example 1 except that 100% by mass of PET was used and the film thickness was changed. The polyester film of this comparative example has a retardation of 3000 nm or more, but only contains ethylene glycol, and since the NZ coefficient is high, rainbow spots were observed when observed from an oblique direction.

<Comparative Example 3>
A film was formed in the same manner as in Example 1 except that 100% by mass of PET was used and the film thickness was changed. Since the polyester film of this comparative example has a retardation of less than 3000 nm and contains only ethylene glycol, rainbow spots were observed when observed from the front and diagonal directions.

<Comparative Example 4>
A film was formed in the same manner as in Example 1 except that 80% by mass of PET and 20% by mass of PBT-a were used. The polyester film of this comparative example contains both ethylene glycol and butylene glycol, but because the amount of alkylene glycol having 3 or more carbon atoms is as high as 19.5 mol%, breakage frequently occurs during the passage of the film, and a continuous film sample is obtained. Couldn't get.

<Comparative Example 5>
The film was formed at the same composition ratio as in Example 1, with the line speed increased about 2.5 times, and the film thickness was about 19 μm. Although the polyester film of this comparative example contains both ethylene glycol and butylene glycol, since the retardation value is less than 3000 nm, rainbow spots were observed when observed from the front and oblique directions.

<Comparative Example 6>
The film was formed at the same composition ratio as in Example 10, and the film speed was increased by about 2.5 times to make the film thickness about 18 μm. The polyester film of this comparative example contains both ethylene glycol and butylene glycol, but since the retardation value was less than 3000 nm, rainbow spots were observed when observed from the front and diagonal directions.

  By using the liquid crystal display device, polarizing plate, and polarizer protective film of the present invention, it is possible to contribute to thinning and cost reduction of the display device without reducing visibility due to rainbow spots, Industrial applicability is extremely high.

Claims (7)

A polarizer protective film comprising a polyester film having a retardation of 3000 to 30000 nm,
The polyester constituting the polyester film is a mixture of polyester (A) and polyester (B),
The polyester (A) is a polyester composed of an aromatic dicarboxylic acid component and ethylene glycol as a glycol component,
The polyester (B) is a polyester composed of an aromatic dicarboxylic acid component and a glycol component containing at least an alkylene glycol having 3 or more carbon atoms.
Polarizer protective film. When the refractive index in the slow axis direction in the plane of the polyester film is Ny, the refractive index in the direction perpendicular to the slow axis in the plane is Nx, and the refractive index in the thickness direction is Nz, The polarizer protective film of Claim 1 whose NZ coefficient represented by (Nz-Ny) / (Nx-Ny) is 1.55 or less.   3. The polyester according to claim 1, wherein ethylene glycol is 85 to 97 mol% and alkylene glycol having 3 or more carbon atoms is 3 to 15 mol% when the total glycol component is 100 mol%. The polarizer protective film of description. The polarizer protection according to claim 1, wherein the polyester (A) is polyethylene terephthalate and / or polyethylene naphthalate, and the polyester (B) is polytrimethylene terephthalate and / or polybutylene terephthalate. the film.   The polarizer protective film in any one of Claims 1-4 whose thickness of the said polyester film is 20 micrometers-100 micrometers.   The polarizing plate by which the polarizer protective film in any one of Claims 1-5 was laminated | stacked on the at least one surface of the polarizer.   A liquid crystal display device comprising a backlight, a liquid crystal cell, and a polarizing plate disposed on both sides of the liquid crystal cell, wherein at least one polarizing plate is the polarizing plate according to claim 6.