KR101893741B1 - Multilayer polyester film - Google Patents

Abstract

An object of the present invention is to provide a polarizing plate which is excellent in balance of characteristics such as slipperiness and transparency and which has excellent handling properties in a post-process such as a manufacturing process or a polarizing plate production process of a liquid crystal display device and is excellent in low optical coherence And an object of the present invention is to provide such an adhesive polyester film which can be suitably used in the present invention.
In order to solve the above problems, the adhesive polyester film of the present invention is a polyester film having a coating layer on at least one side thereof, wherein the coating layer contains a zirconia / titania mixed particle A, a lubricant particle B and a binder resin , The zirconia content of the zirconia / titania mixed particle A is 10 to 90 mass% with respect to the total mass of zirconia and titania, and the average particle diameter of the lubricant particle B is 200 nm or more.

Description

Multilayer polyester film < RTI ID = 0.0 >

The present invention relates to an adhesive polyester film excellent in transparency, which can ensure low coherence capable of solving the problem of rainbow stains. More particularly, the present invention relates to an adhesive polyester film which can be suitably used in high-precision optical applications due to less occurrence of fine scratches.

A hard coat film obtained by laminating a transparent hard coat layer on a front surface of a display, a decorative material, etc. of a touch panel, a computer, a TV, and a liquid crystal display device is used. As a transparent plastic film of a substrate, a transparent polyester film is generally used, and in order to improve the adhesion between the polyester film as a substrate and the hard coat layer, a coating layer having such adhesiveness is often provided as an intermediate layer thereof .

The hard coat film is required to have temperature, humidity, durability against light, transparency, chemical resistance, scratch resistance and antifouling property. Further, in many cases, it is used for a surface of a display or a decorative material, so visibility and designability are required. For this reason, in order to suppress glare and iris color due to reflected light when viewed from an arbitrary angle, it is generally preferable to provide an antireflection layer having a multilayer structure in which a high refractive index layer and a low refractive index layer are laminated on the upper layer of the hard coat layer .

However, in applications such as displays and decorative materials, additional large-screen (large-sized) and high-definition screens are required in recent years, and the demand level for suppressing iris color (interference unevenness) under fluorescent lamps is increasing. In addition, since a fluorescent lamp has a mainstream of three wavelengths for the reproducibility of daylight color, it is easy to cause unevenness of interference. In addition, a demand for cost reduction due to the simplification of the antireflection layer is also increasing. For this reason, it is required to suppress interference non-uniformity as much as possible with a hard coat film which does not include an antireflection layer.

The iridescent color (interference unevenness) of the hard coat film is caused by a difference in refractive index (for example, 1.62 to 1.65) of the polyester film as the base material and the refractive index (for example, 1.49) of the hard coat layer made of acrylic resin or the like . A coating layer is provided on a polyester film as a base material to reduce the refractive index difference between layers so as to prevent occurrence of interference unevenness so that the refractive index difference between the polyester film and the coating layer and the refractive index difference between the coating layer and the hard coat layer are made small And a method of controlling the refractive index of the coating layer by the content of the resin constituting the coating layer and the high refractive index additive.

BACKGROUND ART [0002] Conventionally, in the field of adhesive films for optical use, there has been known a technique in which rainbow stains are reduced by including specific fine particles in the adhesive layer (see, for example, Patent Document 1). However, this conventional technique shows a certain performance in view of adhesion and rainbow stain restraint. However, there is a problem that scratches tend to occur due to poor slipperiness. When other particles are added to improve slipperiness, transparency There is a problem that a balance of slipperiness, transparency, and low coherence for rainbow stain reduction can not be achieved.

Japanese Patent Application Laid-Open No. 2007-203712

With the development of mobile technology, mobile phones, car navigation systems, electronic books and other portable devices are being used in outdoor areas. In addition, the portable device is mostly displayed by a liquid crystal panel in terms of thinning. In such a field, for example, in the case of a mobile phone equipped with a touch panel, it is a hard coat film for protecting the surface of a display. The hard coat film is provided on the back side of a hard coat film such as an interference pattern or an icon sheet by reflected light at both interfaces, In the application of casting, the drawbacks of visibility due to interference fringe are becoming more prominent.

However, when a high refractive index additive is added in a large amount in order to obtain a high degree of low coherence, the transparency is impaired and low coherence and transparency can not be achieved at the same time. In addition, since there is a use for a fixed-size display, a lubricant is added in order to suppress scratches, and transparency can not be maintained even if the slidability is improved.

Further, in order to improve the productivity in recent years, strong friction has been applied to the coating layer as the post-processing speed increases such as stacking of the hard coat layer and slit processing, and the thickness fluctuation due to the occurrence of scratches on the coating layer, Quality fluctuation is a problem. Particularly, since the resin used for increasing the refractive index has a relatively high hardness and tends to be broken, the scratch resistance of the coated layer tends to increase as the coated layer suppresses unevenness of interference.

Therefore, an optical-bonding polyester film having an effect of suppressing interference unevenness and having high transparency and high adhesiveness to a hard coat layer, which does not cause scratches on the coating layer even in high-speed processing, is desperately required.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art. That is, an object of the present invention is to provide a liquid crystal display device which is excellent in balance of properties such as slipperiness and transparency, has excellent handling properties in a manufacturing process or a post-process such as a polarizing plate production process of a liquid crystal display device, has few scratches, And which can be suitably used in excellent optical applications.

Means for Solving the Problems The present inventors have intensively studied in order to achieve these objects, and have completed the present invention. That is, the present invention has the following configuration.

1. A polyester film having a coating layer on at least one side thereof, wherein the coating layer contains a zirconia / titania mixed particle A, a lubricant particle B and a binder resin, and the total of zirconia and titania in the zirconia / The content of zirconia to the mass is 10 to 90 mass%, and the average particle diameter of the lubricant particle B is 200 nm or more.

2. The adhesive polyester film according to the first aspect, wherein the zirconia / titania mixed particle A has an average particle diameter of 5 to 200 nm.

3. The adhesive polyester film according to the first or second aspect, wherein the content of the lubricant particles B in the solid content of the coating layer is 0.1 to 20 mass%.

4. The adhesive polyester film described in any one of 1 to 3 above, wherein the content ratio of the zirconia / titania mixed particle A to the solid content of the coating layer is 2 to 50 mass%.

5. The adhesive polyester film according to any one of the first to fourth aspects, which has at least one function selected from the group consisting of a hard coat layer, an antiglare layer, an antireflective antireflective layer, an antireflective layer and a low- Layer laminated polyester film.

The present invention can ensure low coherence capable of suppressing rainbow stains, has a good balance of transparency and slippery property, has less scratches, and is excellent in handling properties in a later step such as a production process or a polarizing plate production process of a liquid crystal display device It is possible to provide the adhesive polyester film which can be suitably used in this excellent optical use.

(Polyester film)

The polyester film used as the base material in the present invention is a film composed of a polyester resin and is mainly composed of a polyester comprising at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate and polyethylene naphthalate A film is preferred. Further, the third component monomer may be a film made of a copolymer polyester in the above-mentioned polyester. Among these polyester films, a polyethylene terephthalate film is most preferable in terms of balance between physical properties and cost.

The polyester film may be a single layer or a multilayer. In addition, various additives may be contained in the respective layers of the polyester resin if necessary within the range of the effect of the present invention. Examples of additives include antioxidants, light stabilizers, antigelling agents, organic wetting agents, antistatic agents, ultraviolet absorbers, surfactants and the like.

(Coated layer)

The adhesive polyester film of the present invention is obtained by laminating the adhesive coated layer on the polyester base material film as described above. The coating layer contains a zirconia / titania mixed particle A (hereinafter sometimes simply referred to as a particle A), a lubricant particle B (hereinafter, simply referred to as a particle B), and a binder resin.

Particle A is a zirconia / titania mixed particle. The mixed particles in the present invention are a group of particles containing both zirconia and titania in an aggregated state in which zirconia and titania are dispersed singly in a single liquid and do not form a composite. Of course, in the coating layer, the liquid component is almost evaporated in the drying step or the hardening step and is lost. Since the coating layer contains such a particle A, the balance between slip and transparency is excellent, and high transparency and low coherence can be ensured. The liquid is preferably an aqueous liquid for easy formation of a coating layer by a so-called inline coating method which will be described later.

The particle A may contain other components than zirconia / titania, and may be an inorganic particle or an organic particle. Although it is not particularly limited, examples thereof include metal oxides such as silica, titanium dioxide, zirconium oxide, talc and kaolinite, Inorganic particles inactive to polyester such as calcium phosphate and barium sulfate are exemplified.

The ratio of the total mass of zirconia and titania to the mass (not including the mass of the liquid) of the particle A as the mixed particles is preferably 70 mass% or more, more preferably 80 mass% or more, still more preferably 90 mass %. Of course, it may be 100% by mass. When the ratio of the mass of zirconia and titania in the particle A is 70 mass% or more, it is preferable that the slip property and the transparency are balanced.

The mass ratio of zirconia to the total mass of zirconia and titania constituting the particles A as the mixed particles is preferably 10 mass% or more, more preferably 20 mass% or more, still more preferably 30 mass% or more, , Preferably not less than 40 mass%, even more preferably not less than 50 mass%, and most preferably not less than 55 mass%. If the mass ratio of zirconia to the total mass of zirconia and titania is 10 mass% or more, the surface roughness is not excessively large, and slipperiness with the guide roll becomes appropriate, and scratches are unlikely to occur. Therefore, the haze is not increased and the transparency is excellent.

The mass ratio of zirconia to the total mass of zirconia and titania constituting the particle A is preferably 90 mass% or less, more preferably 85 mass% or less, further preferably 80 mass% or less, 77% by mass or less. When the mass ratio of zirconia to the total mass of zirconia and titania is 90 mass% or less, there is no case where the surface roughness is too small, proper slipperiness is maintained, handling property is good, scratches are unlikely to occur during unwinding, Do.

The mass ratio of titania to the total mass of zirconia and titania constituting the particle A is preferably 10 mass% or more, more preferably 15 mass% or more, further preferably 20 mass% or more, particularly preferably 23 mass% %. When the mass ratio of titania to the total mass of zirconia and titania is 10 mass% or more, slidability is improved, handling is improved, and scratch resistance is improved, which is preferable. However, the larger the mass ratio of titania to the total mass of zirconia and titania means that the mass ratio of zirconia decreases, it is preferably 90 mass% or less, more preferably 80 mass% or less, Is not more than 70 mass%, particularly preferably not more than 60 mass%, more preferably not more than 50 mass%, and most preferably not more than 45 mass%.

The average particle diameter of the particles A is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 15 nm or more, and particularly preferably 20 nm or more. The average particle diameter of the particles A is preferably 5 nm or more, since it is difficult to agglomerate.

The average particle diameter of the particles A is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less, and particularly preferably 60 nm or less. When the average particle diameter of the particles A is 200 nm or less, transparency is preferably good.

The particles B are preferably selected from the group consisting of silica, kaolinite, talc, hard calcium carbonate, heavy calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, titanium dioxide, Inorganic particles such as calcium silicate, aluminum hydroxide, hydrous isosite, magnesium carbonate and magnesium hydroxide; (2) inorganic particles such as acrylic or methacrylic, vinyl chloride, vinyl acetate, nylon, styrene / acrylic, styrene / butadiene or polystyrene / acrylic , Polystyrene / isoprene, polystyrene / isoprene, methyl methacrylate / butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane, phenol, diallyl phthalate and polyester And organic particles. Among them, silica is particularly preferably used in order to impart appropriate slip property to the application layer.

The average particle diameter of the particles B is preferably 200 nm or more, more preferably 250 nm or more, still more preferably 300 nm or more, and particularly preferably 350 nm or more. If the average particle diameter of the particles B is 200 nm or more, it is difficult to aggregate and the slippery property can be ensured.

The average particle diameter of the particles B is preferably 2,000 nm or less, more preferably 1,500 nm or less, still more preferably 1,000 nm or less, and particularly preferably 700 nm or less. When the average particle diameter of the particles B is 2,000 nm or less, transparency is maintained, and the particles do not fall off, which is preferable.

The surface treatment of the particles A and B may be performed. As the surface treatment method, there are a physical surface treatment such as a plasma discharge treatment or a corona discharge treatment, and a chemical surface treatment using a coupling agent, and the use of a coupling agent is preferable. As the coupling agent, an organoalkoxy metal compound (e.g., titanium coupling agent, silane coupling agent) is preferably used. When the particle B is silica, treatment with a silane coupling agent is particularly effective. As the surface treating agent for the particles B, it may be used for performing the surface treatment before preparing the coating liquid, or may be added to the layer as an additive in preparing the coating liquid. Of course, it may be used for the particle A.

The binder resin constituting the coating layer is not particularly limited as long as it is a resin that brings about the adhesiveness. Specific examples of the polymer include a polyester resin, an acrylic resin, a urethane resin, a polyvinyl resin (such as polyvinyl alcohol), a polyalkylene glycol , Polyalkyleneimine, methylcellulose, hydroxyethylcellulose, and the like. Among them, polyester resin, acrylic resin and urethane resin are preferably used from the viewpoints of particle retention and adhesion. Further, in consideration of affinity with the polyester film, a polyester resin is most suitable. These binder resins may be used in combination.

The polyester resin may be 100% by mass or more, preferably 10% by mass or more and 90% by mass or less, of the total solid components in the coating layer. And more preferably 20 mass% or more and 80 mass% or less. When the content of the polyester resin is 90 mass% or less, adhesion with the hard coat layer under high temperature and high humidity is preferably maintained. Conversely, if the content is 10% by mass or more, the presence of another urethane resin or the like is preferable because the adhesiveness with the polyester film at room temperature, high temperature and high humidity is maintained.

In the present invention, the coating layer may be formed to include a crosslinking agent in order to form a crosslinking structure in the coating layer. By including the crosslinking agent, it becomes possible to further improve the adhesion under high temperature and high humidity. Specific examples of the cross-linking agent include urea-based, epoxy-based, melamine-based, isocyanate-based, oxazoline-based and carbodiimide-based ones. Of these, melamine-based, isocyanate-based, oxazoline-based, and carbodiimide-based cross-linking agents are preferable from the viewpoint of stability over time of the coating liquid and improvement in adhesion under high temperature and high humidity treatment. In addition, a catalyst or the like may be suitably used as needed in order to promote the crosslinking reaction.

The content of the crosslinking agent in the coating layer is preferably 5% by mass or more and 50% by mass or less based on the total solid components. More preferably, it is 10 mass% or more and 40 mass% or less. When the amount is 10% by mass or more, the strength of the resin of the coating layer is maintained, the adhesiveness under high temperature and high humidity is good, and if it is 40% by mass or less, flexibility of the resin of the coating layer is maintained and adhesiveness at room temperature and high temperature and high humidity is maintained.

The content of the particles A in the coating layer is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and particularly preferably 5% by mass or more. When the content of the particles A in the coating layer is 2 mass% or more, the refractive index of the coating layer can be kept high and the low coherency can be effectively obtained.

The content of the particles A in the coating layer is preferably 50 mass% or less, more preferably 40 mass% or less, still more preferably 30 mass% or less, particularly preferably 20 mass% or less. When the content of the particles A in the coating layer is 50 mass% or less, the film-forming property is preferably maintained.

The content of the particles B in the coating layer is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and further preferably 1 mass% or more. When the content of the particles B in the coating layer is 0.1% by mass or more, it is preferable that appropriate slippage is maintained.

The content of the particles B in the coating layer is preferably 20 mass% or less, more preferably 15 mass% or less, and further preferably 10 mass% or less. When the content of the particles B in the coating layer is 20 mass% or less, the haze is kept low, which is preferable from the viewpoint of transparency.

The film thickness of the coating layer is preferably 0.001 m or more, more preferably 0.01 m or more, still more preferably 0.02 m or more, and particularly preferably 0.05 m or more. When the film thickness of the coating layer is 0.001 탆 or more, good adhesion is preferable.

The film thickness of the coating layer is preferably 2 m or less, more preferably 1 m or less, still more preferably 0.8 m or less, and particularly preferably 0.5 m or less. When the film thickness of the application layer is 2 m or less, there is no fear that blocking will occur, which is preferable.

The coating layer may contain a surfactant for the purpose of improving the leveling property upon application and removing the foam of the coating liquid. The surfactant may be any of a cationic, anionic, and nonionic surfactant, but a silicone, acetylene glycol or fluorine surfactant is preferred. It is preferable that these surfactants are contained in the coating layer in such a range as not to impair the suppressing effect and the adhesion property of the iris color under the fluorescent lamp.

In order to impart different functionality to the coating layer, various additives may be contained in such a range as not to impair the effect of suppressing the iris color under the fluorescent lamp and the adhesion. Examples of the additives include fluorescent dyes, fluorescent brighteners, plasticizers, ultraviolet absorbers, pigment dispersants, foam inhibitors, defoamers, preservatives and the like.

As a coating method, a so-called in-line coating method in which a polyester base film is coated at the same time and a so-called off-line coating method in which a polyester base film is coated with a separate coater after film formation can be applied. .

As a coating method, any known method can be used as a method for applying the coating liquid to a polyethylene terephthalate (hereinafter abbreviated as PET) film. For example, a reverse roll coating method, a gravure coating method, a kiss coating method, a die coater method, a roll brush method, a spray coating method, an air knife coating method, a wire bar coating method, a pipe doctor method, . These methods are applied alone or in combination.

In the present invention, a method of applying a coating layer on a polyester film includes a method of applying a coating liquid containing a solvent, particles, and a resin to a polyester film, followed by drying. Examples of the solvent include an organic solvent such as toluene, water, or a mixture of water and a water-soluble organic solvent. Preferably, water alone or a water-soluble organic solvent is mixed with water in view of environmental problems.

The solid content concentration of the coating liquid varies depending on the kind of the binder resin and the kind of the solvent, but is preferably 2% by mass or more, more preferably 4% by mass. The solid concentration of the coating liquid is preferably 35 mass% or less, and more preferably 15 mass% or less.

The drying temperature after coating is preferably 80 deg. C or more, more preferably 250 deg. C or less, depending on the type of binder resin, the type of solvent, the presence of the crosslinking agent, the solid content concentration and the like.

The surface roughness (Ra) of the applied layer is preferably 0.01 nm or more, more preferably 0.1 nm or more, still more preferably 0.2 nm or more, and particularly preferably 0.5 Nm. On the other hand, the upper limit of the surface roughness Ra of the coating layer is preferably 200 nm or less, more preferably 100 nm or less, further preferably 80 nm or less, and particularly preferably 50 nm or less.

(Production of adhesive polyester film for optical use)

The adhesive polyester film for optical use of the present invention can be produced by a general method for producing a polyester film. For example, a polyester resin is melted and extruded in a sheet form, and the unoriented polyester molded is stretched in the longitudinal direction at a temperature not lower than the glass transition temperature in the longitudinal direction using the speed difference of the roll, and then stretched in the transverse direction by a tenter Followed by heat treatment.

The polyester film of the present invention may be a uniaxially stretched film or a biaxially stretched film. However, when a biaxially stretched film is used as a protective film on the front surface of a liquid crystal panel, color irregularities of iridescence are not observed even when viewed from above the film surface, The color irregularity of the iridescence shape may be observed.

This phenomenon is attributable to the fact that the biaxially stretched film is made of an ellipsoid of refractive index having a different refractive index in the running direction, the width direction and the thickness direction, and has a retardation of zero according to the transmission direction of light in the film (the refractive index ellipsoid ) Direction. Therefore, when the liquid crystal display screen is observed at a specific direction in the oblique direction, a point where retardation becomes zero may be generated, and a color irregular color irregularity occurs concentrically around the point. When the angle from the position immediately above the film surface (normal direction) to the position where the color irregularity of the iridescence shape is visible is denoted by?, This angle? Increases as the birefringence in the film surface becomes larger, and irregular color irregularity becomes hard to be seen. In the case of a biaxially stretched film, the angle &thetas; tends to be small, so that the uniaxially stretched film is preferable because iridescence-like color unevenness becomes hard to be seen.

However, in the case of a complete uniaxial (uniaxial) film, the mechanical strength in the direction orthogonal to the alignment direction is significantly lowered, which is undesirable. It is preferable that the present invention has biaxial (biaxial symmetry) in a range that does not cause color irregularity of a substantially irregular shape, or does not cause irregular color irregularity in a viewing angle range required for a liquid crystal display screen .

(Laminated polyester film)

The laminated polyester film mainly used for optical use of the present invention is obtained by providing a hard coat layer or the like made of an electron beam, an ultraviolet curable acrylic resin, a siloxane-based thermosetting resin or the like on the coating layer of the adhesive polyester film of the present invention Loses.

It is also a preferable form to provide the functional layer on the application layer of the adhesive polyester film of the present invention. The functional layer is a layer having functionality such as antiglare layer, antireflection antireflection layer, antireflection layer, low reflection layer and antistatic layer in addition to the above-mentioned hard coat layer for the purpose of preventing or inhibiting flashing, suppressing rainbow stains, suppressing scratches . The functional layer may be any of various kinds well known in the art, and the kind thereof is not particularly limited. Each function layer will be described below.

For example, a known hard coat layer can be used to form the hard coat layer, and it is not particularly limited. However, it is also possible to use a resin composition which is polymerized and / or reacted by irradiation with heat, chemical reaction, electron beam, Can be used. Examples of such a curable resin include melamine-based, acrylic-based, silicone-based and polyvinyl alcohol-based curable resins. Photocurable acrylic curable resins are preferred from the viewpoint of obtaining high surface hardness or optical design. Examples of the acryl-based curable resin include polyfunctional (meth) acrylate-based monomers and acrylate-based oligomers. Examples of the acrylate oligomer include polyester acrylate, epoxy acrylate, urethane acrylate, Based, polybutadiene acrylate-based, and silicon acrylate-based. A coating composition for forming the above optical functional layer can be obtained by mixing a reaction diluent, a photopolymerization initiator, a sensitizer, and the like with these acrylate-based curable resins.

The hard coat layer may have an anti-glare function (anti-glare function) for scattering external light. The antiglare function (anti-glare function) is obtained by forming irregularities on the surface of the hard coat layer. In this case, the haze of the film is ideally 0 to 50%, more preferably 0 to 40%, and particularly preferably 0 to 30%. Of course, 0% is ideal, and may be 0.2% or more and 0.5% or more.

Therefore, the application of the film of the present invention is mainly used for LCDs such as prism lens sheet, AR (anti-reflection) film, hard coat film, diffuser plate and crush prevention film, flat TV, A near-infrared absorbing filter which is a member of a front plate for a plasma display, a transparent conductive film such as a touch panel or an electroluminescence, and the like.

As the acrylic resin cured by the electron beam or ultraviolet ray for forming the hard coat layer described above and more specifically having the acrylate functional group, for example, a polyester resin, a polyether resin, an acrylic resin, an epoxy resin An oligomer or prepolymer such as a (meth) acrylate of a polyfunctional compound such as a resin, a urethane resin, an alkyd resin, a spiroacetal resin, a polybutadiene resin, a polythiol polyene resin or a polyhydric alcohol, (Meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and the like, and multifunctional monomers such as trimethylolpropane tri , Tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, penta It may be used containing less pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate and the like.

However, in the case of an electron beam or an ultraviolet ray hardening type resin, it is preferable to use, as a photopolymerization initiator, at least one selected from the group consisting of acetophenone, benzophenone, meihylbenzoyl benzoate,? -Amyloxime ester, tetramethylthiuram monosulfide, As the sensitizer, n-butylamine, triethylamine, tri-n-butylphosphine and the like can be mixed and used.

In addition, the silicone-based (siloxane-based) thermosetting resin can be produced by hydrolysis and condensation reaction of an organosilane compound alone or in a mixture of two or more species under an acid or base catalyst. Particularly, in the case of low reflection, mixing and hydrolysis and condensation reaction of at least one kind of fluorosilane compound is more preferable for improvement of low refractive index, stain resistance and the like.

(Production of laminated polyester film)

The method for producing the laminated polyester film in the present invention will be described by taking the adhesive polyester film as an example, but it is not limited to this.

The above-mentioned electron beam, the ultraviolet curable acrylic resin or the siloxane-based thermosetting resin is applied to the coated layer surface of the above-mentioned adhesive polyester film. When the application layer is provided on both surfaces, it is applied to at least one coating layer surface. The coating liquid is not particularly required to be diluted, but may be diluted with an organic solvent according to necessity such as viscosity, wettability, coating film thickness, etc. of the coating liquid. The coating layer is formed by coating the above-mentioned coating liquid on the above-mentioned film, drying it if necessary, and curing the coating layer by irradiation with electron rays or ultraviolet rays in accordance with the curing conditions of the coating liquid.

In the present invention, the thickness of the hard coat layer is preferably 1 to 15 mu m. If the thickness of the hard coat layer is 1 占 퐉 or more, the effects on the chemical resistance, scratch resistance and antifouling property of the hard coat layer are effectively exhibited. On the other hand, if the thickness is 15 m or less, the flexibility of the hard coat layer is maintained, and cracks or the like do not occur, which is preferable.

As the scratch resistance, it is preferable that the scratches are not conspicuous when viewed from the naked eye when the coated surface is abraded with a black ground. If the scratches are not conspicuous in the above evaluation, scratches are less likely to occur during passage through the guide roll, which is preferable from the viewpoint of handling and the like.

Since the lower limit of the coefficient of static friction (μs) is preferably 0.3, and when it is 0.3 or more, there is no problem of excessive slippage, so that it is easy to roll up by a hard chromium plating roll in the manufacturing process, . The upper limit of the coefficient of static friction (μs) is preferably 0.5, and when it is 0.5 or less, there is no risk of causing scratches on the film as a contact mating surface when winding up.

Since the lower limit of the coefficient of dynamic friction (μd) is preferably 0.4, and if it is 0.4 or more, there is no problem of excessive slippage, so that it is easy to roll up with a roll of hard chrome plating in the manufacturing process, . The upper limit of the coefficient of dynamic friction (μd) is preferably 0.6, and when it is 0.6 or less, there is no risk of causing scratches on the film which becomes the contact mating surface when winding up.

Since the polyester film of the present invention is mainly used as an adhesive film for optical applications, it is preferable that the polyester film has high transparency. The lower limit of the haze is ideally 0%, and the closer to 0% the better. The upper limit of the haze is preferably 2%, and when it is 2% or less, the light transmittance is favorable, and a clear image can be obtained in the liquid crystal display device. The haze of the polyester film can be measured by, for example, a method described later.

The adhesion between the adhesive coating layer and the hard coat layer is preferably 80% by lower limit, and preferably 100% by the evaluation according to a measuring method described later. If it is 80% or more, the adhesion between the coating layer and the hard coat layer is sufficiently maintained.

The lower limit is preferably 10%, and the upper limit of the high-temperature high-humidity adhesion property is preferably 100% with respect to the adhesiveness of the adhesive layer and the hard coat layer under the high-temperature high- If it is 10% or more, the adhesiveness between the adhesive layer and the hard coat layer is generally satisfied under high temperature and high humidity conditions, and the passing property in the post-processing step is generally satisfied. More preferably, it is 50% or more.

It is preferable that the polarizer-protective polyester film forming the hard coat should not show any unevenness of interference by the evaluation method described later. If the unevenness of interference by the evaluation method can not be confirmed, the visibility of the liquid crystal image device is preferable.

The adhesive polyester film of the present invention can be used for various purposes, and is preferably used in a process for producing a polarizer used in a liquid crystal display device, and is particularly preferably used as a protective film of a polarizer constituting a polarizer. Usually, the polarizer is polyvinyl alcohol, and the adhesive polyester film of the present invention is adhered to the polarizer by using an adhesive containing a polyvinyl alcohol or a crosslinking agent added thereto as necessary. At this time, it is more preferable that the coated layer of the adhesive polyester film of the present invention is used toward the opposite surface, not the surface to be bonded to the polarizer. On the surface of the adhesive polyester film of the present invention to be bonded to the polarizer, the adhesive layer comprising a polyester resin, a polyvinyl alcohol resin and a crosslinking agent as described in, for example, International Publication No. 2012/105607 It is preferable that it is laminated.

Example

Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples. The evaluation method used in the present invention is as follows.

(1) average particle diameter

[Measurement by Scanning Electron Microscope]

The average particle diameter of the particles can be measured by the following method. The particles were photographed with a scanning electron microscope (SEM), and the maximum diameter (the distance between the two most distant points) of 300 to 500 particles was measured at a magnification of one smallest particle of 2 to 5 mm, The average value is taken as the average particle diameter. The average particle diameter of the particles present in the coating layer in the present invention can be measured by this measurement method.

[Dynamic light scattering method]

The average particle size of the particles can be determined by dynamic scattering when producing particles or films. The sol was diluted with a dispersion medium, and the average particle size was obtained by measuring the particle size with a submicron particle analyzer N4 PLUS (manufactured by Beckman Coulter Co.) using the parameters of the dispersion medium and calculating by the cumulant method. In the dynamic light scattering method, the average particle size of the particles in the sol is observed, and when the particles are aggregated, the average particle size of the aggregated particles is observed.

(2) Refractive index of particles

The refractive index of the particles can be measured by the following method. The inorganic particles were dried at 150 캜 and pulverized by induction. The powder was immersed in solvent 1 (having a lower refractive index than that of the particles), and solvent 2 (having a refractive index higher than that of the particles) was added in small amounts until the particles became almost transparent Respectively. The refractive index of this solution was measured using an Abbe refractometer (Abbe's refractometer manufactured by Atago Co., Ltd.). The measurement was performed at 23 deg. C, D line (wavelength: 589 nm). The solvent 1 and the solvent 2 can be mixed with each other and selected according to the refractive index, for example, 1,1,1,3,3,3-hexafluoro-2-propanol, 2-propanol, chloroform, carbon tetrachloride, And a solvent such as glycerin.

(3) The haze of the adhesive polyester film

The haze of the adhesive polyester film was measured using a turbidimeter (NDH2000, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K 7136: 2000.

(4) Adhesion

On this adhesive layer of the polyester film obtained in the examples, the hard coat layer described in the section for forming the hard coat layer was formed. The adhesion of the hard coat layer to the substrate film is determined in accordance with 8.5.1 of JIS-K5400-1990 by using a nonwoven polyester film having a hard coat formed thereon.

More specifically, a cutter-shaped cut line passing through the hard coat layer and reaching the substrate film is drawn on the hard coat layer surface using a cutter guide having a gap of 2 mm between gaps. Subsequently, a cellophane adhesive tape (manufactured by Nichiban Co., Ltd., No. 405, 24 mm wide) is attached to the cut surface of the checkerboard-like cut line and rubbed with an eraser to completely adhere. Thereafter, the cellophane adhesive tape was vertically pulled off from the hard coat layer side of the hard coat laminated polarizer protective film, and the number of checkerboard peeled from the hard coat layer side of the hard coat laminated polarizer protective film was visually counted, Adhesion between the layer and the substrate film is determined. In addition, the partly peeled checkerboard is counted as a peeled checkerboard.

(5) Humidity Resistance

The polarizer-protecting laminated film on which the hard coat was formed was allowed to stand in an environment of 85 ° C and 85RH% in a high-temperature and high-humidity bath for 500 hours. Subsequently, the hard coat laminated polarizer protective film was taken out and left at room temperature for 12 hours. Thereafter, the adhesion between the hard coat layer and the substrate film was determined in the same manner as above, and the heat-wettability was evaluated.

(6) Static friction coefficient, kinetic friction coefficient (μs, μd)

The friction coefficient of the polyester film obtained in the examples was measured using Tensilon (Toyo Baldwin, RTM-100) in accordance with JIS K7125-1999 Plastic-Film and Sheet Friction Coefficient Test Method.

(7) Improvement of interference pattern (iris color)

A hard coat layer was formed on this adhesive layer of the adhesive polyester film for optical use obtained in each Example. The adhesive polyester film for optical formation on which the hard coat was formed was cut into an area of 10 cm (film width direction) × 15 cm (film length direction) to prepare a sample film. A black glossy tape (vinyl tape No. 21, black, manufactured by Nitto Denko Co., Ltd.) was attached to the surface opposite to the hard coat layer side of the obtained sample film. Using this three-wavelength type main whiteness (National Pakulk FL 15EX-N 15W) as a light source, the positional relationship (the distance from the light source) in which the most reflection is visually seen from above at an angle 40 to 60 cm, angle of 15 to 45 degrees).

Divide the results of visual observation by the following criteria. In addition, five people who are familiar with the evaluation perform observation, and the highest grade is the evaluation grade. For example, if two grades are equal, the center of the three grades is employed. For example, if ◎ and ○ are two each, △ is one person, ○ is ◎, ◎ is one person, ○ and △ are two people, ○ is ◎, △ is two people each and ○ is one person And "? &Quot;, respectively.

◎: iris color is not seen from observation from all angles

○: A slight iris color appears at any angle

?: A slight iris color was observed

X: Clear iris color was observed

(8) scratch resistance of the applied layer

An adhesive polyester film for optical use of 3 cm (film width direction) × 20 cm (film length direction) was attached to a rubbing fastness tester (RT-200 manufactured by Dai-Igarashi KK) Using a black substrate (thickness 80 탆, arithmetic average surface roughness 0.03 탆) at the contact portion of the loaded film (2 cm x 2 cm, 200 g) and the sample film attached thereto, a distance of 10 cm was measured at a speed of 20 seconds 3 times. The sample film obtained on the black paper was lifted and visually confirmed whether or not the scratch occurred.

○: The occurrence of scratches on the black ground was not confirmed, or slight scratches were confirmed depending on the place

△: A slight scratch was observed on the black background as a whole

X: The occurrence of scratches on the black ground is clearly confirmed

(9) Glass transition temperature

10 mg of a resin sample was heated at a rate of 20 占 폚 / min over a temperature range of 25 to 300 占 폚 using a differential scanning calorimeter (DSC6200, manufactured by Seiko Instruments Inc.) in accordance with JIS K7121-1987 to measure an extrapolated glass transition The initiation temperature was defined as the glass transition temperature.

(10) Number average molecular weight

0.03 g of the resin was dissolved in 10 ml of tetrahydrofuran and the solution was filtered through a GPC-LALLS apparatus low angle light scattering photometer LS-8000 (Tetrahydrofuran solvent, reference: polystyrene) / Minute, column (Shodex KF-802, 804, 806 manufactured by Showa Denko K.K.) was used to measure the number average molecular weight.

(11) Resin composition

The resin was dissolved in deuterated chloroform, and subjected to 1 H-NMR analysis using a nuclear magnetic resonance spectrometer (NMR) Gemini-200 manufactured by Bariansa, and the mole% ratio of each composition was determined from the integration ratio.

(12) Surface roughness (Ra)

Ra was measured by Surfcom (registered trademark) 304B (manufactured by Tokyo Seimitsu Co., Ltd.) in accordance with JIS-B0601-2001. The measurement conditions were cutoff 0.08 占 퐉, stylus radius 2 占 퐉, measurement length 0.8 mm, and measurement speed 0.03 mm / sec.

(Polymerization of polyester resin)

194.2 parts by mass of dimethyl terephthalate, 184.5 parts by mass of dimethyl isophthalate, 14.8 parts by mass of dimethyl-5-sodium sulfoisophthalate, 233.5 parts by mass of diethylene glycol, and 233.5 parts by mass of diethylene glycol were added to an autoclave made of stainless steel equipped with a stirrer, a thermometer and a partial reflux condenser. , 136.6 parts by mass of ethylene glycol and 0.2 parts by mass of tetra-n-butyl titanate were placed, and the transesterification reaction was carried out at 160 ° C to 220 ° C for 4 hours. Subsequently, the temperature was raised to 255 ° C, the pressure in the reaction system was gradually reduced, and the reaction was conducted at a reduced pressure of 30 Pa for 1 hour and 30 minutes to obtain a copolymer polyester resin (I). The resulting copolymer polyester resin (I) was light yellow transparent. The reduced viscosity of the copolymer polyester resin (I) was measured and found to be 0.70 dl / g. The glass transition temperature by DSC was 40 占 폚 and the number average molecular weight was 20,000.

The composition of the copolymer polyester resin (I) is as follows.

Dicarboxylic acid: 49 mol% of terephthalic acid, 48 mol% of isophthalic acid, 3 mol% of 5-sodium isophthalic acid,

Diol component: 40 mol% of ethylene glycol, 60 mol% of diethylene glycol,

(Production of polyester water dispersion)

30 parts by mass of the copolymerized polyester resin (I) and 15 parts by mass of ethylene glycol-n-butyl ether were placed in a reactor equipped with a stirrer, a thermometer and a reflux apparatus, and the mixture was heated and stirred at 110 ° C to dissolve the resin. After the resin was completely dissolved, 55 parts by mass of water was slowly added to the polyester solution with stirring. After the addition, the solution was cooled to room temperature while stirring to obtain a milky white polyester aqueous dispersion (I?) Having a solid content of 28.2 mass%.

(Production of polyurethane water dispersion)

A four-necked flask equipped with a stirrer, a Dimroth condenser, a nitrogen inlet tube, a silica gel drying tube and a thermometer was charged with 43.75 parts by mass of 4,4-dicyclohexylmethane diisocyanate, 12.85 parts by mass of dimethylolbutanoic acid, 153.41 parts by mass of hexamethylene carbonate diol, 0.03 parts by mass of dibutyltin dilaurate and 84.00 parts by mass of acetone as a solvent were added and stirred at 75 ° C for 3 hours under a nitrogen atmosphere to confirm that the reaction solution reached a predetermined amine equivalent Respectively. Next, the reaction solution was cooled to 40 占 폚, and then 8.77 parts by mass of triethylamine was added thereto to obtain a polyurethane prepolymer solution. Next, it was added to 450 g water in a reaction vessel equipped with a high-speed stirrer available homo disper, and was adjusted to 25 ℃, 2,000 min ^- number was dispersed was added to the polyurethane prepolymer solution was mixed with stirring to ^1. Thereafter, acetone and part of water were removed under reduced pressure to prepare a water-soluble polyurethane resin solution (II) having a solid content of 37% by mass. The glass transition temperature of the obtained polyurethane resin (II) was -30 占 폚.

(Polymerization of Block Polyisocyanate Crosslinking Agent)

A flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 100 parts by mass of a polyisocyanate compound having an isocyanurate structure (Dyuranate TPA, manufactured by Asahi Kasei Chemicals) having hexamethylene diisocyanate as a raw material, 100 parts by mass of propylene glycol monomethyl ether 55 parts by mass of acetate and 30 parts by mass of polyethylene glycol monomethyl ether (average molecular weight of 750) were placed and kept at 70 占 폚 for 4 hours in a nitrogen atmosphere. Thereafter, the temperature of the reaction solution was lowered to 50 캜, and 47 parts by mass of methyl ethyl ketoxime was added dropwise. The infrared spectrum of the reaction solution was measured to confirm that the absorption of the isocyanate group was lost, and a block polyisocyanate water dispersion (III) having a solid content of 75 mass% was obtained.

(Polymerization of oxazoline crosslinking agent)

A flask equipped with a thermometer, a nitrogen gas introducing tube, a reflux condenser, a dropping funnel and a stirrer was charged with a mixture of 58 parts by mass of ion-exchanged water as an aqueous medium and 58 parts by mass of isopropanol and a polymerization initiator (2,2'-azobis Propane) dihydrochloride) was added thereto. On the other hand, 16 parts by mass of 2-isopropenyl-2-oxazoline as a polymerizable unsaturated monomer having an oxazoline group in a dropping funnel, 10 parts by mass of methoxypolyethylene glycol acrylate (average addition mol number of ethylene glycol: 9 mol, manufactured by Shin Nakamura Chemical Co., , And 32 parts by mass of methyl methacrylate, and the resulting mixture was added dropwise at 70 DEG C over 1 hour in a nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was stirred for 9 hours and cooled to obtain a water-soluble resin (IV) having an oxazoline group with a solid content concentration of 40 mass%.

(Polymerization of Carbodiimide Crosslinking Agent)

In a flask equipped with a stirrer, a thermometer and a reflux condenser, 168 parts by mass of hexamethylene diisocyanate and 220 parts by mass of polyethylene glycol monomethyl ether (M400, average molecular weight: 400) were added and stirred at 120 DEG C for 1 hour. 26 parts by mass of dicyclohexylmethane diisocyanate and 3.8 parts by mass of 3-methyl-1-phenyl-2-phospholin-1-oxide as a carbodiimidization catalyst (2 mass% based on the total isocyanate) And further stirred at 185 캜 for 5 hours under a nitrogen stream. The infrared spectrum of the reaction solution was measured to confirm that the absorption at a wavelength of 2,200 to 2,300 cm ^-1 was lost. The mixture was cooled to 60 DEG C and 567 parts by mass of ion-exchanged water was added to obtain a carbodiimide water-soluble resin (V) having a solid content of 40% by mass.

(Epoxy-based crosslinking agent)

Denacol EX-521 (solid content concentration: 100%) manufactured by Nagase Chemtex Co., Ltd. was used as the epoxy cross-linking agent (epoxy cross-linking agent (VI)).

(Melamine-based crosslinking agent)

As a melamine crosslinking agent, Beckamine M-3 (solid content concentration: 60%) manufactured by DIC was used (melamine crosslinking agent (VII)).

(Zirconia particles)

2283.6 g of pure water and 403.4 g of oxalic acid dihydrate were charged into a 3 liter glass container and heated to 40 DEG C to prepare a 10.72 mass% oxalic acid aqueous solution. While stirring the aqueous solution, 495.8 g of zirconium oxycarbonate powder (ZrOCO ₃ , manufactured by AMR International Corp., containing 39.76 mass% in terms of ZrO ₂ ) was slowly added thereto, and the mixture was stirred for 30 minutes. Heating was performed. Subsequently, 1747.2 g of a 25.0 mass% aqueous solution of tetramethylammonium hydroxide (manufactured by Tama Chemical Industry Co., Ltd.) was gradually added over 1 hour. At this point, the mixed solution was slurry-like and contained 4.0% by mass in terms of ZrO ₂ . The slurry was transferred into an autoclave vessel made of stainless steel and hydrothermally treated at 145 ° C for 5 hours. The product after the hydrothermal treatment was completely solitary due to the absence of a non-corrosive agent. The obtained sol contained 4.0% by mass of ZrO ₂ and had an average particle diameter of 19 nm by a dynamic light scattering method at a pH of 6.8. Further, the sol had a transmittance of 88% as measured by adjusting the ZrO ₂ concentration to 2.0% by mass with pure water. When the particles were observed by a transmission electron microscope, most of the agglomerated particles of ZrO ₂ primary particles were around 7 nm. 4,000 g of a zirconia sol having a ZrO ₂ concentration of 4.0% by mass obtained by performing the hydrothermal treatment was washed and concentrated while gradually adding pure water using an ultrafiltration apparatus to obtain a ZrO ₂ concentration of 13.1 mass%, a pH of 4.9, a ZrO ₂ concentration of 13.1 mass % Of a zirconia sol having a transmittance of 76%.

3.93 g of a 20 mass% citric acid aqueous solution and 11.0 g of a 25 mass% aqueous solution of tetramethylammonium hydroxide were added to 300 g of a zirconia sol having a ZrO ₂ concentration of 13.1 mass% obtained by the above cleaning and concentration, and further concentrated in an ultrafiltration apparatus Thereby, 129 g of a high-concentration zirconia sol having a ZrO ₂ concentration of 30.5% by mass was obtained. The obtained high concentration zirconia sol had a pH of 9.3 and an average particle size of 19 nm by the dynamic light scattering method. Further, the zirconia sol was free from sediment and was stable for more than one month under the condition of 50 占 폚.

(Titania particles)

12.09 kg of an aqueous solution of titanium tetrachloride containing 7.75% by mass of titanium tetrachloride (manufactured by Osaka Titanium Technologies Co., Ltd.) in terms of TiO ₂ , and 4.69 kg of ammonia water containing 15% by mass of ammonia (manufactured by Ube Goseon Co., Ltd.) To prepare a white slurry liquid having a pH of 9.5. The slurry was then filtered and then washed with pure water to obtain 9.87 kg of a hydrated titanic acid cake having a solid content of 10 mass%. Next, to this cake, 11.28 kg of hydrogen peroxide water (manufactured by Mitsubishi Gas Chemical Co., Ltd.) containing 35 mass% of hydrogen peroxide water and 20.00 kg of pure water were added, and the mixture was heated at 80 DEG C for 1 hour under stirring, 57.52 kg was added to obtain 98.67 kg of an aqueous solution of peroxide titanic acid containing 1% by mass in terms of TiO ₂ as the peroxide titanic acid. The aqueous solution of potassium peroxide was transparent yellowish brown and had a pH of 8.5.

Then, the peroxide mixture of titanic acid aqueous solution of cation exchange resin to 98.67 ㎏ (Mitsubishi Chemical Co., Ltd.) 4.70 ㎏, and here the tartaric acid potassium (Showa Kakogawa Co., Ltd.) for containing 1% by mass SnO ₂ in terms of the reference 12.33 kg of potassium stannate aqueous solution was slowly added under stirring. Next, the cation exchange resin containing potassium ions and the like was separated and then placed in an autoclave (120 L, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and heated at a temperature of 165 캜 for 18 hours.

Next, the obtained mixed aqueous solution was cooled to room temperature and then concentrated with an ultrafiltration membrane device (ACV-3010, manufactured by Asahi Kasei Corporation) to obtain titanium-based fine particles (hereinafter, referred to as "P-1" ) Was obtained. The solids contained in the sol thus obtained were measured by the above-mentioned method and found to be titanium-based fine particles (primary particles) comprising a composite oxide containing titanium and tin having a rutile crystal structure. The content of the metal component contained in the titanium-based fine particles was measured and found to be 87.2% by mass of TiO ₂ , 11.0% by mass of SnO ₂ and 1.8% by mass of K ₂ O based on the oxide content of each metal component. The pH of the mixed aqueous solution was 10.0. Further, the water-dispersed sol containing the titanium-based fine particles is transparent milky white, the average particle diameter of the titanium-based fine particles contained in the water-dispersed sol is 35 nm, and the distribution frequency of the coarse particles having a particle diameter of 100 nm or more is 0 %. The refractive index of the obtained titanium-based fine particles was found to be 2.42.

(Zirconia / titania mixed particles)

The zirconia particles and the titania particles thus obtained were mixed in respective proportions to prepare zirconia / titania mixed particles having a solid content concentration of 13 mass%.

(Formation of hard coat layer)

A coating solution for forming a hard coat layer having the composition shown below was applied on the surface opposite to the surface to be bonded to the polarizer of the polyester film prepared in the following Examples using a # 10 wire bar and dried at 70 캜 for 1 minute to prepare a solvent . Subsequently, the film coated with the hard coat layer was irradiated with ultraviolet rays of 300 mJ / cm 2 using a high-pressure mercury lamp to obtain a polarizer protective film having a hard coat layer having a thickness of 5 탆.

Hard coat layer forming coating liquid

Methyl ethyl ketone 65.00 mass%

27.20 mass% of dipentaerythritol hexaacrylate

(A-DPH manufactured by Shin-Nakamura Chemical Co., Ltd.)

Polyethylene diacrylate 6.80 mass%

(Shin-Nakamura Chemical A-400)

Photopolymerization initiator 1.00 mass%

(Irgacure 184 manufactured by Ciba Specialty Chemicals)

(Example 1)

(Preparation of coating liquid)

A coating liquid having the following composition was prepared.

Water 34.94 parts by mass

Isopropyl alcohol 30.00 parts by mass

Particle A-1 7.24 parts by mass

  (Zirconia / titania mixed particles having an average particle diameter of 23 nm,

   Zirconia / mass ratio of zirconia to titania total mass of 75 mass%

   Solid content concentration 13 mass%)

Particle B-1 0.90 parts by mass

  (Silica sol having an average particle diameter of 450 nm, solid concentration of 40% by mass)

17.92 parts by mass of a polyester water dispersion (I?)

  (Solid content concentration: 28.2 mass%)

2.90 parts by mass of a block isocyanate crosslinking agent (III)

  (Solid concentration 75% by mass)

Surfactant 0.30 parts by mass

  (Fluorine-based, solid concentration of 10% by mass)

High boiling point solvent 3.00 parts by mass

0.26 parts by mass

(Production of this adhesive polyester film)

The PET resin pellets having an intrinsic viscosity (solvent: phenol / tetrachloroethane = 60/40) of 0.62 dl / g as a raw material for a film raw material and containing substantially no particles were subjected to a heat treatment under reduced pressure of 133 Pa And dried. Thereafter, the mixture was supplied to an extruder, melt extruded into a sheet form at about 280 DEG C, and rapidly solidified on a rotary cooling metal roll maintained at a surface temperature of 20 DEG C to solidify to obtain an unstretched PET sheet.

This unstretched PET sheet was heated to 100 캜 by a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction by a roll group having a peripheral speed to obtain a uniaxially stretched PET film.

Subsequently, the coating liquid was coated on one side of the PET film by a roll coating method and then dried at 80 DEG C for 15 seconds. The coating amount after drying after the final stretching was adjusted to be 0.12 g / m 2. Subsequently, the film was stretched by 4.0 times in the width direction at 150 DEG C by a tenter, heated at 230 DEG C for 0.5 second in a state where the length in the film width direction was fixed, further relaxed in the width direction of 3% at 230 DEG C for 10 seconds, Thereby obtaining this adhesive polyester film having a thickness of 38 mu m.

(Example 2)

Except that the particle A-2 in which the mass ratio of zirconia to the total mass of zirconia and titania was 50% by mass was used instead of the particle A-1 of the coating liquid, the adhesive polyester film ≪ / RTI >

(Example 3)

Except that the particle A-3 in which the mass ratio of zirconia to the total mass of zirconia and titania was 25% by mass in place of the particle A-1 of the coating liquid, the adhesive polyester film ≪ / RTI >

(Example 4)

This adhesive polyester film was obtained in the same manner as in Example 1 except that a coating liquid having the following composition was prepared and used in place of the coating liquid prepared and used in Example 1.

Water 37.23 parts by mass

Isopropyl alcohol 30.00 parts by mass

Particle A-1 3.79 parts by mass

  (Zirconia / titania mixed particles having an average particle diameter of 23 nm,

   Zirconia / mass ratio of zirconia to titania total mass of 75 mass%

   Solid content concentration 13 mass%)

Particle B-1 0.95 parts by mass

  (Silica sol having an average particle diameter of 450 nm, solid concentration of 40% by mass)

18.77 parts by mass of a polyester water dispersion (I?)

  (Solid content concentration: 28.2 mass%)

3.03 parts by mass of a block isocyanate crosslinking agent (III)

  (Solid concentration 75% by mass)

Surfactant 0.30 parts by mass

  (Fluorine-based, solid concentration of 10% by mass)

High boiling point solvent 3.00 parts by mass

0.27 parts by mass

(Example 5)

This adhesive polyester film was obtained in the same manner as in Example 1 except that a coating liquid having the following composition was prepared and used in place of the coating liquid prepared and used in Example 1.

Water 32.85 parts by mass

Isopropyl alcohol 30.00 parts by mass

Particle A-1 10.39 parts by mass

  (Zirconia / titania mixed particles having an average particle diameter of 23 nm,

   Zirconia / mass ratio of zirconia to titania total mass of 75 mass%

   Solid content concentration 13 mass%)

Particle B-1 0.87 parts by mass

  (Silica sol having an average particle diameter of 450 nm, solid concentration of 40% by mass)

17.15 parts by mass of a polyester water dispersion (I?)

  (Solid content concentration: 28.2 mass%)

2.80 parts by mass of a block isocyanate crosslinking agent (III)

  (Solid concentration 75% by mass)

Surfactant 0.30 parts by mass

  (Fluorine-based, solid concentration of 10% by mass)

High boiling point solvent 3.00 parts by mass

0.25 parts by mass

(Example 6)

This adhesive polyester film was obtained in the same manner as in Example 1 except that a coating liquid having the following composition was prepared and used in place of the coating liquid prepared and used in Example 1.

Water 39.17 parts by mass

Isopropyl alcohol 30.00 parts by mass

Particle A-1 7.24 parts by mass

  (Zirconia / titania mixed particles having an average particle diameter of 23 nm,

   Zirconia / mass ratio of zirconia to titania total mass of 75 mass%

   Solid content concentration 13 mass%)

Particle B-1 0.90 parts by mass

  (Silica sol having an average particle diameter of 450 nm, solid concentration of 40% by mass)

Polyurethane water dispersion (II) 13.70 parts by mass

  (Solid content concentration: 37% by mass)

2.90 parts by mass of a block isocyanate crosslinking agent (III)

(Solid concentration 75% by mass)

Surfactant 0.30 parts by mass

  (Fluorine-based, solid concentration of 10% by mass)

High boiling point solvent 3.00 parts by mass

0.26 parts by mass

(Example 7)

This adhesive polyester film was obtained in the same manner as in Example 1 except that a coating liquid having the following composition was prepared and used in place of the coating liquid prepared and used in Example 1.

Water 34.94 parts by mass

Isopropyl alcohol 30.00 parts by mass

Particle A-1 7.24 parts by mass

  (Zirconia / titania mixed particles having an average particle diameter of 23 nm,

   Zirconia / mass ratio of zirconia to titania total mass of 75 mass%

   Solid content concentration 13 mass%)

Particle B-1 0.90 parts by mass

  (Silica sol having an average particle diameter of 450 nm, solid concentration of 40% by mass)

Polyester water dispersion (I?) 13.27 parts by mass

  (Solid content concentration: 28.2 mass%)

Polyurethane water dispersion (II) 4.98 parts by mass

  (Solid content concentration: 37% by mass)

2.90 parts by mass of a block isocyanate crosslinking agent (III)

  (Solid concentration 75% by mass)

Surfactant 0.30 parts by mass

  (Fluorine-based, solid concentration of 10% by mass)

High boiling point solvent 3.00 parts by mass

0.26 parts by mass

(Example 8)

The adhesive polyester film was obtained in the same manner as in Example 1 except that the block isocyanate crosslinking agent (III) in the coating liquid was changed to the water-soluble resin (IV) having an oxazoline group and the content thereof was controlled.

(Example 9)

This adhesive polyester film was obtained in the same manner as in Example 1 except that the block isocyanate crosslinking agent (III) in the coating liquid was changed to the carbodiimide water-soluble resin (V) and the content thereof was adjusted.

(Example 10)

The adhesive polyester film was obtained in the same manner as in Example 1 except that the block isocyanate crosslinking agent (III) in the coating liquid was changed to the melamine crosslinking agent (VII) and the content thereof was controlled.

(Example 11)

This adhesive polyester film was obtained in the same manner as in Example 1 except that the block isocyanate crosslinking agent (III) in the coating liquid was changed to epoxy crosslinking agent (VI) and the content thereof was adjusted.

(Example 12)

This adhesive polyester film was obtained in the same manner as in Example 1 except that the particle A-4 having a mean particle size of 40 nm was used instead of the particle A-1 of the coating liquid.

(Example 13)

This adhesive polyester film was obtained in the same manner as in Example 1 except that the particle A-5 having a mean particle diameter of 30 nm was used instead of the particle A-1 of the coating liquid.

(Example 14)

The adhesive polyester film was obtained in the same manner as in Example 1 except that the film thickness of the application layer was changed to 0.05 mu m.

(Example 15)

The adhesive polyester film was obtained in the same manner as in Example 1 except that the film thickness of the coating layer was changed to 0.075 mu m.

(Example 16)

The adhesive polyester film was obtained in the same manner as in Example 1 except that the film thickness of the coating layer was changed to 0.125 탆.

(Example 17)

This adhesive polyester film was obtained in the same manner as in Example 1 except that a coating liquid having the following composition was prepared and used in place of the coating liquid prepared and used in Example 1.

Water 35.40 parts by mass

Isopropyl alcohol 30.00 parts by mass

Particle A-1 7.26 parts by mass

  (Zirconia / titania mixed particles having an average particle diameter of 23 nm,

   Zirconia / mass ratio of zirconia to titania total mass of 75 mass%

   Solid content concentration 13 mass%)

Particle B-1 0.36 parts by mass

  (Silica sol having an average particle diameter of 450 nm, solid concentration of 40% by mass)

17.98 parts by mass of a polyester water dispersion (I?)

  (Solid content concentration: 28.2 mass%)

2.90 parts by mass of a block isocyanate crosslinking agent (III)

  (Solid concentration 75% by mass)

Surfactant 0.30 parts by mass

  (Fluorine-based, solid concentration of 10% by mass)

High boiling point solvent 3.00 parts by mass

0.26 parts by mass

(Example 18)

This adhesive polyester film was obtained in the same manner as in Example 1 except that a coating liquid having the following composition was prepared and used in place of the coating liquid prepared and used in Example 1.

Water 34.48 parts by mass

Isopropyl alcohol 30.00 parts by mass

Particle A-1 7.22 parts by mass

  (Zirconia / titania mixed particles having an average particle diameter of 23 nm,

   Zirconia / mass ratio of zirconia to titania total mass of 75 mass%

   Solid content concentration 13 mass%)

Particle B-1 1.44 parts by mass

  (Silica sol having an average particle diameter of 450 nm, solid concentration of 40% by mass)

17.88 parts by mass of a polyester water dispersion (I?)

  (Solid content concentration: 28.2 mass%)

2.90 parts by mass of a block isocyanate crosslinking agent (III)

  (Solid concentration 75% by mass)

Surfactant 0.30 parts by mass

  (Fluorine-based, solid concentration of 10% by mass)

High boiling point solvent 3.00 parts by mass

0.26 parts by mass

(Comparative Example 1)

The adhesive polyester film was obtained in the same manner as in Example 1 except that the non-mixed zirconia single particle A-6 containing no titania was used instead of the particle A-1 of the coating liquid.

(Comparative Example 2)

Except that zirconia-free non-mixed titania-based single particle A-7 was used instead of the particle A-1 of the coating liquid and the mass% was adjusted in consideration of the solid content concentration. Thereby obtaining a cast polyester film.

(Comparative Example 3)

This adhesive polyester film was obtained in the same manner as in Example 1 except that a coating liquid having the following composition was prepared and used in place of the coating liquid prepared and used in Example 1.

Water 35.71 parts by mass

Isopropyl alcohol 30.00 parts by mass

Particle A-1 7.27 parts by mass

  (Zirconia / titania mixed particles having an average particle diameter of 23 nm,

   Zirconia / mass ratio of zirconia to titania total mass of 75 mass%

   Solid content concentration 13 mass%)

28.58 parts by mass of a polyester water dispersion (I?)

  (Solid content concentration: 28.2 mass%)

1.38 parts by mass of a block isocyanate crosslinking agent (III)

  (Solid concentration 75% by mass)

Surfactant 0.30 parts by mass

  (Fluorine-based, solid concentration of 10% by mass)

High boiling point solvent 3.00 parts by mass

0.26 parts by mass

The adhesive polyester film obtained by each example had a satisfactory scratch resistance, a suitable coefficient of static friction and a coefficient of dynamic friction, satisfactory results in terms of transparency, adhesiveness, resistance to humidity and heat, and low cohesion . On the other hand, the adhesive polyester film obtained in Comparative Example 1 did not contain zirconia in the particle A in the coating layer, and thus was not satisfactory in terms of heat and humidity resistance. Further, the adhesive polyester film obtained in Comparative Example 2 did not contain titania in the particle A in the coating layer, and thus was not satisfactory in scratch resistance. The adhesive polyester film obtained in Comparative Example 3 had a large coefficient of friction because it did not contain the lubricant particles B in the coating layer.

(Example 19)

On the application layer of the adhesive polyester film obtained in Example 1, a coating liquid for forming an antiglare layer having the following composition was applied using a # 5 wire bar and dried at 70 DEG C for 1 minute to remove the solvent. Subsequently, a film coated with the antiglare layer was irradiated with ultraviolet rays of 300 mJ / cm 2 using a high-pressure mercury lamp to obtain a laminated polyester film having an antiglare layer with a thickness of 5 탆. A desired laminated polyester film imparted with a flame retardancy was obtained.

· Coating liquid for forming an antiglare layer

Toluene 34 parts by mass

50 parts by mass of pentaerythritol triacrylate

Silica (average particle diameter 1 占 퐉) 12 parts by mass

1 part by mass of silicone (leveling agent)

1 part by mass of photopolymerization initiator

(Irgacure 184 manufactured by Ciba Specialty Chemicals)

(Example 20)

A coating liquid for forming a medium refractive index layer having the following composition was applied on the coating layer of the adhesive polyester film obtained in Example 1 using a bar coater and dried at 70 DEG C for 1 minute and then coated with 400 mJ / cm < 2 > to obtain a medium refractive index layer having a dry film thickness of 5 mu m. Next, a coating solution for forming a high refractive index layer having the composition below was formed on the formed medium refractive index layer using a bar coater in the same manner as the medium refractive index layer, and a coating liquid for forming a low refractive index layer Refractive index layer in the same manner as in the case of the intermediate refractive index layer to obtain a laminated polyester film in which the antireflection layer was laminated. A preferable laminated polyester film having antireflection properties was obtained.

The coating liquid for forming a medium refractive index layer (refractive index: 1.52)

70 parts by weight of dipentaerythritol hexaacrylate

1,6-bis (3-acryloyloxy-2-hydroxypropyloxy) hexane

30 parts by mass

Photopolymerization initiator 4 parts by mass

(Irgacure 184 manufactured by Ciba Specialty Chemicals)

100 parts by mass of isopropanol

Coating liquid for forming a high refractive index layer (refractive index: 1.64)

ITO fine particles (average particle diameter 0.07 占 퐉) 85 parts by mass

15 parts by mass of tetramethylolmethane triacrylate

5 parts by mass of a photopolymerization initiator (KAYACURE BMS, manufactured by Nippon Kayaku Co., Ltd.)

Butyl alcohol 900 parts by mass

Coating liquid for forming a low refractive index layer (refractive index: 1.42)

1,10-diacryloyloxy-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorodecane 70 parts by weight

10 parts by mass of dipentaerythritol hexaacrylate

60 parts by mass of silica gel fine particles (XBA-ST, manufactured by Nissan Chemical Industries, Ltd.)

5 parts by mass of a photopolymerization initiator (KAYACURE BMS, manufactured by Nippon Kayaku Co., Ltd.)

Claims (8)

Wherein the coating layer contains a zirconia / titania mixed particle A, a lubricant particle B and a binder resin, and the zirconia / titania mixed particle A has a total mass of zirconia and titania Wherein the content ratio of zirconia to zirconia is 10 to 90 mass%, the average particle diameter of the lubricant particle B is 200 nm or more, and the surface roughness (Ra) of the applied layer is 200 nm or less. The method according to claim 1,
This adhesive polyester film has an average particle diameter of zirconia / titania mixed particle A of 5 to 200 nm. 3. The method according to claim 1 or 2,
Wherein the content of the lubricant particle B relative to the solid content of the coating layer is 0.1 to 20% by mass. 3. The method according to claim 1 or 2,
Wherein the content of the zirconia / titania mixed particle A in relation to the solid content of the coating layer is 2 to 50 mass%. The method of claim 3,
Wherein the content of the zirconia / titania mixed particle A in relation to the solid content of the coating layer is 2 to 50 mass%. A laminate having a functional layer selected from the group consisting of a hard coat layer, an antiglare layer, an antireflective antireflective layer, an antireflective layer and a low reflective layer on a coating layer of the adhesive polyester film according to claim 1 or 2 Polyester film. A laminated polyester film having on an application layer of the adhesive polyester film according to claim 3 at least one functional layer selected from the group consisting of a hard coat layer, an antiglare layer, a antireflection antireflection layer, an antireflection layer and a low reflection layer. A laminated polyester film having on the application layer of the adhesive polyester film according to claim 4 at least one functional layer selected from the group consisting of a hard coat layer, an antiglare layer, a antireflection reflective layer, an antireflection layer and a low reflective layer.