KR20120024809A - Highly adhesive polyester film for optical use - Google Patents

Abstract

Provides an optically easy-adhesive polyester film which suppresses the iris-colored body under fluorescent lamps, is excellent in adhesion to the hard coat layer, adhesion under high temperature and high humidity (humidity heat resistance), and chipping resistance of the coating layer. do.
As an easily-adhesive polyester film for optics which has a coating layer containing a polyester resin, particle | grains A, and particle | grains B on at least one side of a polyester film, the said polyester resin is naphthalenedicarboxylic acid as an acid component, and the following: The dicarboxylic acid component represented by Formula (1) and / or the diol component represented by following formula (2), The said particle | grain A is metal oxide particle of refractive index 1.7 or more and 3.0 or less, The said particle B, The easily-adhesive polyester film for optics which is a particle | grain with an average particle diameter of 200 nm or more and 700 nm or less.
(1) HOOC- (CH ₂ ) _n -COOH (wherein n is an integer of 4≤n≤10)
(2) HO- (CH ₂ ) _n -OH (wherein n is an integer of 4≤n≤10)

Description

Highly adhesive polyester film for optical use

The present invention relates to an easily adhesive polyester film for optics. For example, it is mounted on the front surface of a display screen such as a touch panel, a liquid crystal panel (LCD), a CRT (CRT), a plasma display (PDP), an organic electroluminescence (organic EL) of a TV or a computer. The present invention relates to an optically easy-adhesive polyester film provided with anti-reflective property that suppresses reflection of light, glare, iris color, etc., and excellent adhesion to the hard coat layer and adhesion after high temperature and high humidity treatment.

The hard coat film which laminated | stacked the transparent hard coat layer is used for the front surface of displays, decorative materials, such as a touch panel, a computer, a TV, a liquid crystal display device, and the like. Moreover, as a transparent plastic film of a base material, the transparent biaxially-oriented polyester film is generally used, and in order to improve the adhesiveness of the polyester film which is a base material, and a hard-coat layer, application | coating which has easy contactability as these intermediate | middle layers is carried out. Often, floors are installed.

The hard coat film is required to be resistant to temperature, humidity, light, transparency, chemical resistance, scratch resistance, antifouling properties, and the like. Moreover, since a hard coat film is often used for the surface of a display, a decorative material, etc., visibility and designability are calculated | required. Therefore, in order to suppress glare, iris color, etc. by the reflected light when viewed from an arbitrary angle, the antireflection layer of the multilayer structure which laminated | stacked the high refractive index layer and the low refractive index layer mutually on top of the hard-coat layer is provided. It is generally done.

However, in applications such as displays and decorative materials, in recent years, additional large screens (large area) and high quality have been required, and with this, the level of demand for suppression of iris color (interference nonuniformity), especially under fluorescent lamps, has increased. have. In addition, in the fluorescent lamp, the three-wavelength type has become mainstream for reproducibility of daylight color, and interference nonuniformity tends to appear more easily. In addition, the demand for cost reduction due to the simplification of the antireflection layer is also increasing. Therefore, it is desired to suppress interference nonuniformity as much as possible only by the hard coat film which does not add an antireflection layer.

The iris color (interference nonuniformity) of a hard coat film arises because the difference of the refractive index (for example, 1.62-1.65) of the polyester film which is a base material, and the refractive index (for example, 1.49) of the hard-coat layer which consists of acrylic resins is large. It is known. In order to reduce the refractive index difference between laminations and to prevent the occurrence of interference nonuniformity, a coating layer is provided on the polyester film as the base material, and 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 small. The method of controlling the refractive index of an application layer by content of resin which comprises an application layer, and a high refractive index additive is disclosed. As such a method, for example, (1) one containing a water-soluble polyester resin and a water-soluble metal chelate compound or a metal acylate compound (Patent Document 1), and (2) one containing a polymer binder and a high refractive index metal oxide. (Patent Document 2) and the like have been proposed.

When the occurrence of interference nonuniformity is suppressed by the methods (1) and (2), it is important to control the thickness of the coating layer. By providing the coating layer, the reflected light generated at the hard coat layer-coating layer interface and the reflected light generated at the coating layer-polyester film interface are generated. This is because it is necessary to control the coating layer thickness within. Therefore, when the thickness of an application layer exceeds a predetermined range, the interference nonuniformity by these reflected light will generate | occur | produce. Therefore, in the method of said (1), (2), it was necessary to control the coating layer thickness very strictly on the production management.

Japanese Patent No. 3632044 Japanese Patent Publication No. 2004-54161

With the development of mobile technology, the use of mobile devices such as mobile phones, car navigation systems and electronic books is expanding. In such a field, the drawback of the visibility by the interference fringe is more present in the use which designs on the back surface of a hard-coat film, such as the icon sheet of the mobile telephone of a touchscreen, for example.

However, in recent years, from the viewpoint of improving production efficiency, various solvents excellent in quick drying and leveling have been used as solvents for the coating liquid for hard coat layer formation. Among them, dissolving the coating layer provided on the polyester film To be used. Therefore, even if the coating layer which has a specific thickness is provided by the said method, the coating layer thickness may change with the solvent of the coating liquid for hard-coat layer formation, and interference nonuniformity may not be suppressed.

Moreover, in the method of said (2), since the main component of the polyester resin used for controlling refractive index is a naphthalenedicarboxylic acid component or a short-chain diol component, the hardness of resin composition is comparatively high, and it is a firm coating layer. It is. Therefore, there existed a situation which the particle | grains in an application layer fell (powder falls) at the time of film cutting, and adheres as a foreign material.

In addition, in order to improve productivity in recent years, as the post-processing process such as lamination of the hard coat layer and the slit processing are accelerated, strong friction is applied to the coating layer, and chipping of the coating layer has not been a problem in the past. Thickness fluctuations and quality fluctuations are a challenge. In particular, since the resin used for increasing the refractive index is relatively high in hardness and easily broken, the chipping of the coating layer tends to be larger as the coating layer suppresses interference unevenness.

Therefore, there is a demand for an optically adhesive polyester film having an effect of suppressing interference nonuniformity that can be widely applied to various solvents, less chipping of the coating layer even in high-speed processing, and having a stable interference nonuniformity reducing effect. That is, the present invention suppresses the iris-like color under fluorescent lamps, and is excellent in adhesion to the hard coat layer, adhesion under high temperature and high humidity, and further has optical chipping resistance of the coating layer even in high-speed post-processing. It is an object to provide an adhesive polyester film and an optically laminated polyester film obtained by laminating a hard coat layer on the film.

As a result of earnestly examining the coating layer composition, the present inventor has added large particles having an average particle diameter of 200 nm or more and 700 nm or less to a coating layer having a predetermined refractive index, and thus stably interferes with thickness fluctuations. The surprising effect of being able to suppress the nonuniformity is found, and further, chipping of the coating layer can be remarkably suppressed by using a polyester resin containing a long chain dicarboxylic acid component having a specific carbon number and / or a long chain diol component. It discovered that it was possible and came to obtain the laminated polyester film for optics of this invention.

That is, this invention is an easily-adhesive polyester film for optics which has a coating layer containing a polyester resin, particle | grains A, and particle | grains B on at least one side of a polyester film, The said polyester resin is a naphthalene as an acid component. Dicarboxylic acid, the dicarboxylic acid component represented by following formula (1), and / or the diol component represented by following formula (2), The said particle | grain A is metal oxide particle of refractive index 1.7 or more and 3.0 or less. The said particle | grain B is an easily adhesive polyester film for optics whose average particle diameter is 200 nm or more and 700 nm or less.

(1) HOOC- (CH ₂ ) _n -COOH (wherein n is an integer of 4≤n≤10)

(2) HO- (CH ₂ ) _n -OH (wherein n is an integer of 4≤n≤10)

Moreover, this invention is the said easily adhesive polyester film for optics characterized by including a crosslinking agent in the said application layer.

The present invention is also characterized in that the crosslinking agent is at least one crosslinking agent selected from a urea crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, an isocyanate crosslinking agent, an oxazoline crosslinking agent, and a carbodiimide crosslinking agent. It is an adhesive polyester film.

Moreover, this invention is an optical laminated polyester film formed by laminating | stacking the hard-coat layer which consists of an electron beam or an ultraviolet curable acrylic resin, or a siloxane-type thermosetting resin on the application layer of the said easily-adhesive polyester film for optics.

The easy-adhesive polyester film for optics of the present invention is excellent in suppressing interference nonuniformity when the hard coat layer is laminated on the easily adhesive layer of the film, and also has good adhesion with the hard coat layer and adhesion (moisture heat resistance) under high temperature and high humidity. At the same time, the chipping property of the coating layer can be significantly suppressed. Therefore, it is very suitable as a base film of the optical laminated polyester film which laminated | stacked the hard-coat layer.

(Polyester film)

The polyester film used as a base material in this invention is a film comprised from a polyester resin, and mainly makes one or more types of polyethylene terephthalate, a polypropylene terephthalate, a polybutylene terephthalate, and a polyethylene naphthalate a component. . Among these polyester resins, polyethylene terephthalate is most preferred in terms of balance between physical properties and cost. Moreover, these polyester films can improve chemical resistance, heat resistance, mechanical strength, etc. by biaxially stretching.

In addition, the biaxially stretched polyester film may be a single layer or a multilayer. Moreover, as long as it is in the range which shows the effect of this invention, each of these layers can be made to contain various additives in a polyester resin as needed. As an additive, antioxidant, a light resistant agent, an antigelling agent, an organic wetting agent, an antistatic agent, a ultraviolet absorber, surfactant, etc. are mentioned, for example.

Moreover, in order to improve the handling characteristics, such as activity, winding property, and blocking resistance of a film, and abrasion characteristics, such as abrasion resistance and scratch resistance, it is made to contain inert particle in the polyester film which is a base material. There is a case. However, in order to use the film of this invention as a base film of an optical member, it is calculated | required that it is excellent in handling property, maintaining high transparency. Specifically, when used as an optical member, the transparency is preferably 85% or more, more preferably 87% or more, still more preferably 88% or more, 89 of the optically adhesive polyester film More than% is even more preferred, and more than 90% is particularly preferred.

In addition, it is preferable that content of the inert particle in a base film is as small as possible for a high definition. Therefore, it is preferable to set it as the multilayer structure which contained particle | grains only in the surface layer of a film, or to make microparticles | fine-particles contain only a coating layer without containing particle | grains substantially in a film.

In particular, from the viewpoint of transparency, when the inert particles are not substantially contained in the polyester film, in order to improve the handling properties of the film, inorganic and / or heat resistant polymer particles are contained in the aqueous coating liquid, and the unevenness is formed on the surface of the coating layer. It is important to form.

In addition, "the inert particle does not contain substantially", for example, in the case of an inorganic particle, 50 ppm or less, Preferably it is 10 ppm, when the element derived from a particle is quantitatively analyzed by fluorescence X-ray analysis. Hereinafter, most preferably, the content falls below the detection limit. This is because, even if the particles are not actively added to the base film, the contaminant derived from foreign foreign matter, the raw material resin or the contamination adhered to the line or the device in the manufacturing process of the film may peel off and be mixed in the film. .

In addition, when making a base film into a multilayered structure, the two-layered three-layered constitution which does not contain inert particle substantially in an intermediate | middle layer, and contains inert particle only in outermost layer is compatible with transparency and workability, and is preferable.

Moreover, in the use which moldability is calculated | required, you may use the base film which provided moldability with the polyester resin containing a copolymerization component.

(Coating layer)

In the easily-adhesive film for optics of this invention, the polyacid containing naphthalenedicarboxylic acid as a acid component, the dicarboxylic acid component represented by following formula (1), and / or the diol component represented by following formula (2). It is important to provide it in the coating layer containing ester resin, the metal oxide particle (particle A) of refractive index 1.7 or more and 3.0 or less, and the particle | grains (particle B) of 200 nm-700 nm of average particle diameters. That is, it is based on the following achievement means of this invention.

(1) HOOC- (CH ₂ ) _n -COOH (wherein n is an integer of 4≤n≤10)

(2) HO- (CH ₂ ) _n -OH (wherein n is an integer of 4≤n≤10)

(1) Refractive Index Control of Coating Layer

The optical easily adhesive film of this invention needs to adjust the refractive index of an application layer to the vicinity of the intermediate | middle of a hard-coat layer and a base polyester film. Since the refractive index of the hard coat layer varies depending on the composition of the resin used for the hard coat layer, the refractive index of the coating layer is preferably adjusted accordingly, and specifically, the refractive index of the coating layer is in the range of 1.6 to 1.7. Need to be adjusted. By doing in this way, each interface refractive index difference is made small and interference nonuniformity is suppressed. In general, in the case of the coating layer having easy adhesiveness, since the refractive index is low (about 1.50), in order to control the refractive index of the coating layer in the above range, in this application, the resin used in the coating layer is used as an acid component as naphthalenedicarboxylic acid. Using a polyester resin containing, a metal oxide particle (particle A) having a refractive index of 1.7 or more and 3.0 or less is further added. By such a structure, it can be set as the coating layer with high refractive index, having adhesiveness. The detail of these compositions is mentioned later.

(2) Particles having a mean particle size of 200 nm or more and 700 nm or less (particle B)

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the coating layer composition, the inventor discovered the interference nonuniformity suppression effect by adding the particle | grains (particle B) of 200 nm-700 nm of average particle diameters to an application layer, and came to this invention. As a reason for particle B to exhibit such an effect, this inventor thinks as follows. Unevenness | corrugation is formed in the interface of a coating layer and a hard-coat layer by adding particle | grains with a comparatively large average particle diameter to a coating layer. This uneven structure causes light scattering at the interface between the coating layer and the hard coat layer. It is thought that such random light scattering causes disturbance of the phase of the reflected light generated at the interface between the coating layer and the base polyester film, and as a result, an effect of suppressing interference nonuniformity occurs. Since the coating layer of the optically easy-adhesive film of this application has such a structure, it does not need to control coating thickness highly like the conventional technique, and it became wide application also as the coating liquid for hard-coat layer formation which consists of various solvents.

Moreover, it discovered that adhesiveness with a hard-coat layer improves as an effect which added particle | grain B to the coating layer. It is considered that this is because the unevenness is formed at the interface between the coating layer and the hard coat layer, thereby increasing the interface area between the coating layer and the hard coat layer, and advantageously acting on the adhesiveness.

In order for particle B to exhibit the said effect, it is preferable that the thickness of an application layer is smaller than the average particle diameter of particle B, and the thickness of an application layer is preferably less than 1/1 of the average particle diameter of particle B, and is 1/2 or less More preferred. Moreover, 1/15 or more of the average particle diameter of the particle | grains B is preferable, as for the thickness of an application layer, 1/10 or more are more preferable, and 1/7 or more is more preferable. If the thickness of an application layer is less than 1/15 of the average particle diameter of particle | grain B, transparency may fall.

(3) Polyester resin containing long-chain dicarboxylic acid component and / or diol component

The coating layer of the present invention uses relatively large particles having an average particle diameter of 200 nm or more and 700 nm or less while using a relatively hard polyester resin containing a naphthalenedicarboxylic acid component as described above. Therefore, when the line speed in post-processing process is raised by the improvement of productivity efficiency, it can be considered that chipping of an application layer and falling of a particle generate | occur | produce. As a result of earnestly examining the inventors, the present inventors have found that by using a long-chain dicarboxylic acid component and / or a diol component as a component of the polyester resin, it exhibits remarkable chipping resistance of the coating layer. .

That is, the polyester resin used for the coating layer of this invention is naphthalenedicarboxylic acid as a acid component, the dicarboxylic acid component represented by following formula (1), and / or the diol component represented by following formula (2). It includes.

(1) HOOC- (CH ₂ ) _n -COOH (wherein n is an integer of 4≤n≤10)

(2) HO- (CH ₂ ) _n -OH (wherein n is an integer of 4≤n≤10)

Thus, by containing the acid component and / or diol component which have a carbon component of a specific length, it provides flexibility to a polyester resin and is easy to hold | maintain, even if it is a comparatively large particle, chipping of a coating layer and particle | grains The fall of can be suppressed remarkably. On the other hand, when n is less than 4, such an effect is not acquired and chipping property of an application layer may arise. Moreover, when n exceeds 10, the refractive index which a polyester resin shows may fall, and the suppression effect of the iris color under a fluorescent lamp may become inadequate. Moreover, 9 or less are more preferable and, as for the upper limit of said n, 8 or less are more preferable.

Here, chipping resistance of an application layer can be measured by the measuring method mentioned later. That is, in the chipping resistance test of the coating layer mentioned later, it is preferable that it is below the grade which can confirm a powder fall slightly with a place on a black mount, More preferably, a powder fall on a black mount cannot be confirmed. (That is, there is no powder fall in the chipping resistance test of the coating layer described later). The degree of powder fall can be confirmed by visual observation, fluorescence X-ray analysis, XMA, ESCA, and the like. Here, the absence of powder fall means that more specifically, when the powder is an inorganic particle, the inorganic particle on the earth is below the detection limit in the fluorescent X-ray analysis.

According to the above aspect, the present invention controls the iris color under a fluorescent lamp while maintaining adhesion to the hard coat layer and adhesion under high temperature and high humidity, and further, excellent chipping resistance of the coating layer. Have In addition, the structure of this invention is described in detail below.

In this invention, it is necessary to contain a polyester resin in an application layer, and it is necessary to contain naphthalenedicarboxylic acid as an acid component of the said polyester resin. By containing naphthalenedicarboxylic acid, refractive index increases and it becomes easy to control iris-color in under fluorescent lamp. In addition, the heat and moisture resistance can be improved.

As such naphthalenedicarboxylic acid, 2, 6- naphthalenedicarboxylic acid is preferable. The molar ratio of the naphthalenedicarboxylic acid in the polyester resin is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, even more preferably 60 mol% or more as an acid component. Do. Moreover, 90 mol% or less is preferable as an acid component, and, as for the ratio of the said naphthalenedicarboxylic acid in a polyester resin, 85 mol% or less is more preferable, 80 mol% or less is further more preferable. Although the ratio of the said naphthalenedicarboxylic acid in a polyester resin is adjusted suitably so that the refractive index of an application layer with particle | grains A may be in the above-mentioned range, when it is less than 20 mol%, the addition amount of particle | grains A increases and adhesiveness falls There is. Moreover, when it exceeds 90 mol%, the adhesiveness of resin may fall.

Moreover, it is necessary for the polyester resin of this invention to contain at least naphthalenedicarboxylic acid, the dicarboxylic acid component of following formula (1), and / or the diol component of following formula (2) as an acid component. The dicarboxylic acid component of the following formula (1) and / or the diol component of the following formula (2) in the polyester resin is preferably 10 mol% or more, more preferably 15 mol% or more, further 20 mol% or more desirable. Moreover, 70 mol% or less is preferable, as for the dicarboxylic acid component of following formula (1) and / or the diol component of following formula (2) in the said polyester resin, 60 mol% or less is more preferable, 50 mol% The following is more preferable. If the dicarboxylic acid component of the following formula (1) and / or the diol component of the following formula (2) in a polyester resin is less than 10 mol%, chipping resistance of an application layer will deteriorate depending on the ratio of another component. In some cases, if it is 70 mol% or more, the refractive index is lowered, and the effect of suppressing the iris color under the fluorescent lamp may be insufficient. In addition, about the structural component of a polyester resin, it can carry out also suitably by NMR and a mass analyzer.

(1) HOOC- (CH ₂ ) _n -COOH (wherein n is an integer of 4≤n≤10)

(2) HO- (CH ₂ ) _n -OH (wherein n is an integer of 4≤n≤10)

As dicarboxylic acid component of Formula (1), adipic acid, sebacic acid, azelaic acid, etc. are mentioned. Moreover, butanediol, hexanediol, etc. are mentioned as a diol component of Formula (2).

The polyester resin is water or an aqueous solvent containing less than 50% by mass of a water-soluble organic solvent (e.g., alcohol, alkyl cellosolve, ketone, or ether), or an organic solvent (e.g., toluene, acetic acid). Dissolved or dispersed in ethyl, etc.) may be used.

When a polyester resin is used as an aqueous coating liquid, a water-soluble or water-dispersible polyester resin is used. For such water solubilization or water oxidation, a compound containing a sulfonate group or a compound containing a carboxylate group is copolymerized. It is preferable to make it.

Moreover, as long as it is a range which shows the effect of this invention, as an acid component in a polyester resin, terephthalic acid, isophthalic acid, a phthalic acid, an inorganic phthalic acid, 14-cyclohexanedicarboxylic acid, trimellitic acid, a pyromellitic acid, a dimer acid , 5-sodium sulfoisophthalic acid, 4-sodium sulfonaphthalene-2,7-dicarboxylic acid, or the like may be used. Examples of the diol component include ethylene glycol, propane glycol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanedimethanol, xylene glycol, and ethylene oxide adducts of bisphenol A.

It is preferable to contain the said polyester resin in 30 mass% or more and 90 mass% or less in all solid components in an application layer. More preferably, they are 40% mass% or more and 80 mass% or less. When there is much content of a polyester resin, adhesiveness with the hard-coat layer under high temperature, high humidity falls, On the contrary, when there is little content, adhesiveness with a polyester film under normal temperature and high temperature, high humidity falls.

In this invention, in order to form a crosslinked structure in an application layer, you may contain a crosslinking agent. By containing a crosslinking agent, it becomes possible to further improve adhesiveness under high temperature, high humidity. Moreover, since solvent resistance with respect to a hard-coat coating liquid solvent improves by introduce | transducing a crosslinked structure into a coating layer, expression of the interference fringe by the change of a coating layer thickness can be suppressed more preferable. Examples of the crosslinking agent include urea, epoxy, melamine, isocyanate, oxazoline, carbodiimide and the like. Among these, melamine type, isocyanate type, oxazoline type, and carbodiimide type are preferred from the stability of the coating solution with time and the effect of improving the adhesion under high temperature and high humidity treatment. In addition, in order to accelerate the crosslinking reaction, a catalyst or the like is suitably used as necessary.

As content in the coating layer of a crosslinking agent, 5 mass% or more and 50 mass% or less are preferable in all solid components. More preferably, they are 10 mass% or more and 30 mass% or less. When there is little, the intensity | strength of resin of a coating layer falls, adhesiveness under high temperature, high humidity falls, and in many cases, flexibility of resin of a coating layer falls, and adhesiveness under constant temperature and high temperature, high humidity falls.

In the present invention, it is necessary to contain metal oxide particles (particles A) having a refractive index of 1.7 or more and 3.0 or less in the coating layer. Examples of such metal oxides include TiO ₂ (refractive index 2.7), ZnO (refractive index 2.0), Sb ₂ O ₃ (refractive index 1.9), SnO ₂ (refractive index 2.1), ZrO ₂ (refractive index 2.4), Nb ₂ O ₅ (refractive index 2.3), CeO ₂ (refractive index 2.2), Ta ₂ O ₅ (refractive index 2.1), Y ₂ O ₃ (refractive index 1.8), La ₂ O ₃ (refractive index 1.9), In ₂ O ₃ (refractive index 2.0), Cr ₂ O ₃ (refractive index 2.5) And composite oxides containing these metal atoms. The coating layer of this invention contains these metal oxides 1 type (s) or 2 or more types. If the refractive index of a metal oxide particle is 1.7 or more, it is preferable at the point which adjusts the refractive index of an application layer in the said range. Moreover, when the refractive index of a metal oxide particle is 3.0 or less, it is preferable at the point which maintains transparency of a film.

As content in the coating layer of metal oxide particle, it is preferable to control by the relationship between the refractive index of the metal oxide particle to be used, and the refractive index of the hard-coat layer to apply, Specifically, it is 2 mass% or more in all the solid components, More preferably, 5 mass% or more and 70 mass% or less are preferable. As a minimum of content of a metal oxide particle, 7 mass% or more is more preferable, and 8 mass% or more is more preferable. Moreover, as an upper limit of content of a metal oxide particle, 50 mass% or less is more preferable, 30 mass% or less is more preferable, 20 mass% or less is more preferable, 15 mass% or less is especially preferable. According to the refractive index of a hard-coat layer, metal oxide particle is added within the said range, and the refractive index of an application layer is adjusted in the range of 1.5-1.7, Preferably it is 1.6-1.7. When content of a metal oxide particle is less than 2 mass% or less than 5 mass%, it may become difficult to adjust the refractive index of an application layer to the said range. Moreover, when content of a metal oxide particle exceeds 70 mass%, since the adhesiveness of a coating layer may fall, it is unpreferable. Although the average particle diameter of a metal oxide particle is not specifically limited, It is preferable in it being 1-100 nm from the point which maintains transparency of a film.

In the present invention, it is necessary to contain particles (particles B) having an average particle diameter of 200 nm or more and 700 nm or less in the coating layer. Particle B is (1) silica, kaolinite, talc, hard calcium carbonate, heavy calcium carbonate, zeolite, alumina, barium sulfate, carbon black, zinc oxide, zinc sulfate, zinc carbonate, titanium dioxide, satin white, aluminum silicate, diatomaceous earth, Inorganic particles such as calcium silicate, aluminum hydroxide, hydrous halide, magnesium carbonate, magnesium hydroxide, (2) acrylic or methacryl, vinyl chloride, vinyl acetate, nylon, styrene / acrylic, styrene / butadiene, polystyrene / acrylic , Polystyrene / isoprene, polystyrene / isoprene, methyl methacrylate / butyl methacrylate, melamine, polycarbonate, urea, epoxy, urethane, phenol, diallyl phthalate, polyester, etc. Organic particle | grains are mentioned.

It is preferable that the said particle | grains (particle B) is 200-700 nm in average particle diameter. When the particle size is small, the unevenness of the interface between the coating layer and the hard coat layer is small, the scattering effect is reduced, and the effect of suppressing the iris-like color under the fluorescent lamp is likely to be insufficient. When large, transparency of an application layer may worsen.

It is preferable that the particle (particle B) has a spherical shape that is difficult to aggregate. When the particles aggregate, the effect of scattering decreases, and the effect of suppressing the iris-like color under the back tends to be insufficient, and there may be optical defects. In addition, in view of exerting the light scattering effect of the particles, the spherical particles are considered to be preferable. In addition, the particle B is preferably colorless and transparent from the viewpoint of maintaining the transparency of the film.

The average particle diameter of the particle | grains in the coating layer of this invention image | photographs the cross section of an easily adhesive film at 120,000 times magnification using a transmission electron microscope (TEM), and the largest diameter of ten or more particle | grains which exist in the cross section of a coating layer. Can be measured and their average value can be obtained. In that case, in order to remove the foreign material and the particle | grains of particle | grains A, it is preferable to select | require and average an average particle | grain of 100 nm or more.

As content in the coating layer of particle | grain B, 0.5 mass% or more and 5 mass% or less are preferable in all the solid components. As an upper limit of content in the coating layer of particle | grain B, 4 mass% or less is more preferable, 3 mass% or less is more preferable, and 2 mass% or less is especially preferable. In a small case, the scattering effect is reduced, and the effect of suppressing the iris color under the fluorescent lamp tends to be insufficient. In many cases, not only the transparency of an application layer worsens, but film | membrane strength falls.

It is also possible to make a coating layer contain surfactant for the purpose of the improvement of the leveling property at the time of application | coating, and the defoaming of a coating liquid. The surfactant may be any one of cationic, anionic and nonionic, but a silicone, acetylene glycol or fluorine-based surfactant is preferable. It is preferable to contain these surfactant in an application layer in the range which does not impair the suppression effect of adhesive iris color, or adhesiveness under a fluorescent lamp.

In order to impart different functionality to the coating layer, various additives may be contained within a range that does not impair the suppression effect or adhesion of the color of the iris under the fluorescent lamp. As said additive, a fluorescent dye, a fluorescent brightener, a plasticizer, a ultraviolet absorber, a pigment dispersant, an inhibitor, an antifoamer, a preservative, etc. are mentioned, for example.

In this invention, the method of apply | coating and drying the coating liquid containing a solvent, particle | grain, and resin to a polyester film as a method of providing a coating layer on a polyester film is mentioned. Examples of the solvent include an organic solvent such as toluene, water, or a mixed system of water and a water-soluble organic solvent. Preferably, a water-soluble organic solvent is mixed with water alone or water from the viewpoint of environmental problems.

(Laminated Polyester Film for Optics)

The optical laminated polyester film of this invention is obtained by providing the hard coat layer which consists of an electron beam or an ultraviolet curable acrylic resin or a siloxane-type thermosetting resin in the application layer of the polyester film mentioned above.

An acrylic resin cured by an electron beam or ultraviolet rays, having an acrylate-based functional group, for example, a relatively low molecular weight polyester resin, a polyether resin, an acrylic resin, an epoxy resin, a urethane resin, an alkyd resin, and a spiroacetal Oligomers or prepolymers such as (meth) acrylates of polyfunctional compounds such as resins, polybutadiene resins, polythiolpolyene resins, and polyhydric alcohols, and ethyl (meth) acrylates, ethylhexyl (meth) acrylates, and styrene as reactive diluents. Monofunctional monomers and polyfunctional monomers such as methyl styrene and N-vinylpyrrolidone, for example, trimethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acryl Latene, diethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaeryth The thing containing a lititol hexa (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, etc. can be used.

However, in the case of electron beam or ultraviolet curable resin, acetophenones, benzophenones, Michler's benzoyl benzoate, (alpha)-amyl oxime ester, tetramethyl thiuram monosulfide, thioxanthones are mentioned as a photoinitiator in resin mentioned above. As a photosensitizer, n-butylamine, triethylamine, tri-n-butylphosphine, etc. can be mixed and used.

In addition, the siloxane-based thermosetting resin can be produced by hydrolyzing and condensing a single or two or more types of organosilane compounds under an acid or base catalyst. In particular, in the case of low reflectance, it is better to mix one or more kinds of fluorosilane compounds, and to perform hydrolysis and condensation reaction in the improvement of low refractive index, pollution resistance, etc.

(Production of an easily adhesive polyester film for optical)

Although the polyethylene terephthalate (it abbreviates as PET) film is demonstrated to an example about the manufacturing method of the optically easy adhesive polyester film of this invention, it is not limited to these naturally.

After sufficiently drying the PET resin in vacuum, the extruder is supplied to an extruder, and the melted PET resin at about 280 ° C. is melt-extruded in a sheet form on a rotary cooling roll from a T die, and cooled and solidified by electrostatic application to obtain an unstretched PET sheet. A single layer structure may be sufficient as the said unstretched PET sheet, and the multilayer structure by a coextrusion method may be sufficient as it. Moreover, it is preferable not to contain inert particle substantially in PET resin. Moreover, in the case of a multilayer structure, the two or three layer structure which does not contain inert particle substantially in an intermediate | middle layer and contains only inert particle only in outermost layer is compatible with transparency and workability, and is preferable.

The obtained unstretched PET sheet is stretched at 2.5 to 5.0 times in the longitudinal direction with a roll heated at 80 to 120 ° C to obtain a uniaxially stretched PET film. Moreover, the edge part of a film is gripped with a clip, it guides to the hot air zone heated at 70-140 degreeC, and it extends | stretches 2.5-5.0 times in the width direction. Subsequently, it is led to a heat treatment zone of 160 to 240 ° C, heat treatment is performed for 1 to 60 seconds, and crystal orientation is completed.

In any step of this film manufacturing process, a coating liquid is applied to at least one side of the PET film to form the coating layer. Even if it forms in an application layer on both surfaces of a PET film, there is no problem in particular. It is preferable that solid content concentration of the resin composition in a coating liquid is 2 to 35 weight%, Especially preferably, it is 4 to 15 weight%.

The method for apply | coating this coating liquid to PET film can use a well-known arbitrary method. For example, reverse roll coating method, gravure coating method, kiss coating method, die coater method, roll brush method, spray coating method, air knife coating method, wire bar coating method, pipe doctor method, impregnation coating method, curtain coating method Etc. can be mentioned. These methods are coated alone or in combination.

In this invention, after apply | coating and drying the said coating liquid to the PET film after unstretched or uniaxial stretching, it is extended | stretched in at least one axial direction, and is formed by performing heat processing subsequently.

In this invention, it is preferable that the thickness of the coating layer finally obtained is 20-350 nm, and the application amount after drying is 0.02-0.5 g / m <2>. If the coating amount of the coating layer is less than 0.02 g / m 2, not only the effect on the adhesiveness is almost eliminated, but also the suppression of the iris-like color under the fluorescent lamp tends to be insufficient. On the other hand, when application amount exceeds 0.5 g / m <2>, the suppression effect of the iris-like color under fluorescent lamps will become inadequate easily.

The coating layer of the easily-adhesive polyester film for optics obtained by this invention has favorable adhesiveness with respect to the hard-coat layer which consists of an electron beam or an ultraviolet curable acrylic resin or a siloxane-type thermosetting resin. In addition to the optical use, good adhesive strength is obtained. Specifically, an adhesive such as a photosensitive layer, a diazo photosensitive layer, a mat layer, a magnetic layer, an inkjet ink receiving layer, a hard coat layer, an ultraviolet curable resin, a thermosetting resin, a printing ink or a UV ink, a dry laminate or an extrusion laminate, a metal or Thin film layers obtained by vacuum deposition of inorganic substances or their oxides, electron beam deposition, sputtering, ion plating, CVD, plasma polymerization, etc., organic barrier layers, and the like can be given.

(Production of laminated polyester film for optics)

Although the PET film is demonstrated as an example about the manufacturing method of the optical laminated polyester film of this invention, it is not limited to these naturally.

The said electron beam or an ultraviolet curable acrylic resin or a siloxane-type thermosetting resin is apply | coated to the application layer surface of the easily-adhesive polyester film for optics mentioned above. When the coating layers are provided on both surfaces, they are applied to at least one coating layer surface. Although the coating liquid does not need to be specifically diluted, even if it dilutes with the organic solvent as needed, such as the viscosity of a coating liquid, wettability, coating film thickness, there is no problem in particular. After apply | coating the said coating liquid to the above-mentioned film, it is made to dry as needed, and a coating layer hardens an application layer by electron beam or ultraviolet irradiation and heating according to the hardening conditions of a coating liquid, and forms a hard-coat layer.

In this invention, it is preferable that the thickness of a hard-coat layer is 1-15 micrometers. If the thickness of the hard coat layer is less than 1 µm, the effect on chemical resistance, scratch resistance, antifouling property, etc. as the hard coat layer is almost eliminated. On the other hand, when the thickness exceeds 15 µm, the flexibility of the hard coat layer is lowered, and the possibility of cracking or the like increases.

Although the laminated polyester film for optics obtained by this invention can be used for a wide range of uses, it can be set as a favorable antireflection film especially by further providing an antireflection layer in an upper layer. Formation of such an antireflection layer is performed by providing a single refractive index layer of inorganic materials such as high refractive index ZnO, TiO ₂ , CeO ₂ , SnO ₂ , ZrO ₂ , or low refractive index MgF ₂ , SiO ₂ , or a metal material. These layers are formed in a single layer or multiple layers of a coating layer made of a resin composition containing an inorganic material, a metal material, or the like having a high refractive index or a low refractive index, such as vapor deposition, sputtering, plasma CVD, or the like.

Example

Next, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited to a following example naturally. In addition, the evaluation method used by this invention is as follows.

(1) intrinsic viscosity

According to JIS K 7367-5, it measured at 30 degreeC using the mixed solvent of phenol (60 mass%) and 1,1,2,2- tetrachloroethane (40 mass%) as a solvent.

(2) refractive index

The refractive index of the hard-coat layer measured about the film | membrane which hardened | cured each resin used for the hard-coat layer using the Abbe refractive index meter based on JISK71142.

The refractive index of particle | grains A suspended the particle | grains A dried at 90 degreeC in various 25 degreeC liquids from which refractive index differs, and measured the refractive index of the liquid which a suspension looks the most transparent with the Abbe refractometer.

(3) Average particle size

A sample of the optically laminated polyester film was embedded in visible light curable resin (D-800, manufactured by Nippon Electron Co., Ltd.), and then exposed to visible light at room temperature to cure. From the obtained embedding block, ultra-thin sections having a thickness of about 70 to 100 nm were prepared using ultra microtomes equipped with diamond knives, and dyed in ruthenium tetraoxide vapor for 30 minutes. This dyed ultrathin section was observed using a transmission electron microscope (manufactured by Nippon Electronics Co., Ltd., TEM2010) to observe a cross section of the hard coat layer, and photographed. The magnification of the photograph is appropriately set in the range of 10,000 to 100,000 times. In this embodiment, the magnification was 80,000 times (acceleration voltage 200 kv). When the average particle diameter of the particle | grains A was calculated | required, 10 or more particle | grains whose particle diameter is about 100 nm or more were selected from the electron micrograph, the maximum diameter of those particle | grains was measured, and the average value was calculated | required. This is for the purpose of excluding the particle | grains whose particle | grains A, the foreign material, etc. which are not the particle | grains B of this application clearly are small.

(4) Improvement of interference nonuniformity (iris image color)

The laminated polyester film for optics was cut out by the area of 10 cm (film width direction) x 15 cm (film longitudinal direction), and the sample film was produced. On the opposite side to the hard coat layer of the obtained sample film, black gloss tape (Nitto Electric Co., Ltd., vinyl tape No 21; black) was stuck together. Positional relationship (distance from the light source) where the hard coat surface of this sample film is the top surface, and the three-wavelength main white (National Paruk, F.L 15EX-N 15W) is used as a light source and the reflection is most visible to the naked eye from the top. 40-60 cm and the angle of 15-45 degrees with respect to the repair of the film surface).

The results observed with the naked eye are ranked according to the following criteria. In addition, observation is performed by five people who are familiar with the evaluation, and makes the most rank the evaluation rank. In the case of equal numbers in two ranks, the center of the rank divided into three was adopted. For example, if ◎ and ○ are each 2 and △ is 1, ○ is 1, ◎ is 1, and ○ and △ are each 2, ○, ◎ and △ are each 2 and ○ is 1 In each case, o is adopted.

◎: The iris image color is not seen even from observation from all angles

○: depending on the angle slightly iris color is visible

(Triangle | delta): Slightly iris image color is observed.

X: A certain iris image color is observed.

(5) adhesive

In the laminated polyester film for optics, 100 grid | lattice cut lines which penetrate a hard-coat layer and reach | attach a base film are drawn on the hard-coat layer surface using the cutter guide of 2 mm gap | interval. Subsequently, a cellophane adhesive tape (Nichiban Co., Ltd. No. 405; 24 mm width) was affixed to the grid-shaped cut line surface, and it rubbed with an eraser and was made to fully adhere. Thereafter, the cellophane adhesive tape is vertically removed from the hard coat layer surface of the optical laminated polyester film, and the number of grids peeled from the hard coat layer surface of the optical laminated polyester film is visually counted, and the hard coat layer is obtained from the following formula. And the adhesiveness of the base film. In addition, the part which peeled partially in the grid was also counted as the peeled grid, and the rank was divided according to the following reference | standard.

Adhesion (%) = (1-number of stripped grids / 100) × 100

◎: 100%

○: 99-90%

△: 90-70%

×: 69 ~ 0%

(6) heat and moisture resistance

The laminated polyester film for optics was left to stand in 60 degreeC, 95 RH% of environment for 500 hours in the high temperature, high humidity tank, Then, the laminated polyester film for optics was taken out and left to stand at room temperature and room temperature for 12 hours. Then, the adhesiveness of a hard-coat layer and a base film was calculated | required in the same way as said (5), and rank division was performed based on the following reference | standard.

◎: 100%

○: 99-90%

△: 90-70%

×: 69 ~ 0%

(7) chipping resistance of coating layer

3 cm (film width direction) x 20 cm (film length direction) of the optically easy-adhesive polyester film was attached to the friction fastness tester (RT-200, Daisei Scientific Co., Ltd. product), and the weight (300 g) was suspended Using a aluminum foil (thickness: 80 µm, arithmetic mean surface roughness: 0.03 µm) at the contact portion of the load head (2 cm × 2 cm, 200 g) and the sample film, the distance of 10 cm was 10 reciprocating at a speed of 1 round trip 20 seconds. I was. The sample film obtained on the assay board was raised and visually confirmed whether the powder fell off.

(Double-circle): It cannot confirm that a powder fall on the black earth.

(Circle): It can be seen that some powder falls with a place on a black site.

(Triangle | delta): It can be seen that a little powder fall on the black earth as a whole.

X: Powder fall off can be confirmed reliably on black earth.

In addition, the said arithmetic mean surface roughness is the value measured on condition of the following using the non-contact surface shape measurement system (Vert Scan R550H-M100).

(Measuring conditions)

Measurement mode: WAVE mode

? Objective lens: 50 times

0.5 × Tube lens

Measuring area 187 × 139 ㎛

(8) Total light transmittance of the easily-adhesive polyester film for optics

The total light transmittance of the obtained easy-adhesive polyester film for optics was measured based on JISK7105 "Optical characteristic test method of plastic."

(Polymerization of Polyester Resin)

In a stainless steel autoclave equipped with a stirrer, a thermometer, and a partial reflux cooler, 302.9 parts by mass of dimethyl 2,6-naphthalenedicarboxylic acid, 47.4 parts by mass of dimethyl-5-sodium sulfoisophthalate, and 198.6 mass of ethylene glycol Part 1, 118.2 parts by mass of 1,6-hexanediol and 0.4 part by mass of tetra-n-butyl titanate were added, and a transesterification reaction was carried out from 160 ° C to 220 ° C over 4 hours. Furthermore, 121.4 weight part of sebacic acid was added, and esterification reaction was performed. Subsequently, it heated up to 255 degreeC, and after pressure-reducing the reaction system gradually, it was made to react for 1 hour and 30 minutes under reduced pressure of 30 Pa, and co-polyester resin (A-1) was obtained. The obtained copolyester resin was pale yellow transparent.

In the same manner, copolyester resins (A-2) to (A-11) of different compositions were obtained. About these co-polyester resin, the result of the composition and the weight average molecular weight measured by <^1> H-NMR is shown in Table 1.

(Adjustment of aqueous dispersion of polyester)

20 mass parts of polyester resins (A-1) and 15 mass parts of ethylene glycol t-butyl ether were put into the reactor provided with the stirrer, the thermometer, and the reflux apparatus, and it heated and stirred at 110 degreeC, and melt | dissolved resin. After the resin was completely dissolved, 65 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 prepare an aqueous dispersion (B-1) of milky polyester having a solid content of 20% by mass. Similarly, water dispersion is produced using polyester resin (A-2)-(A-12) instead of polyester resin (A-1), and water dispersion (B-2)-(B-12) It was.

(Polymerization of Block Polyisocyanate Crosslinking Agent)

100 parts by mass of a polyisocyanate compound (Asahi Kasei Chemicals, Duranate TPA) having an isocyanurate structure using hexamethylene diisocyanate as a raw material in a flask equipped with a stirrer, a thermometer and a reflux condenser, propylene glycol monomethyl ether 55 parts by mass of acetate and 30 parts by mass of polyethylene glycol monomethyl ether (average molecular weight 750) were added, and the mixture was maintained at 70 ° C. for 4 hours under a nitrogen atmosphere. Thereafter, the reaction solution temperature was lowered to 50 ° C, and 47 parts by mass of methyl ethyl ketooxime was added dropwise. The infrared spectrum of the reaction solution was measured to confirm that absorption of the isocyanate group was lost, thereby obtaining a blocked polyisocyanate aqueous dispersion (C) having a solid content of 75% by mass.

(Polymerization of oxazoline-based crosslinking agent)

In a flask equipped with a thermometer, a nitrogen gas introduction tube, a reflux cooler, a dropping funnel, and a stirrer, 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 (2- 4 parts by mass of amidinopropane) -dihydrochloride) was added. On the other hand, 16 mass parts of 2-isopropenyl 2-oxazoline as a polymerizable unsaturated monomer which has an oxazoline group in a dropping funnel, methoxy polyethyleneglycol acrylate (average number of moles of ethylene glycol-9 mol, Shinnakamura chemical | chemistry) Manufacture) 32 mass parts and the mixture of 32 mass parts of methyl methacrylates were thrown in, and it dripped at 70 degreeC under nitrogen atmosphere over 1 hour. After completion of the dropwise addition, the reaction solution was stirred for 9 hours and cooled to obtain a water-soluble resin (D) having an oxazoline group having a solid content of 40% by mass.

(Polymerization of Carbodiimide-Based Crosslinking Agent)

168 parts by mass of hexamethylene diisocyanate and 220 parts by mass of polyethylene glycol monomethyl ether (M400, average molecular weight 400) were added to a flask equipped with a stirrer, a thermometer, and a reflux condenser, followed by stirring at 120 ° C for 1 hour. 26 parts by mass of 4'-dicyclohexylmethane diisocyanate and 3.8 parts by mass of 2-methyl-1-phenyl-2-phosphorene-1-oxide (2% by weight based on total isocyanate) as a carbodiimidization catalyst And it stirred at 185 degreeC under nitrogen stream further for 5 hours. The infrared spectrum of the reaction solution was measured, and it was confirmed that absorption at wavelengths 2200 to 2300 cm ^-1 was lost. It cooled to 60 degreeC, added 567 mass parts of ion-exchange water, and obtained the carbodiimide water-soluble resin (E) of 40 mass% of solid content.

Example 1

(1) Adjustment of coating liquid

The following ceramics were mixed to prepare a coating liquid. Particle A is SnO ₂ having a refractive index of 2.1 and particle B is silica particles having an average primary particle size of about 500 nm.

40.16 mass% of water

Isopropanol 30.00 mass%

Polyester aqueous dispersion (B-1) 18.19 mass%

Block polyisocyanate aqueous dispersion (C) 2.08 mass%

Particle A 9.37 Mass%

(Daki Chemical Cerames S-8, solid content concentration 8% by mass)

Particle B 0.17 mass%

(Nippon Shokubai Shihosuta KEW50, solid content concentration 15% by mass)

0.03 mass% of silicone type surfactant

(100% solids concentration)

(2) Preparation of an easily adhesive polyester film for optics

As a film raw material polymer, PET resin pellet which has an intrinsic viscosity of 0.62 dl / g and does not contain particle | grains substantially was dried at 135 degreeC under reduced pressure of 133 Pa for 6 hours. Then, it supplied to the extruder, melt-extruded in the sheet form at about 280 degreeC, and solidified rapidly by the electrostatic application method on the rotating cooling metal roll maintained at the surface temperature of 20 degreeC, and obtained the unstretched PET sheet.

The unstretched PET sheet was heated to 100 ° C. with a heated roll group and an infrared heater, and then stretched 3.5 times in the longitudinal direction with a roll group having a circumferential speed difference to obtain a uniaxially stretched PET film.

Subsequently, after apply | coating the said coating liquid to the single side | surface of PET film by the roll coat method, it dried at 80 degreeC for 20 second. In addition, it adjusted so that the application amount after final (after biaxial stretching) drying might be 0.15 g / m <2>. Subsequently, with a tenter, it extended | stretched 4.0 times in the width direction at 120 degreeC, heated for 0.5 second at 230 degreeC in the state which fixed the length of the width direction of the film, and further relaxed | treated in the width direction of 3% for 10 second at 230 degreeC. Was carried out to obtain an easily adhesive polyester film for optics having a thickness of 100 µm. When observed with the electron microscope, the thickness of the coating layer was 120 nm. The evaluation results are shown in Table 2.

(3) Production of optically laminated polyester film

The coating liquid (C-1) for hard-coat layer formation of the following composition is apply | coated to the application layer surface of the said easily adhesive polyester film for optics using # 10 wire bar, it is dried at 70 degreeC for 1 minute, and a solvent is removed. It was. Subsequently, 300 mJ / cm <2> of ultraviolet-rays were irradiated to the film which apply | coated the hard-coat layer using the high pressure mercury lamp, and the optical laminated polyester film which has a hard-coat layer of thickness 5micrometer was obtained. The refractive index of the hard coat layer was 1.55.

Coating liquid for hard coat layer formation (C-1)

Isopropanol 48.47 mass%

Dipentaerythritol hexaacrylate 21.25 mass%

(Shin-Nakamura Chemical A-DPH)

Polyethylene diacrylate 5.67 mass%

(Shin-Nakamura Chemical A-400)

ZrO ₂ sol 23.61 mass%

(Nissan Chemical Industries, Ltd. OZ-30M, solid content concentration 30% by mass)

1.00 mass% of photopolymerization initiator

(Irucure 184 made by Ciba specialty chemicals company)

Comparative Example 1

Except having changed the polyester aqueous dispersion into B-10, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Comparative Example 2

An optically laminated polyester film was obtained in the same manner as in Example 1 except that Particle A was changed to SiO ₂ (Nissan Chemical Industries, Snowtex ZL, solid content concentration: 40 mass%) having a refractive index of 1.46.

Comparative Example 3

Except having excluded particle B, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Comparative Example 4

Except having changed particle B into the coating liquid for hard-coat layer formation (C-2), it carried out similarly to Example 1, and obtained the laminated polyester film for optics. The refractive index of the hard coat layer was 1.55.

Coating liquid for hard coat layer formation (C-2)

Methyl ethyl ketone 39.00 mass%

Toluene 9.47 mass%

Dipentaerythritol hexaacrylate 21.25 mass%

(Shin-Nakamura Chemical A-DPH)

Polyethylene diacrylate 5.67 mass%

(Shin-Nakamura Chemical A-400)

SnO ₂ sol 23.61 mass%

(Isahara Industrial FSS-10T, solid content concentration 30% by mass)

1.00 mass% of photopolymerization initiator

(Irucure 184 made by Ciba specialty chemicals company)

Comparative Example 5

An optically laminated polyester film was obtained in the same manner as in Example 1 except that the particle B was changed to silica particles having an average particle diameter of 100 nm (Nissan Chemical Industries' Snowtex ZL, solid content concentration: 40 mass%).

Comparative Example 6

The laminated polyester film for optics was obtained like Example 1 except having changed particle B into the organic particle | grains (Eposuta MS by Nippon Shokubai) of 2000 nm of average particle diameters.

Comparative Example 7

The laminated polyester film for optics was obtained like Example 1 except having changed the polyester aqueous dispersion into B-11.

Comparative Example 8

The laminated polyester film for optics was obtained like Example 1 except having changed the polyester aqueous dispersion into B-12.

Example 2

Except having changed the coating liquid below, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

44.54 mass% of water

Isopropanol 30.00 mass%

Polyester water dispersion (B-1) 12.21 mass%

Block polyisocyanate aqueous dispersion (C) 3.67 mass%

Particle A 9.38 Mass%

(Dakihaha Cerames S-8, solid content concentration 8% by mass)

Particle B 0.17 mass%

(Nippon Shokubai Shihosuta KEW50, solid content concentration 15% by mass)

0.03 mass% of silicone type surfactant

(100 mass% of solid content concentration)

Example 3

Except having changed the coating liquid below, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

37.29 mass% of water

Isopropanol 30.00 mass%

Polyester water dispersion (B-1) 22.09 mass%

1.04 mass% of blocked polyisocyanate aqueous dispersions (C)

Particle A 9.38 Mass%

(Daki Chemical Cerames S-8, solid content concentration 8% by mass)

Particle B 0.17 mass%

(Nippon Shokubai Shihosuta KEW50, solid content concentration 15% by mass)

0.03 mass% of silicone type surfactant

(100 mass% of solid content concentration)

Example 4

Except having changed the coating liquid below, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

35.76 mass% of water

Isopropanol 30.00 mass%

Polyester water dispersion (B-1) 24.17 mass%

Block polyisocyanate aqueous dispersion (C) 0.49 mass%

Particle A 9.38 Mass%

(Daki Chemical Cerames S-8, solid content concentration 8% by mass)

Particle B 0.17 mass%

(Nippon Shokubai Shihosuta KEW50, solid content concentration 15% by mass)

0.03 mass% of silicone type surfactant

(100 mass% of solid content concentration)

Example 5

An optically laminated polyester film was obtained in the same manner as in Example 1 except that the particle B was changed to silica particles having an average particle diameter of 230 nm (fusochemical industrial quattron PL-20, solid content concentration of 24 mass%).

Example 6

The laminated polyester film for optics was obtained like Example 1 except having changed particle B into the acryl particle (Gantz Chemical make Gantzpal PM-030, solid content concentration 41 mass%) of an average particle diameter of 300 nm.

Example 7

An optically laminated polyester film was obtained in the same manner as in Example 1 except that the particle B was changed to silica particles having an average particle diameter of 450 nm (MP4540M manufactured by Nissan Chemical Industries, 40 mass% of solid content concentration).

Example 8

The laminated polyester film for optics was obtained like Example 1 except having changed particle B into the crosslinked polystyrene particle (Grossdell 207-S by Mitsui Chemicals, 53 mass% of solid content concentration) of 700 nm of average particle diameters.

Example 9

Particles A were ZrO ₂ with a refractive index of 2.4 (ZR-40BL manufactured by Nissan Chemical Industries, 40 mass% of solid content), and particles B were silica particles having an average particle diameter of 230 nm (Quottron PL-20 manufactured by Fuso Chemical Industry, 24 mass% of solid content). Except having changed into), it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 10

Particles A were ZrO ₂ with a refractive index of 2.4 (ZR-40BL manufactured by Nissan Chemical Industries, 40 mass% of solid content), and particles B were acrylic particles having an average particle diameter of 300 nm (Gantz Pearl PM-030 manufactured by Gantz Chemicals, 41 mass% of solid content). Except having changed into, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 11

Particle A was changed to ZrO ₂ with a refractive index of 2.4 (ZR-40BL manufactured by Nissan Chemical Industry, 40 mass% of solid content concentration), and particle B was changed to silica particles having a mean particle size of 450 nm (MP4540M manufactured by Nissan Chemical Industry, 40 mass% solid content). Except having been carried out similarly to Example 1, the optical laminated polyester film was obtained.

Example 12

A refractive index of the particles 2.4 ZrO ₂ (manufactured by Nissan Chemical Industries ZR-40BL, a solid concentration of 40 mass%), except that changes in the same manner as Example 1 to obtain an optical laminated polyester film.

Example 13

Particles A were ZrO ₂ with a refractive index of 2.4 (ZR-40BL manufactured by Nissan Chemical Industries, 40 mass% of solids concentration), and particles B were crosslinked polystyrene particles having an average particle diameter of 700 nm (Grossdel 207-S manufactured by Mitsui Chemicals, 53 mass% of solids concentration). Except having changed into), it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 14

Particle A was TiO ₂ having a refractive index of 2.7 (TTO-W-5 manufactured by Ishihara Industries, 30 mass% of solid content concentration), and silica particle (Quottron PL-20 manufactured by Fuso Chemical Industry, 24 mass mass concentration of 230 nm) was used as particle B. Except having changed into%), it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 15

Particles A were TiO ₂ with a refractive index of 2.7 (TTO-W-5 manufactured by Ishihara Industries, solids concentration 30 mass%), and particles B were acrylic particles having an average particle diameter of 300 nm (Gantz Pearl PM-030 manufactured by Gantz Chemicals, 41 mass% solids concentration). Except having changed into), it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 16

Change Particle A to TiO ₂ with a refractive index of 2.7 (TTO-W-5 manufactured by Ishihara Industries, 30 mass% of solid content concentration) and Silica Particles (MP4540M manufactured by Nissan Chemical Industry, 40 mass% solids concentration) with an average particle diameter of 450 nm Except having done, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 17

An optically laminated polyester film was obtained in the same manner as in Example 1 except that the particle A was changed to TiO ₂ having a refractive index of 2.7 (TTO-W-5 manufactured by Ishihara Industries, 30 mass% of solid content concentration).

Example 18

TiO ₂ with a refractive index of 2.7 (TTO-W-5 manufactured by Ishihara Industrial Co., Ltd., 30 mass% of solid content concentration), and crosslinked polystyrene particles (Grossdel 207-S manufactured by Mitsui Chemical Co., Ltd. Except having changed into%), it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 19

Except having changed into the coating liquid for hard-coat layer formation (C-2), it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 20

The laminated polyester film for optics was obtained like Example 1 except having changed the block polyisocyanate aqueous dispersion (C) into the water-soluble resin (D) which has an oxazoline group.

Example 21

Except having changed the block polyisocyanate aqueous dispersion (C) into carbodiimide water-soluble resin (E), it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 22

The laminated polyester film for optics was obtained like Example 1 except having changed the block polyisocyanate aqueous dispersion (C) into melamine resin (Bacamine M-3 by Dainippon Ink, 60 mass% of solid content concentration).

Example 23

Except having changed the polyester aqueous dispersion into B-2, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 24

Except having changed the polyester aqueous dispersion into B-3, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 25

Except having changed the polyester aqueous dispersion into B-4, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 26

The laminated polyester film for optics was obtained like Example 1 except having changed the polyester aqueous dispersion into B-5.

Example 27

Except having changed the polyester aqueous dispersion into B-6, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 28

The laminated polyester film for optics was obtained like Example 1 except having changed the polyester aqueous dispersion into B-7.

Example 29

Except having changed the polyester aqueous dispersion into B-8, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 30

Except having changed the polyester aqueous dispersion into B-9, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

Example 31

Except having changed the coating liquid below, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

40.16 mass% of water

Isopropanol 30.00 mass%

Polyester water dispersion (B-1) 24.27 mass%

Block polyisocyanate aqueous dispersion (C) 2.78 mass%

Particle A 2.59 Mass%

(Ishihara industry production TTO-W-5, solid content concentration 30 mass%)

Particle B 0.17 mass%

(Nippon Shokubai Shihosuta KEW50, solid content concentration 15% by mass)

0.03 mass% of silicone type surfactant

(100 mass% of solid content concentration)

Example 32

Except having changed the coating liquid below, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

40.16 mass% of water

Isopropanol 30.00 mass%

Polyester water dispersion (B-1) 24.97 mass%

Block polyisocyanate aqueous dispersion (C) 2.86 mass%

Particle A 1.81 mass%

(Ishihara industry production TTO-W-5, solid content concentration 30 mass%)

Particle B 0.17 mass%

(Nippon Shokubai Shihosuta KEW50, solid content concentration 15% by mass)

0.03 mass% of silicone type surfactant

(100 mass% of solid content concentration)

Example 33

Except having changed the coating liquid below, it carried out similarly to Example 1, and obtained the laminated polyester film for optics.

40.16 mass% of water

Isopropanol 30.00 mass%

Polyester water dispersion (B-1) 25.91 mass%

Block polyisocyanate aqueous dispersion (C) 2.96 mass%

Particle A 0.77 mass%

(Ishihara industry production TTO-W-5, solid content concentration 30 mass%)

Particle B 0.17 mass%

(Nippon Shokubai Shihosuta KEW50, solid content concentration 15% by mass)

0.03 mass% of silicone type surfactant

(100 mass% of solid content concentration)

The optical laminated polyester film of the comparative example 1 does not contain naphthalenedicarboxylic acid as an acid component in polyester resin. Therefore, since the refractive index of an application layer falls, the effect of suppressing iris color under fluorescent lamps is insufficient.

As the particle | grains A, the silica with low refractive index is used for the optical laminated polyester film of the comparative example 2. Therefore, since the refractive index of an application layer falls, the effect of suppressing iris color under fluorescent lamps is insufficient.

The optically laminated polyester film of Comparative Example 3 does not contain Particle B having an average particle diameter of 200 nm or more and 700 nm or less. Therefore, since there is no light scattering effect at the hard coat layer / coating layer interface, the effect of suppressing the iris color under the fluorescent lamp is inferior. Moreover, since there is no interface irregularities formed by the particles B, the contact area with the hard coat layer is lowered, resulting in poor adhesiveness and moisture heat resistance.

The optically laminated polyester film of Comparative Example 4 does not contain Particle B having an average particle diameter of 200 nm or more and 700 nm or less. In addition, it changed into the coating liquid for hard-coat layer formation (C-2). C-2 dissolves or swells a part of the coating interface, disturbs the design of the hard coat layer / coating layer interface, and has no light scattering effect at the hard coat layer / coating layer interface. Inhibitory effect of iris color is less. Moreover, since there is no interface irregularities formed by the particles B, the contact area with the hard coat layer is lowered, resulting in poor adhesiveness and moisture heat resistance.

The optically laminated polyester film of Comparative Example 5 contains particles having an average particle diameter of 100 nm as Particle B. Therefore, since there is no light scattering effect at the hard coat layer / coating layer interface, the effect of suppressing the iris color under the fluorescent lamp is inferior. In addition, since there is little interface uneven | corrugation formation by particle | grains B, the contact area with a hard-coat layer falls, and adhesiveness and moisture heat resistance are inferior.

Although the laminated polyester film for optics of the comparative example 6 contained the particle | grains of average particle diameter 2000nm as particle B, adhesiveness fell.

The easily adhesive polyester film for optics of the comparative example 7 does not contain the long-chain dicarboxylic acid component and the long-chain diol component as a composition component of a polyester resin. Therefore, chipping resistance of an application layer is inferior.

The easily adhesive polyester film for optics of the comparative example 8 contains the dicarboxylic acid component and diol component in which n exceeds 10 in Formula (1) and Formula (2) as a composition component of a polyester resin. . Therefore, when the hard coat layer is laminated, the effect of suppressing interference nonuniformity is inferior.

The easily-adhesive polyester film for optics of the present invention has good processability, and is excellent in antireflection property of suppressing the reflection of light, glare, iris color, etc. when a hard coat layer is laminated on the coating layer of the film. In addition, since it has excellent adhesion to the hard coat layer and adhesion at high temperature and high humidity (humidity and heat resistance), the touch panel, the liquid crystal display (LCD), the CRT of a TV or a computer (CRT), the plasma display (PDP), and the organic electroluminescence As a base film of an antireflection film which is attached as a front surface or an icon sheet of a display screen such as a nessene (organic EL), and which provides antireflection to suppress reflection of external light, glare, iris color, and the like. Suitable.

Claims (4)

As an easily-adhesive polyester film for optics which has a coating layer containing a polyester resin and particle | grains A and particle | grains B on at least one side of a polyester film,
The said polyester resin contains naphthalenedicarboxylic acid as a acid component, the dicarboxylic acid component represented by following formula (1), and / or the diol component represented by following formula (2),
Particle A is a metal oxide particle having a refractive index of 1.7 or more and 3.0 or less,
The easily-adhesive polyester film for optics whose said particle B is particle | grains of 200 nm-700 nm of average particle diameters.
(1) HOOC- (CH ₂ ) _n -COOH (wherein n is an integer of 4≤n≤10)
(2) HO- (CH ₂ ) _n -OH (wherein n is an integer of 4≤n≤10) The method of claim 1,
The easily-adhesive polyester film for optics, wherein the coating layer contains a crosslinking agent. The method of claim 2,
The crosslinking agent is at least one crosslinking agent selected from a urea crosslinking agent, an epoxy crosslinking agent, a melamine crosslinking agent, an isocyanate crosslinking agent, an oxazoline crosslinking agent, and a carbodiimide crosslinking agent. Optical lamination by laminating | stacking the hard-coat layer which consists of an electron beam or an ultraviolet curable acrylic resin, or a siloxane-type thermosetting resin to the application layer of the easily-adhesive polyester film for optics of any one of Claims 1-3. Polyester film.