TW200810924A - Hard-coated film and optical functional film - Google Patents

Abstract

A hardcoat film is characterized in that it is obtained by laminating an adhesiveness modifying substrate film formed with an adhesiveness modifying layer B which contains a copolymerized PEs and a PU on one or both sides of a thermoplastic resin film A with a hardcoat layer C containing an inorganic microparticle in the surface of the adhesiveness modifying layer B on either side of the film, wherein the adhesiveness modifying layer B has a microphase separation structure and a nanophase separation structure, and in the range from the interface between the adhesiveness modifying layer B and the hardcoat layer C to a depth of 20 nm, when the cut face of the hardcoat film is observed by using a scanning probe microscope in phase determination mode, the area rate of the PU phase of the adhesiveness modifying layer B is 30% or more and 60% or less.

Description

[Technical Field] The present invention relates to a hard coating film mainly used for a member for a leader, an antireflection film using the film, a light diffusion sheet, and a prism lens sheet 'near infrared ray shielding film An optical functional film such as a transparent conductive film or an anti-glare film. In detail, the hard coating layer containing the substrate film and inorganic fine particles, and other optical functional layers (hard coating layer, light diffusion layer, edge)

A hard coating film having excellent adhesion to a mirror layer, an infrared ray absorbing layer, a transparent conductive layer, an antiglare layer or the like and excellent in scratch resistance, and an optical functional film using the same. [Prior Art] Generally, a hard coating film for a member of a display such as a liquid crystal display (LCD) or a plasma display panel (PDP) is laminated with a thermoplastic resin film and a hard coating (HC) via an adhesive modified resin layer. Floor. Further, the optical functional film for a display is usually used by bonding an optical functional film having different functions via an adhesive layer. However, the demand for large flat panel displays in the low-priced market in recent years has grown. Therefore, in the member for display, a composite film in which another optical functional layer is laminated on one hard coating film has been developed. For example, in a liquid crystal display (LCD), an anti-reflection layer (AR layer) for preventing reflection of external light, and a lens layer for concentrating or diffusing light may be laminated on a hard coating film. An optical functional composite film for an optical functional layer such as a light-diffusing layer that increases brightness. In the thermoplastic resin film which becomes a substrate of a hard coating film, polyethylene terephthalate (PET), polyamide, acrylic acid, polycarbonate (PC) 200810924, triacetyl cellulose (TAC), A transparent film formed of a cyclic polyolefin or the like. Among these base films, in particular, from the viewpoint of excellent transparency, dimensional stability, and chemical resistance, a biaxially oriented polyester film is widely used as a thermoplastic resin film of various optical functional films.

In general, in the case of a biaxially oriented polyester film or a biaxially oriented polyimide film like a biaxially oriented thermoplastic film, there is a lack of various coatings, adhesives, inks, etc. due to the highly crystalline alignment of the film surface. The shortcomings of the adhesion. Therefore, in the surface of the biaxially oriented thermoplastic resin film hitherto, there has been proposed a method of imparting easy adhesion by various methods. Further, in a film which does not have a polar group like a polyolefin film, since adhesion to various coating materials, adhesives, inks, and the like is extremely insufficient, it is proposed to perform physical treatment such as corona discharge treatment or flame treatment beforehand. After the chemical treatment, a method of imparting easy adhesion to the surface of the film by various methods is given. For example, it is generally known to provide an adhesive modified layer containing an adhesive modified resin such as a film, a polyester, an acrylic, a polyurethane, or an acrylic graft polyester on the surface of a thermoplastic resin film by a coating method. Further, a method of imparting easy adhesion to a thermoplastic resin film is provided. In the coating method, the thermoplastic resin film before the end of the crystal alignment is widely used in the industry, and the solution containing the above resin or the dispersion in which the resin is dispersed by the dispersion medium is directly or optionally subjected to a corona discharge treatment. The aqueous coating liquid is applied to a substrate film to be stretched in at least one axial direction after drying, followed by heat treatment to complete the crystal alignment of the thermoplastic resin film (so-called in-line coating method), or After the production of the thermoplastic resin film, a water-based or solvent-based coating liquid is applied to the film on 200810924, and then dried (so-called off-line coating method).

In the process of increasing the size and cost of the display, such as LCDs and PDPs, the production speed is being increased in the process of optical functional films used as components. With such a high speed of the process, the stress accompanying the hardening shrinkage becomes more likely to occur at the interface between the hard coating layer, the diffusion layer, the enamel-like functional layer and the base film. Therefore, in order to manufacture a display, when the optical functional film is cut into a specific size, if the adhesion at the above interface is insufficient, there is a problem that the end portion is particularly likely to be peeled off. When the film is rolled up into a cylindrical shape, or when the production speed is increased during the process, the influence of the interface peeling due to the squeezing at the time of dicing becomes more remarkable, and the conventional level of adhesion becomes insufficient. Further, in order to form the functional layer such as the ruthenium layer or the diffusion layer, the processing agent used is directly coated with the processing agent on the substrate film from the viewpoint of a reduction in environmental load, without being diluted with an organic solvent. There are many situations on it. Therefore, since the wetting improvement effect of the organic solvent on the adhesion-modifying layer is not sufficiently obtained, higher adhesion is required. On the other hand, in applications where smoothness is emphasized in the form of a hard coating layer, in order to reduce the viscosity of the processing agent to obtain a good leveling effect, a processing agent diluted with an organic solvent is often used. In this case, moderate solvent resistance is required for the adhesion-modifying layer of the adhesive-modified substrate film. In order to improve the adhesion between the functional layer and the base film, a resin having a low glass transition temperature is generally used for the resin constituting the adhesive reforming layer. However, in the case of using a resin having a low glass transition temperature, in 200810924, the adhesive-modified substrate film is continuously wound into a cylindrical shape, and when the film is wound up from the cylindrical film, the blocking resistance tends to be lowered. In addition, in recent years, in order to reduce the cost, the processing machine for laminating the hard coat layer or the diffusion layer to the base film has been enlarged, and the diameter of the easy-to-adhere film used as the base film has been increased. It is also large. With this, in order to prevent the winding deviation of the cylinder, when winding under high tension, the winding core of the cylinder is pressed to be pressed at a high pressure.

Adhesion is easy to occur. In order to improve the anti-blocking property, a method of imparting irregularities to the surface of the adhesive-modified substrate film to reduce the contact area is generally employed. In order to impart unevenness to the surface of the film and to be contained in the adhesive layer or the base film, a method of increasing the content of inorganic particles or organic particles or a method of using particles having a large particle size is generally employed. However, since the refractive index of the particles which are generally commercially available is different from the refractive index of the resin used in the adhesion modifying layer, and the voids are formed around the particles as the film is stretched, such methods may occur. The light transmittance of the film is lowered, the haze is increased, and the like. In particular, the transparency required for the substrate film of the optical functional film is lowered. In other words, in the conventional method, as the speed of the process is increased or the diameter of the cylinder of the film is increased, a new problem arises, and it is extremely difficult to improve the adhesion to the functional layer or the anti-blocking property while maintaining the transparency. . In addition, in recent years, in order to prevent adhesion to the light guide plate, to improve transmittance, or to reduce curl, the optically functional film is provided with a hard coating layer on both surfaces of the base film, or in a 稜鏡 lens layer. Or the case where the surface of the opposite side of the optical functional layer like the light diffusion layer is also laminated with a hard coating layer

More than 200810924. In particular, the hard-coated film is usually a thermosetting resin or an ultraviolet curable resin-like ionizing radiation-curable resin, and a thin hard coating film (hard coating layer) having a thickness of 3 to 1 μm is formed on the thermoplastic resin film. However, since the thickness of the hard coating layer is thinner than the base film, the hardness of the hard coating film itself is affected by the base film and does not become sufficiently high. Therefore, in order to improve the scratch resistance of the hard coating layer, it is considered to contain inorganic particles in the hard coating layer.

On the other hand, when the inorganic particles are contained in the hard coating layer, the ratio of the curing resin in the hard coating layer is lowered, so that it is in the interface between the adhesion-modifying layer and the hard coating layer of the adhesive-modified base film. The adhesion will be reduced. In particular, it is known that a biaxially oriented polyester film is inferior in adhesion to a coating agent containing an acrylic resin as a main component used in a tantalum lens or a hard coating layer. Therefore, there are various proposals for forming an adhesive modified layer made of a polyurethane or the like on the surface of the polyester film (see, for example, Patent Document 1). However, the adhesion-modifying layer formed of the polyurethane is formed to improve the adhesion to the functional layer such as the hard coating layer, but the adhesion to the polyester film as the substrate is insufficient, and as a result, the adhesion is improved. The interface between the modified layer and the functional layer is insufficient. In particular, the adhesion between the adhesive layer and the hard coating layer containing the inorganic particles is remarkably deteriorated. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 6-340049. Further, it has been proposed to provide a resin having a copolymerized polyester and a polyurethane as a main constituent component on a base film formed of biaxially aligned polyethylene terephthalate by an in-line coating method. The composition layer is a method for improving the adhesion between the base polyester film and the functional layer such as ink (for example, see Patent Document 2) 200810924. Specifically, a water-dispersible coating liquid containing a copolymerized polyester and a polyurethane (= 20/80; mass%) is applied onto a polyester film stretched in the longitudinal direction by a shaft, and then guided to a tenter. The machine was allowed to dry, and after transverse stretching, it was heat-set at 220 ° C to obtain an easily bondable biaxially oriented polyester film. Patent Document 2: Japanese Patent Publication No. 64-6025

However, in the method described in Patent Document 2, although the adhesiveness is improved, the functional layer such as the base film and the hard coat layer or the diffusion layer which are required for the base film used in the optical functional film in recent years is particularly advanced. The adhesion between the modified layer and the hard coating layer containing the inorganic particles is insufficient. The applicant of the present invention proposed to provide a resin composition layer of a copolymerized polyester and a polyurethane and an inorganic particle having a moderate particle diameter on a substrate film formed by biaxially-aligned polyethylene terephthalate. In addition, a laminated polyester film which can sufficiently satisfy the adhesion at the market level and has few optical defects while maintaining the transparency of the extremely important characteristics of the optical base film (see, for example, Patent Documents 3 and 4). Specifically, it is disclosed on a polyester film which is longitudinally stretched by a shaft, and coated with a copolymerized polyester, a polyurethane (=20/80; mass%) and two kinds of vermiculite particles having different average particle diameters. After the water-dispersible coating liquid of the anionic surfactant, it is guided to a tenter, dried, and transversely stretched, and then heat-set at 240 ° C to obtain an easily bondable biaxially oriented polyester film. The easy-adhesive biaxial alignment polyester film obtained in Patent Documents 3 and 4 has excellent adhesion, anti-blocking property, and transparency, and optical defects such as impurities and scratches are greatly improved to satisfy Specially required by the previous -10- 200810924. However, as described above, with the reduction in cost in recent years and the large screen size of the display, the base film, the hard coat layer, the diffusion layer, the ruthenium layer and the like required for the base film for the optical functional film are required. The level of adhesion between the layers and the level of anti-blocking properties tend to be stricter year after year. In particular, the adhesion between the adhesive layer and the hard coating layer containing the inorganic particles cannot sufficiently satisfy the quality required on the market today. Patent Document 3: Japanese Laid-Open Patent Publication No. Hei 11-32327 No. 1. Patent Document 4: JP-A-2000-246855.

Further, in order to improve the uniformity of the adhesion, the applicant of the present invention has proposed an invention relating to a film roll which has been reduced in the amount of coating which is easy to change (for example, refer to Patent Document 5). In the examples of Patent Document 5, it is described that a copolymerized polyester and a polyurethane (= 5 0/5 0 ; mass %) and an average particle diameter are coated on a polyester film which is longitudinally stretched in the longitudinal direction. 1.4 μπι of vermiculite particles and a water-dispersible coating liquid of a fluorine-based surfactant are dried in a drying oven at 120 ° C, then transversely stretched, and then heat-set at 220 ° C. The second biaxially oriented polyester film. The obtained film reel uniformly has excellent adhesion throughout the film reel to meet the market demand level. However, the adhesion to the interface between the adhesion-modifying layer and the hard coating layer containing the inorganic particles is not sufficiently sufficient. Further, in order to improve the scratch resistance, it is proposed to apply a coating on a polyethylene terephthalate film which is easy to apply, and it is applied to a resin of 100 parts by mass. 40 parts by mass of an ionizing radiation hardening type hard coating agent of vermiculite ultrafine particles having a particle diameter of about 50 nm or less, a hard coating film having a dry thickness of about 15 μm and hardened by an electron-11-200810924 line (for example, reference) Patent Document 6). However, although the hard coating film has high hardness and excellent scratch resistance, the hard coating layer does not sufficiently satisfy the requirements of the current market for the adhesion between the adhesive layer and the hard coating layer containing the inorganic particles. quality. Patent Document 6: JP-A-2000- 1 1 2379

On the other hand, there is a proposal for a hard-coated polyethylene terephthalate film which is formed by a copolymerization of a polyester and a melamine crosslinking agent, and a hard coating layer containing no particles. The film is coated (for example, refer to Patent Document 7). However, the hard coating film is not sufficiently satisfactory in terms of the adhesion of the hard coating layer and the hardness of the hard coating layer. Patent Document 7: JP-A-2004-160774. In other words, in the prior art, although high hardness can be maintained, a hard coating film which is excellent in adhesion to high-speed dicing which has been required in recent years, and which is excellent in adhesion to a hard coating layer containing inorganic particles, cannot be obtained. SUMMARY OF THE INVENTION The object of the present invention is to provide a hard coating film having high adhesion and high hardness at the interface between an adhesive layer and an inorganic particle-containing hard coating layer, and a hard coating film using the same Optical functional film. Means for Solving the Problem The above problems can be achieved by the following solutions. That is, the first invention of the present invention is a hard coating film characterized in that the hard coating film is formed on one surface or both surfaces of the thermoplastic resin film A to form a copolymer containing a copolymerized polyester and a polyurethane. Modified layer B -12- 200810924

Next, the modified base film and the hard-coated layer C containing inorganic fine particles on the surface of the adhesive layer B on either side of the film are laminated to form A/B/C or B/A/. Layer B/C composition in which the adhesion modifying layer B has a microphase separation structure or a nano phase separation structure of a polyester (PEs) phase and a polyurethane (PU) phase, and uses a scanning probe microscope When the cut surface of the hard coating film is observed in the phase measurement mode, the adhesion change defined by the following formula (1) is changed from the interface between the adhesion-modified layer B and the hard coating layer C to a depth of 20 nm. The area ratio of the polyurethane phase of the layer B (in the phase image showing the bright phase) is 30% or more and 60% or less. Area ratio (%) of the PU phase = (area of the PU phase/measurement area) x1 (1) The second invention is a hard coating film characterized in that the hard coating film is contained in the thermoplastic resin film A. On one or both sides, an adhesive modified base film having an adhesive layer B containing a copolymerized polyester and a polyurethane, and a surface of the adhesive layer B on either side of the film The hard coating layer C containing inorganic fine particles is composed of a layer of A/B/C or B/A/B/C laminated, wherein the adhesive modified layer B has a polyester (PEs) phase and a polyamine. When the surface of the adhesive layer B is observed in the phase measurement mode using a scanning probe microscope, the micro phase separation structure or the nano phase separation structure of the formate (PU) phase is defined by the following formula (2). The area ratio of the polyester phase (in the phase image showing the dark phase) on the surface of the adhesion-modifying layer B is in the range of 5 μm X 5 μm, and is more than 35 % and less than 90%. The area ratio (%) of the PEs phase = (area of the PEs phase/measured area) χ100. The second invention is a hard coating film according to the first or second invention, wherein the inorganic layer in the hard coating layer C The content of the fine particles is 20 to 80% by mass. In the hard coating film according to the first or second aspect of the invention, the thermoplastic resin film does not contain or contain particles of 5 〇 ppm or less, and contains 0.1 to 20 in the adhesive modified layer. Mass % of particles. The hard coating film according to the fourth aspect of the invention, wherein the particle is a vermiculite particle.

According to a sixth aspect of the invention, there is provided an optical functional film comprising a hard coating layer, a light diffusion layer, and a dome lens on a surface opposite to the hard coating layer C of the hard coating film according to the second and second inventions. At least one optical function layer selected from the layer, the electromagnetic wave absorbing layer, the near-infrared ray shielding layer, and the transparent conductive layer. According to a seventh aspect of the invention, there is provided an optical functional film which is an optical functional film in which an antireflection layer or an antifouling layer is laminated on the hard coating layer C of the hard coating film according to the first or second aspect. Advantageous Effects of Invention The hard coating film of the present invention has a specific micro phase separation structure or a nano phase separation structure in a polyester phase and a polyurethane phase as an intermediate layer of a thermoplastic resin film and a hard coating layer, in the adhesion property. In the cutting surface of the modified layer, the area ratio of the polyurethane phase in the vicinity of the interface with the hard coating layer is within a specific range. Therefore, even if a hard coating layer containing inorganic fine particles is laminated, the adhesion to the hard coating layer can be improved while maintaining high hardness. Further, the adhesion to the optical functional layer such as the diffusion layer or the ruthenium layer is also excellent. Further, by containing only a specific amount of particles of a specific particle size only in the adhesive modifying layer, or in any of the polyester phase or the polyurethane phase on the surface of the adhesive modifying layer, When the particles are biased, the adhesion of the height of -14 to 200810924 can be maintained, and the anti-blocking property, handleability, and scratch resistance can be improved. Therefore, it is suitable as a hard coating film or an optical functional film which requires high transparency. In particular, when the vermiculite particles are contained in the adhesive reforming layer, since the vermiculite particles are biased in the polyurethane phase, the disadvantage of the polyurethane having poor anti-blocking property can be compensated for. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION First, in the present invention, the adhesion and hardness described in the subject will be described.

In the hard coating film of the present invention, the adhesiveness means that the hard coating layer containing the inorganic fine particles is subjected to a checkerboard peeling test (100 squares) 10 times with a tape, and the adhesion between the hard coating layer and the base film is changed. The adhesion of the interface of the layer. In the present invention, those having an adhesiveness as defined by the following formula of 80% or more are regarded as acceptable. It is preferably 85% or more, and particularly preferably 90% or more. Adhesiveness (%) = (1 - number of peeled squares / 100) χ 100 Further, in the adhesive modified base film used in the present invention, the adhesiveness means a solvent-hardened photocurable acrylic A hard coating layer cured by ultraviolet light is formed on the adhesive modified layer of the film, and the board is peeled off by a 10-time checkerboard test (100 squares) with a tape, and the adhesion between the acrylic hard coating layer and the film is changed. The adhesion of the interface of the layer. In the present invention, those having an adhesiveness defined by the following formula of 80% or more are regarded as acceptable. It is preferably 85% or more, and particularly preferably 90% or more. Adhesiveness (%) = (1 - number of squares peeled off / 100) χ 100 -15 - 200810924 Furthermore, the hardness stated in the present invention means that it is evaluated by the pencil hardness test according to JIS-K540G. Pencil hardness." The pencil hardness was the surface of the hard coating layer of the hard coating film, and the pencil hardness test was repeated five times. When the appearance of the flaw or the like was abnormal in any of the tests, the hardness of the pencil used in the test was regarded as the pencil hardness. For example, a pencil of 3H is used for five test operations, and if the appearance is not abnormal once, the pencil hardness of the material is regarded as 3H.

Further, the anti-blocking property of the adhesive-modified substrate film used in the present invention is such that the adhesive layer of the two film samples is laminated in an opposing manner to a pressure of lkgf/cm2. After adhering for 24 hours in an atmosphere of 50° C. and 6〇% RH, the film was peeled off, and the peeled state was determined as “the adhesive layer was not transferred, and it was easily peeled off”. Further, the film having high transparency in the present invention means a film having a haze of 1.5% or less. The preferred haze is 1% or less. In the adhesive modified base film used in the present invention, in order to obtain excellent adhesion and anti-blocking property, it is important to exhibit a specific micro phase separation structure or a nano phase separation structure on the surface of the adhesion modifying layer. . Further, in the hard coating film of the present invention, in order to improve the adhesion between the adhesion-modifying layer of the adhesive modified base film and the hard coating layer containing the inorganic fine particles, the surface of the adhesive modified layer is At the interface with the hard coating layer, it is important to express a specific microphase separation structure or a nano phase separation structure. However, in the hard coating film of the present invention, the adhesion-modifying layer B is an intermediate layer of the thermoplastic resin film A and the hard coating layer C. That is, from the surface of the hard coating film, the phase of the surface of the adhesive reforming layer B could not be observed -16-200810924. Therefore, in the present invention, the hard coating film is cut, and the phase separation structure of the adhesion modifying layer in the vicinity of the interface with the hard coating layer is observed from the cut surface. In the specific phase separation structure of the adhesion-modifying layer in the present invention, the resin composition of the coating liquid for forming the adhesion-modifying layer, the type and concentration of the surfactant, the coating amount, and the adhesion property can be selectively used. Drying conditions of the modified layer, heat setting conditions, and the like are formed by controlling them.

First, the method for producing the adhesive-modified substrate film used in the present invention is exemplified by polyethylene terephthalate (hereinafter abbreviated as PET) as a representative example, but it is of course not limited by the representative example. The nine particles of PET which do not substantially contain particles (the purpose of which is to impart slipperiness) are sufficiently vacuum-dried, supplied to an extruder, melt-extruded into a sheet at 280 ° C, and solidified by cooling. Make unaligned PET sheets. At this time, the molten resin is held at an arbitrary position of about 280 ° C, and high-precision filtration is performed in order to remove impurities contained in the resin. The obtained unaligned sheet was stretched by 2 · 5 to 5.0 times in the longitudinal direction by a roll heated to 80 ° to 120 ° C to obtain a one-axis oriented PET film. Then, an aqueous solution of the copolymerized polyester and polyurethane was applied to one or both sides of the one-axis alignment PET film. In order to apply the above aqueous coating liquid, for example, a reverse roll coating method, a gravure coating method, a kiss coating method, a roll brush method, a spray coating method, an air knife coating method, a wire rod coating method, and a tube scraping method are mentioned. The method is 'impregnation coating method, curtain coating method, etc., and these methods can be carried out singly or in combination. Next, the end of the film was grasped by a jig and guided to a hot air zone which had been heated to 80 to -17 - 200810924 180 ° C, and dried and then stretched 2.5 to 5.0 times in the width direction. Next, it is guided to a heat treatment zone of 220 to 240 ° C, and heat treatment is performed for 1 to 20 seconds to complete the crystal alignment. In the heat treatment process, a relaxation treatment of 1 to 12% may be applied in the width direction or the length direction as needed. First, the phase separation structure of the adhesion-modifying layer of the adhesive-modified substrate film used in the present invention will be described. Next, the raw materials and production conditions for the hard coating film or the optical functional film of the present invention will be described in detail, and the condition factors for controlling the phase separation structure described above are also included.

(1) Phase Separation Structure of Adhesive Modification Layer In the present invention, the adhesive modification layer has a polyester phase (hereinafter also referred to as PEs phase) having a copolymerized polyester as a main component, and a polyamine A microphase separation structure or a nanophase separation structure of a polyurethane phase (hereinafter also referred to as a PU phase) in which an acid ester is used as a main component. In the hard coating film of the present invention, the purpose of using the adhesion-modifying layer B is to improve the adhesion between the hard coating layer containing inorganic fine particles and the thermoplastic resin film. Further, when the same hard coating layer or other optical functional layer is laminated on the surface on the opposite side of the hard coating layer, it is also possible to improve the adhesion between the layers and the thermoplastic resin film. In the present invention, an important feature is that the adhesion modifying layer B has a microphase separation or a nano phase separation structure in a polyester (PEs) phase and a polyurethane (PU) phase, and uses a scanning type. When the probe microscope observes the cut surface of the hard coating film in the phase measurement mode, the adhesion is defined by the following formula in the range from the interface between the adhesion modifying layer B and the hard coating layer C to a depth of 20 nm. The area ratio (PU area ratio) of the polyurethane phase of layer B (in the phase image showing a clear color phase) is 30% or more and 60% or less. Area ratio (%) of the pu phase = (area of pu phase/measured area) xl00 Further, the area ratio of the above PU phase is obtained by γ. In the hard coating film of the present invention in which the thermoplastic resin film/adhesive modified layer/hard coating layer is used as a constituent unit, in order to calculate the area ratio of the pu phase of the adhesive layer of the intermediate layer, it is necessary to be buried in The surface of the internal adhesion modifying layer is exposed.

As a method of exposing the surface of the adhesion-modifying layer, a method of cutting a film from an oblique direction by using a surface interface physical property analysis device (DAICALA, manufactured by WINTES Co., Ltd., SAICAS) is suitable. Next, using a scanning probe microscope (SPM), the phase separation structure was observed from the phase image of the adhesion-modifying layer in the phase measurement mode (phase mode), and the area ratio of the PU phase in the vicinity of the hard coating layer was obtained. In the cutting surface of the adhesive reforming layer, the area ratio of the polyurethane phase in the vicinity of the interface of the hard coating layer has the following technical meaning. When the area ratio of the polyurethane phase exceeds 60%, the ratio of the polyurethane phase becomes relatively large on the surface of the adhesive modified layer at the time of production of the adhesive modified base film. The frequency of anti-adhesion reduction will increase. On the other hand, if the area ratio of the polyurethane phase is less than 30%, the frequency at which the adhesion is lowered increases. In particular, in the solventless hard coating agent or the lens forming resin, the decrease in adhesion is remarkable. In the adhesion modifying layer in the vicinity of the interface with the hard coating layer, the upper limit of the area ratio of the polyurethane phase is preferably 50% from the viewpoint of blocking resistance. On the other hand, the lower limit of the area ratio of the pu phase is preferably 35% from the point of view of the adhesion between the other layers of the hard coating layer or the acrylic resin.

Further, the microphase separation structure or the nano phase separation structure of the PEs phase and the PU phase was observed on the surface of the subsequent reforming layer of the adhesive modified base film before the hard coating layer was laminated. Further, when viewed by a scanning probe microscope in a phase measurement mode, the area ratio of the polyester phase (in the phase image showing a dark phase) in the surface of the adhesion-modifying layer defined by the following formula is 5 μm η 5 μιη The range is more than 35% and less than 90%. Further, in the present invention, when the adhesion-modifying layer is provided on both surfaces of the thermoplastic resin film, any of the adhesion-modifying layers has an area ratio of the same polyester phase as described above. Area ratio (%) of the PEs phase = (area of the PEs phase/measured area) χ 100 The area ratio of the PEs phase in the surface of the J-modified layer is as follows. When the area ratio of the PEs phase is less than 35%, the area ratio of the polyurethane phase becomes relatively large on the surface of the adhesion modifying layer, and the frequency of preventing the blocking property increases. On the other hand, if the area ratio of the P E s phase is 90% or more, the frequency of decrease in the adhesion is increased. In particular, in the case of a solventless hard coating agent, the decrease in adhesion is remarkable. In the surface of the adhesion modifying layer, the lower limit of the area ratio of the PEs phase is preferably 40%, more preferably 45%, and particularly preferably 5% by weight from the viewpoint of blocking resistance. On the other hand, in the surface of the adhesion-modifying layer, the upper limit of the area ratio of the PEs phase is preferably 85 %, more preferably from the point of adhesion to the functional layer formed of the acrylic resin. 80%, especially good 75%. Further, in the present invention, the evaluation of the phase separation structure of the surface of the adhesion-modifying layer is carried out by using a scanning probe microscope (SPM) phase measuring mode -20-200810924 (phase mode). The phase mode is observed by the surface morphology of the normal power mode (DFM mode; when using SPM manufactured by SII Nanotechnology Co., Ltd.) and the phase delay measurement mode. The principle of measuring the phase separation structure of the adhesion modifying layer by the phase measurement mode (phase mode) of the scanning probe microscope (SPM) will be briefly described.

In the phase mode, the phase delay of the cantilever vibration when the DFM is operated is detected. In the DFM operation, the distance between the probe and the sample is controlled so that the vibration amplitude of the resonant cantilever is constant, and the shape is measured. Here, when the signal for vibrating the bimorph (piezoelectric element) that vibrates the cantilever is referred to as an "input signal", in the phase measurement mode, the "input signal" is detected simultaneously with the vibration amplitude. That is, the phase delay of the effective cantilever vibration signal. The phase delay is sensitive to the influence of surface physical properties, and the softer the surface of the sample is delayed. By visualizing the magnitude of the phase delay, the distribution of surface physical properties (referred to as phase image, phase, etc.) can be observed. Therefore, when a plurality of resin phases having different physical properties exist on the surface, the phase separation structure can be evaluated by the present measurement method. However, the evaluation of the phase separation structure of the adhesion-modifying layer may be a frictional force measurement mode or a viscoelasticity measurement mode other than the phase measurement mode in the case of the surface property distribution evaluation mode of the scanning probe microscope. Mode, the most important thing is to choose an observation mode that can evaluate the phase separation structure with good sensitivity. Further, in the phase measurement mode, not only the phase retardation can be detected by the difference in viscoelasticity of the adhesive layer, but also the phase retardation can be detected by the difference in surface physical properties such as the magnitude of the adsorption force. Further, in order to observe the phase separation structure of the cutting surface of the adhesive reforming layer, it is preferable to read the phase image by SPIP software (Version 4.1, manufactured by Image Metrology, Inc.) in order to easily observe the phase separation structure. Color Equalization is applied to enhance contrast. The reason is as follows.

When the surface interface physical property analyzer (SAICAS) is used to cut the inside of the hard coating film from the base film side, it is difficult to completely avoid the deformation of the cutting surface of the adhesive modified layer in the cutting direction. Further, since the inorganic particles contained in the adhesive reforming layer cannot be cut, the damage at the time of cutting around the inorganic particles is such that the occurrence of voids cannot be avoided. By the cutting as described above, in the interface between the adhesive modified layer exposed on the surface and the thermoplastic resin film, the hard coating layer, or the other functional layer, the PU component is dominant in comparison with the PEs component. It is presumed that this is because the PU component is more easily deformed in comparison with the PEs component, and the difference between the physical properties of the PEs component and the physical properties of the thermoplastic resin film adjacent to the adhesive modifying layer is small, and the cutting is performed from the oblique direction. In view of the fact that the thickness of the modified layer is extremely thin, the difference in contrast becomes small. The phase separation structure of the adhesion-modifying layer in the present invention corresponds to a microphase separation structure or a nanophase separation structure from the viewpoint of size. In the adhesive modified base film used in the present invention, when the phase difference image of the surface of the adhesive modified layer (the interface with the hard coating layer) was observed, it was found that the phase separation structure was as follows. When the P E s phase is regarded as a continuous structure having a long axis and a short axis, the continuous structure in which the width in the short axis direction is at most Ιμιη and the length in the long axis direction exceeds Ιμιη is taken as the main body. That is, the area of the portion having the continuous structure of -22-200810924 is 80% or more, preferably 85% or more, and more preferably 90% or more, for the entire area of the PEs phase. Further, the PEs phase dispersed in an island shape does not correspond to the continuous structure described in the above definition, and has a continuous structure inside the adhesive reforming layer, but the end also appears on the surface.

In terms of the size of the continuous structure of the PEs phase, the width in the short axis direction is preferably Ιμπι, more preferably 0.8 μm, more preferably 66 μιη, and particularly preferably 0 · 4 μπι. The lower limit of the width in the short-axis direction is not particularly limited, but the narrowest portion for maintaining the continuous structure is preferably 〇 1 μ m, particularly preferably 0·05 μιη. On the other hand, in terms of the size of the continuous structure of the PEs phase, the length in the long axis direction is preferably more than Ιμηι, more preferably 1.5 μm or more, particularly preferably 2,0 μπι or more, and particularly preferably 2.5 μιη or more. . In the adhesive modified base film used in the present invention, the phase separation structure of the surface of the adhesive modified layer can be known from the representative example shown in Fig. 1 to show a complicated structure which is not visible in nature. Defining the phase separation morphology in one meaning is difficult. The phase separation structure described above can also be expressed in various aspects as follows. For example, if the form of the phase separation structure is expressed as a pattern, it is close to the "dendritic structure" in the description of the literature ("Chemical Dictionary", p. 226, June 15, 54, Showa, The three publications (shares), "corrugated structure" ("pattern", the first 6 6 ~ 1 6 9 pages, 2 0 0 2 · 10 · 1 wild rose (share) company issued), "Camouflage". The phase separation structure of the surface of such an adhesion-modifying layer, in the field of morphology of the polymer blend system, is similar to that of a co-continuous structure. Furthermore, it is also possible to copolymerize polyester and self-crossing. The linked polyurethanes are represented by a mutual mesh intrusion structure formed by the -23 200810924 entanglement. Moreover, in the form, the self-similarity of the PEs phase can also be quantified using the fractal dimension. For example, as shown in Fig. 3, the surface of the adhesion modifying layer is observed by the phase measurement mode of the scanning probe microscope, and the bright phase (polyurethane phase) and the dark phase (polyester phase) are emphasized. In the phase image of the contour of the interface, the complexity of the boundary line of the bright phase and the dark phase (the contour of the interface) is used as an index, and the grid counting method is used, and the fractal dimension obtained from the contour of the interface is used. Can be expressed quantitatively.

When the fractal dimension per unit area is 1, it means a straight line (primary element), and 2 means a solid surface (secondary element). That is, the closer the broken dimension is to 2, the more dense the structure is. On the other hand, the closer the fractal dimension is to 1, the more sparse the structure is. Specifically, on the surface of the adhesion modifying layer of the adhesive-modified substrate film, the contour image of the contour of the interface between the above-mentioned bright phase (polyurethane phase) and the dark phase (polyester phase) is emphasized. The fractal dimension of the boundary line of the bright phase and the dark phase (the outline of the interface) is preferably 1.60 to 1.95 in the measurement area of 5 μιη χ 5 μπι. The upper limit of the above-mentioned fractal dimension is preferably 1.93, and the special system is 1.90. On the other hand, the lower limit of the above-mentioned fractal dimension is more preferably 1.65, and particularly preferably 1.70 °. For example, in the surface of the adhesion modifying layer shown in Fig. 4, the bright phase (polyurethane phase) The fractal dimensions of the boundary line (the contour of the interface) with the dark phase (polyester phase) are 1.89 and 1.90, respectively. Further, Fig. 4 shows the phase image of the first figure representing the phase separation structure of the surface of the adhesion-modifying layer in the present invention, and emphasizes the contour of the interface between the bright phase and the dark phase, and the bright color - 24 - 200810924 A diagram of the boundary line between the phase and the dark phase.

In the present invention, in order to maximize the function of the copolymerized polyester and the polyurethane which are the raw materials of the adhesive reforming layer, the important adhesive reforming layer becomes a microphase separation structure or a nano phase. Phase separation structure. If the two resins are completely compatible, the properties of the two resins are offset, and the excellent properties of the copolymerized polyester or polyurethane are not expected as a whole. In the adhesive modification layer, other phase separation structures which can be taken as the PEs phase and the PU phase are also considered to be dispersed in the PEs phase, and the so-called composite morphology in which the PEs phase is dispersed in the PU phase, that is, the display representative Island structure. Of course, when the island structure is in an incompatible state of the resin, if one resin phase is added, the other is inevitably reduced, and a so-called island is formed. In the present invention, if the manufacturing conditions are controlled, it may be an adhesive layer formed by a separate phase having such an island structure. However, considering the unevenness of the size of the resin phase for forming the island structure or the unevenness of the distribution state, the influence of the shape, the number, and the distribution state of the island phase cannot be ignored. Therefore, there is also a concern about the great influence of the properties of the resin constituting the sea structure. Therefore, it is considered that the phase separation structure of the PEs phase and the PU phase of the present invention is advantageous in maintaining the uniformity of the material in forming a phase separation structure which is mutually coupled to each corner. The phase separation structure showing the sea-island structure of the PEs phase and the PU phase can also be cited as one of the representative aspects of the present invention. Further, as another phase separation structure of the adhesion modifying layer in the present invention, a core-shell structure may be formed. For example, the PU phase surrounds the perimeter of the PEs phase, and the PEs phase surrounds the packet structure. However, in order to form such a core-shell structure -25-200810924, a very high degree of control is required. Moreover, since the core-shell structure is adopted, it is not expected to exhibit excellent material behavior.

Furthermore, as a phase separation structure, a laminated structure in which the PEs phase and the PU phase are alternately arranged side by side may be employed. However, it is desirable that the phases are arranged at approximately equal intervals in parallel, but if the width of the phase is increased, it is difficult to uniformly distribute the P E s phase and the P U phase at the interface of the adhesion modifying layer. There are even defects that affect the quality of the adhesively modified substrate film. By the subtle alienation of the manufacturing conditions, it is possible to adopt a sea-island structure, a core-shell structure, and a laminated structure, and to form such a mixed existence type. However, in the adhesive modification layer, the PE s phase and the PU phase have a certain size, and they are uniformly mixed everywhere, which is important for maintaining quality. Further, the phase separation structure in which the PEs phase and the PU phase are two layers in the thickness direction in the adhesion modifying layer is not preferable in the present invention. In the present invention, in the surface of the adhesion-modifying layer (the interface with the hard coating layer), the PEs phase and the PU phase are uniformly distributed at an appropriate area ratio, which is important from the viewpoint of the effect of the present invention. of. The phase separation structure in the surface of the modified layer or the cutting surface, having a polyester phase containing a copolymerized polyester as a main component and a polyurethane phase containing a polyurethane as a main component, each With an irregular shape. Therefore, these resin phases are arranged on the surface and inside of the adhesive reforming layer, and are arranged irregularly and densely to form a complicated alignment structure. Further, it may have a structure in which the surface of one resin phase is invisible in a state in which the other resin phase is incompatible. Further, in Fig. 3, the black portion indicates the polyester phase, and the white portion indicates the polyurethane phase. -26- 200810924 In the surface of the adhesion modifying layer of the adhesive-modified substrate film, for a unit area (for example, 5 χ 5 μm), when the two resin phases are uniformly arranged in a separated state, one resin phase If the size becomes larger, the size of the other resin phase is limited. Therefore, a large deviation occurs in the presence of the resin phase. As a result, the two resins are separated from each other, and it becomes difficult to maintain a uniform dispersion state. Since the material of the adhesion-modifying layer is uneven, quality management is not good.

In order to cause phase separation of the two resin phases and to present in the adhesion modifying layer in a state of uniform mixing, it is preferred that the shape of the PEs phase is 短μπι in the short axis direction and Ιμπι in the long axis direction. the above. Of course, in the case where the quality is not highly demanded, a relatively large configuration in which the width in the short axis direction is at most about 6 μm is also possible. The phase separation structure of the continuous phase (PEs phase) is a resin composition of a coating liquid for forming an adhesive layer, a type and concentration of a surfactant, a coating amount, and a drying condition of a coating layer. And heat setting conditions, etc., control them, and exhibit a specific microphase separation structure or a nano phase separation structure in the adhesion modifying layer. In summary, as shown in Fig. 1, the phase separation structure of the polyester phase and the polyurethane phase on the surface of the adhesive modification layer is used to exhibit the adhesive modified substrate film of the present invention. A representative model of the effect. Furthermore, the importance of the phase separation structure will be described in detail. In the adhesive modified base film used in the present invention, it is preferred that the adhesive modified layer is a copolymerized polyester component and a polyurethane component as a resin component, and a copolymerized polyester is used as a main component. The PEs phase of the component is phase separated from the PU phase with the polyurethane as a main component, and each phase has a continuous structure -27-200810924. When the two kinds of resins are not uniformly mixed and phase-separated, the base film formed of the thermoplastic resin film has excellent adhesion and has a relatively good solvent resistance. In the case of many resins such as a hard coating layer, a diffusion layer, and an acrylic resin, the polyurethane having excellent adhesion is not able to offset the respective characteristics, and the characteristics of each resin can be fully utilized.

The polyester phase constituting the adhesive reforming layer is preferably composed of a copolymerized polyester alone, but may also contain 0.01 to 40% by mass of a polyurethane. Further, 0.001 to 20% by mass of particles may be contained in the polyester phase. Further, in the polyester phase, a surfactant may be attached or contained in the above resin. Similarly, the polyurethane phase is preferably composed of a polyurethane, and may contain particles, an surfactant, and the like in an amount as described in the above-mentioned copolymerized polyester. In particular, in the case of particles having a high affinity with the polyurethane, during the formation of the adhesion-modifying layer, it is optionally made more in the polyurethane phase than in the polyester phase. Be biased. In general, in a composition obtained by copolymerizing a mixture of a polyester and a polyurethane, usually both are chemically uniform materials, and the chemical replenishment function exhibiting each other's properties or functions is exhibited. Many. On the other hand, in the case of the adhesive modified layer of the polyester phase and the polyurethane phase of the present invention, the polyester phase and the polyurethane phase are physically separated as described above. In the presence of a resin phase, a large variation occurs, and the two resin phases are separated to maintain a structure in which the resin is uniformly dispersed. Each resin has its own properties, and the function of the anti-blocking property is shared by the surface of each resin phase, for example, a copolymerized polyester, and the polyurethane functions to share the adhesion, and each of them is in a phase-separated state. For example, the performance of physical supplemental functions, its function or principle, is a novel technical issue that is completely unknown in the prior art.

In the present invention, the detailed mechanism of the phase separation structure of the adhesion modifying layer is not clear. However, the composition ratio of the copolymerized polyester to the polyurethane, the ratio of the dispersion medium of water to the alcohol, the type of the surfactant, the impurities in the surfactant, the pH of the aqueous coating liquid, the coating amount, and the like The material composition or characteristics of the coating liquid, the balance between the time and temperature of the drying and heat setting treatment, and the subtle conditions of the wind speed can exhibit a specific micro phase separation structure or a nano phase separation structure in the adhesion modifying layer. The examples are easily understood in comparison with the comparative examples. Further, the reaction starting temperature of the isocyanate group which the polycarbamate has has a subtle influence. The phase separation structure referred to herein means that the so-called PEs phase and the two phases of the PU phase maintain physical boundaries, rather than being separated from each other, and the boundary system is not in contact with each other. In the PEs phase, the copolymerized polyester system is mostly concentrated. In the PU phase, the door is mostly offset by the polyurethane. The boundary of the two layers is clearly distinguished, and the separation boundary should be visible in appearance. Therefore, in the case of the present invention, the isocyanic acid of the polyurethane exhibits a complicated separation structure based on the possibility that the side also reacts. The adhesive modified base film used in the present invention has an adhesive modified layer formed of a pes phase and a PU phase, and is, for example, a substrate, a hard coat layer or a diffusion layer formed of a thermoplastic film. There is a function between the functional layers to achieve the same function of the interface function on both sides of the so-called substrate surface and functional level. Thus, both the PEs phase and the PU phase adopt a structure in which the two are separated, and the state of the PEs phase is -29-200810924. The state of the PEs phase is the superior property of the copolymerized polyester originally possessed, and the two sides of the adhesive modified layer (substrate and Next, the interface of the modified layer, the interface between the functional layer such as the subsequent modified layer and the hard coating layer is selected to the maximum extent. That is, the state of the PU phase is such that the excellent properties of the originally possessed polyurethane have a maximum of both sides.

This is because in the film of the adhesion-modified substrate having the adhesion-modifying layer, the surface of the adhesion-modifying layer has a microphase-separated structure or a nanophase-separated structure formed by the PEs phase and the PU phase, so PEs The phase copolymerized polyester is exposed to maximize the properties or functions of the copolymerized polyester. Similarly, the PU phase of the polyurethane is exposed to maximize the properties of the polyurethane. Or function. Therefore, on the surface of the adhesion modifying layer, if the PEs phase and the PU phase are each distributed in a specific range, the properties or functions of the two resins can be maximized. This is due to the unique structure of the laminate, which acts reasonably at the interface between the substrate and the adhesion modifying layer, and at the interface between the adhesion modifying layer and the functional layer. Further, in the present invention, when particles are contained in the resin composition constituting the PEs phase and the PU phase, for example, the vermiculite particles may be biased in the PU phase. It is speculated that this is because the PU phase is closer to the vermiculite particles than the PEs because of the surface energy. When the vermiculite particles are biased in the PU phase, the shortness of the polyurethane, that is, the anti-adhesion property, and the particle content of the entire adhesive reforming layer can be reduced, so that it is beneficial to achieve the function of maintaining transparency. Construction. Similarly, if a particle having a surface energy closer to the copolymerized polyester is selected, it is implicitly selected to bias the particle in the PEs phase. Any one of the structures in which the particles are separated by the PEs phase or the PU phase is not a prior art. -30- 200810924 The desired method can improve the smoothness or adhesion while maintaining transparency. Therefore, it is also of interest in the present invention to augment the micro-phase, the application range of the material design from the structural or nanophase separation structure. (2) Thermoplastic resin film

The thermoplastic resin film used in the present invention is preferably an unaligned sheet obtained by melt-extruding or solution-extruding a thermoplastic resin, and stretching in one axial direction in the longitudinal direction or the width direction as needed, or in two axes. A biaxially stretched thermoplastic resin film which is subjected to heat setting treatment by sequential biaxial stretching or simultaneous biaxial stretching in the direction. Further, the thermoplastic resin film may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, or the like, within the range not impairing the object of the present invention. Surface activation treatment. The thickness of the thermoplastic resin film used in the present invention is in the range of 30 to 300 μm, and can be arbitrarily determined in accordance with the specifications of the use. The upper limit of the thickness of the thermoplastic resin film is preferably 25 μm, particularly preferably 20 μm. On the other hand, the lower limit of the film thickness is preferably 50 μm, particularly preferably 7 5 μm. If the film thickness is less than 50 μm, the rigidity or mechanical strength may be insufficient. On the other hand, if the thickness of the film exceeds 300 μm, the absolute amount of impurities present in the film increases, so that the frequency of optical defects becomes high. Further, the cutting property is also deteriorated when the film is cut into a predetermined width, and the manufacturing cost is increased. Further, since the rigidity is increased, it is difficult to wind the long film into a cylindrical shape. Examples of the thermoplastic resin include polyethylene (poly), polypropylene (ΡΡ), and poly-31-200810924.

Polyolefins such as methylpentene (TPX), polyethylene terephthalate (PET), polyethylene 2,6-naphthalate (PEN), polytetramethylene terephthalate (PTT), Polyester resin such as polybutylene terephthalate (PBT), polyamine (PA) resin such as Nylon 6, Nylon 4, Nylon 66, and Nylon 12, polyimine (PI), poly Amidoxime (PAI), polyether oxime (PES), polyetheretherketone (PEEK), polycarbonate (PC), polyarylate (PAR), cellulose propionate, polyvinyl chloride (PVC), Polyvinylidene chloride, polyvinyl alcohol (PVA), polyetherimide (PEI), polyphenylene sulfide (PPS), polyphenylene ether, polystyrene (PS), aligned polystyrene, raw borneol It is a polymer or the like. Further, these polymers may be used singly, or may contain a small amount of a copolymerization component, or may be blended with one or more other thermoplastic resins. Among these thermoplastic resins, polyethylene terephthalate, propylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, aligned polystyrene, and norbornene polymerization are preferred. , polycarbonate, polyarylate, and the like. Further, a resin having a polar functional group such as polyester or polyamine is preferred from the viewpoint of adhesion to the adhesion-modifying layer. Among them, more preferred are polyethylene terephthalate, polyethylene naphthalate-2,6-ethylene diester, polybutylene terephthalate, propylene terephthalate or the constituents of such resins. The copolymer as a main component is particularly preferably a biaxial alignment film formed of polyethylene terephthalate. For example, as the resin for forming the thermoplastic resin film, when a polyester copolymer having polyethylene terephthalate as a basic skeleton is used, the ratio of the copolymerization component is preferably less than 20 mol%. When it is 20 mol% or more, the film strength, transparency, and heat resistance are deteriorated. Examples of the dicarboxylic acid component which can be used as a copolymerization component include an aliphatic group such as adipic acid or sebacic acid.

200810924 A dicarboxylic acid, an aromatic acid such as isonic acid, citric acid or 2,6-naphthalene dicarboxylic acid, a polyfunctional carboxylic acid such as trimellitic acid or pyromellitic acid. Further, the diol component used as the copolymerization component may, for example, be a fatty acid diol such as diethylene glycol, diol, propylene glycol or neopentyl glycol; or an aromatic diol such as dimethyl; An alicyclic two-average molecular weight of cyclohexanedimethanol or the like of from 150 to 20,000, such as polyethylene glycol. Further, in the above thermoplastic resin, various additives other than the catalyst may be contained within the range not inhibiting the present invention. Examples of the additives include inorganic particles, heat-resistant polymer particles, alkali metals, alkaline earth metal compounds, phosphorus compounds, antistatic agents, ultraviolet agents, light stabilizers, flame retardants, heat stabilizers, antioxidants, gelatinization, and the like. Interface inclusions, etc. From the point of view of the handling property (slip property, ductility, adhesion, air deaeration of the air, etc.) at the time of roll-up or roll-out of the thermoplastic resin film, the particles are It is used to impart a moderate surface unevenness to the surface. Examples of the inorganic particles include calcium carbonate, calcium phosphate, amorphous, crystalline glass pigment, kaolin, talc, titanium dioxide, and shisha-oxidized composite oxide particles, barium sulfate, fluorinated gold, and zeolite. Molybdenum sulfide, mica, etc. Further, examples of the heat resistant polymer include crosslinked polystyrene particles, crosslinked acrylic resin particles, methyl methacrylate particles, benzoguanamine formaldehyde condensation products, light amines, formaldehyde condensate particles, and polytetrafluoroethylene. Ethylene particles, etc. When a polyester film is used as the thermoplastic resin film, the dicarboxylic acid is a 1,4-butylbenzene glycol; a flat effect additive, and the compound wire absorption preventing agent is wound into a circular winding film.矽 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝 氧化铝For applications that require transparency. On the other hand, a titanium oxide-like white pigment is suitable for applications requiring shielding. Further, the particles contained in the thermoplastic resin film may be one type or several types may be used.

The average particle diameter is 〇·〇1 to 2 μπχ, and the particle content in the film is 0.01 to 5 in terms of the balance of the transparency and the handleability in terms of the type of the particles, the average particle diameter, and the amount of addition. • Within the range of 0% by mass, it can be determined according to the use of the film. Further, in the case where the transparency of the adhesive-modified substrate film to be used in the present invention is highly demanded, it is preferable that the thermoplastic resin film does not substantially contain particles which are responsible for lowering the transparency, and is subsequently The modified layer contains the composition of particles. The phrase "substantially free of particles" means that, for example, in the case of inorganic particles, when the inorganic element is quantified by fluorescent X-ray analysis, the content thereof is 50 ppm or less, preferably i 〇 ppm or less, and most preferably Below the limit. In this case, even if particles are not actively added to the base film, the contaminated components from the foreign matter, and the peeling of the dirt adhering to the production line or the device during the process of the raw resin or the film are mixed into the film. Further, the layer structure of the thermoplastic resin film used in the present invention may be a single layer or a laminated structure which imparts a function which cannot be obtained by a single layer. In the case of laminated construction, the co-extrusion method is suitable.情况 When polyester is used as a raw material of a thermoplastic resin film, a method of producing a base film will be described in detail below. The inherent viscosity of the nine polyesters used as the raw material of the film is preferably -34-

200810924 is in the range of 0.45~0.70dl/g. If the intrinsic viscosity is lower than when the film is produced, it becomes easy to break frequently. On the other hand, when it exceeds 0.70 dl/g, the filtration pressure is greatly increased, and it is difficult to reduce the high precision. Further, in the hard coating film of the present invention or the film-forming film, it is preferred to remove impurities in the ester which is a cause of optical defects. In order to remove impurities in the polyester, the molten resin is filtered at any place maintained at about 280 ° C for melting. The filter material for high-precision filtration of the molten resin is not limited. However, in the case of the filter material of the stainless steel sintered body, the removal property of the aggregates of the Si and Ti as the main components and the high-melting organic substance is suitable. Filtration of a filter material for high-precision filtration of a molten resin: a period filtration efficiency of 95%), preferably 15 μm or less. When the amount of the filter material is less than 15 μm, the impurities of 20 μm or more are removed. The filter material having a filtered particle size (initial filtration efficiency of 95%) is used for high-precision filtration of the molten resin. However, in order to obtain a film having few optical defects, this is extremely important in the extrusion process of the molten resin. In the cooling program of the microchip-shaped melt, the periphery of the impurities is subjected to the inhomogeneity of the alignment in the program, and the occurrence of minute occurrence of the lens state occurs. Here, if there is scattering of the lens shell 1 , it will be larger than the actual impurities when viewed by the naked eye, and the difference in thickness can be regarded as the height of the convex portion and the box of the concave portion 0.45 dl / g ', intrinsic viscosity filtration, production The optical function is contained in the time when the raw material is extruded, and the high precision is limited to Sb, Ge, and Cu. The particle size is excellent (the primary filter particle is large and the volume is less than 1 5 μηι or less). : Fine impurities, crystallized in f, its difference in J thickness, !J light will refract or ί. The difference in the slight twist, -35- 200810924 If the convexity of the convexity is more than 1 'and the convex part The 丨 丨 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接 邻接The above situation of the big optical defects.

In order to obtain a highly transparent film, it is preferred that the thermoplastic resin film does not contain particles, and the smaller the particle content, the higher the transparency, and the optical disadvantage of minute irregularities tends to be more distinct. Further, since the surface of the thick film is less likely to be quenched than the thin film, crystallization tends to occur, so that the entire film must be quenched at the time of production of the unaligned sheet. As a method of cooling the unaligned sheet, it is preferable to extrude the molten resin from the slit portion of the die to the rotating cooling drum, and to make the sheet-like melt adhere to the rotating cooling drum, and to make a step Cold method. As a method of cooling the air surface of the unaligned sheet (the opposite surface to the contact surface of the cooling drum), a method of blowing a high-speed air stream to cool is effective. (3) Adhesive modified layer The adhesive modified base film used in the present invention can be obtained by using a copolymer containing a copolymerized polyester and a polyurethane, a dispersion medium containing an aqueous and alcohol, and a surfactant. An aqueous coating liquid as a main constituent component, which is continuously applied to a coating step on one or both sides of a traveling thermoplastic resin film, and a drying step of drying the coating layer (adhesive modifying layer), followed by at least one axial direction The step of stretching, and then forming the stretched coated film as a heat setting treatment step of heat setting treatment, is continuously formed to produce an adhesive layer having a micro phase separation structure or a nano phase separation structure. The substrate film is subsequently modified. Further, at least one crosslinking agent selected from the epoxy crosslinking agent, the melamine crosslinking agent, and the 噚-36 - 200810924 oxazoline crosslinking agent is mixed into the coating liquid to be heat-treated, or may be a total of A crosslinked structure is formed in the polymerized polyester. In the method for producing an adhesive-modified substrate film provided with an adhesion-modifying layer having a microphase-separated structure or a nanophase-separated structure, the above-mentioned copolymerized polyester (PEs) and polyurethane (pu) The mass ratio (PEs/PU) is 30/70 to 70/30, and it is preferable to satisfy the following conditions (a) to (f). Further, the same applies to the case where the crosslinking agent is contained in the coating liquid.

(a) from the application of the coating liquid to the entrance of the drying step, the passage time of the film is less than 2 seconds, (b) in the drying step, at a temperature of 120 to 150 ° C for 0.1 to 5 seconds, In the drying step, the wind speed of the drying wind is 30 m/sec or more, and (d) the heat setting process is continuously divided into a plurality of heat setting zones, and each zone can be independently temperature-controlledly separated, and the film passes through The temperature of the first heat setting zone is 190 to 200 ° C, and the temperature of the heat setting zone set at the highest temperature is 210 to 240 ° C, from the outlet of the first heat setting zone to the heat setting zone set at the highest temperature (and In a few cases, the passage time of the film up to the heat-setting zone on the inlet side is 10 seconds or less, (e) the non-ionic surfactant or the cationic surfactant for the coating liquid, and 0.01 1 is added. 0.18 mass%, (f) The final coating amount of the subsequent modified layer is 0.005 to 0.20 g/m2, and in the production of the above-mentioned adhesive modified base film, it is more preferable to satisfy the following (g) to (() Conditions of i): (g) From the application of the coating liquid to the entrance of the drying step, the film The passage time is less than 1.5 seconds, -37- 200810924 (h) in the drying step, at a temperature of 130~15 0 °C for 0·5~3 seconds, (i) in the heat setting process step, set in The temperature of the heat-set zone of the highest temperature is 225 to 23 ° C, from the outlet of the first heat-set zone to the heat-set zone set at the highest temperature (and at several times, the heat-set zone on the most recent inlet side). The passage time of the film is 5 seconds or less.

Further, in the adhesion-modifying layer which is laminated by the above-described in-line coating method, fine particles having an appropriate particle diameter are formed, and appropriate irregularities are formed on the surface of the adhesion-modified layer to impart slip and winding properties. Scratch resistance. Therefore, it is not necessary to contain fine particles in the thermoplastic resin film, and high transparency can be maintained. In the adhesive modified base film used in the present invention, the three-dimensional center plane average surface roughness (SRa) of the surface of the adhesive modified layer is preferably a smoother of 0.002 to Ο.ΟΙΟμπι. The upper limit of S Ra is, from the point of view of transparency, more preferably 0·0080 μιη, and particularly preferably 0.0060 μπι. On the other hand, the lower limit of SRa is more preferably 〇〇25μπι, especially excellent 0·0030μιη from the viewpoints of handleability and scratch resistance such as slipperiness and windability. It is not preferable that the surface of the modified layer has a smooth surface of less than 0.002 μm, because when the film of the adhesive modified substrate is wound into a cylindrical shape, the anti-blocking property is lowered, or the film is produced. At the time of processing or processing, handling properties such as slip properties and winding properties and scratch resistance are lowered. On the other hand, when the SRa of the surface of the adhesive-modified layer exceeds Ο.ΟΙΟμπι, the haze increases and the transparency deteriorates, so that it is not suitable as a base film of a hard coating film or an optical functional film using the same. In the adhesive modified base film used in the present invention, the adhesive modified layer has the following four structural features, which can be obtained by the following means -38-200810924. (a) microphase separation or nanophase separation in the polyester phase and the polyurethane phase, which have a specific area ratio, (b) the composition ratio of the resin component of the subsequent modified layer can be on the surface and Internal change, (c) When particles are contained in the adhesion modifying layer, the particles are biased in the polyester phase or the polyurethane phase.

Further, the polyester phase having the copolymerized polyester as a main component observed on the surface of the adhesion modifying layer preferably has a continuous structure having a width of at most 1 μm and a length of more than 1 μm, more preferably copolymerization. The polyester phase has a co-continuous structure with the polyurethane phase. By having a fine continuous structure in which the width of the polyester phase having the copolymerized polyester as a main component is at most 1 μm and the length exceeds 1 μm within the range of the area ratio of the PEs phase on the surface of the adhesive reforming layer, Microscopic uniform adhesion can be obtained. In the polyester phase in which the copolymerized polyester is used as a main component, the portion having a width of at most 1 μm is dispersed in the phase separation structure, and the hard layer, the diffusion layer, and the enamel layer are locally adhered to each other. Poor place. If there is a place where the adhesion is poor on the surface of the adhesive reforming layer, there is a giant peeling connection starting from this portion. In order to make the width of the polyester phase to a fine continuous structure of at most 1 μm, it is important to appropriately select the time and heat setting conditions required from the transverse stretching zone to the maximum temperature of the heat setting zone. In particular, if the time required from the transverse stretching zone to the highest temperature zone of the heat setting zone is too long, the phase separation of the adhesion modifying layer is excessively performed, and as a result, the copolymerized polyester is used as a main component. Polyester phase width -39- 200810924 The narrowest place, more than 1 μπι is scattered. The specific heat setting conditions at the time of producing the adhesive-modified base film are described later. In order to control the phase separation structure of the surface of the final adhesive reforming layer, the solvent evaporation rate in the drying step described later and the subsequent heat treatment are extremely important. By controlling the evaporation rate of the solvent in the drying step, the composition ratio of the polyester component to the polyurethane component can be changed in the surface of the adhesive modifying layer.

For example, when a mixed solvent of water/isopropyl alcohol is used, under a weak drying condition, the solvent remains in the solvent on the surface in the late drying stage, and the ratio of water becomes large. Therefore, the ratio of the more hydrophilic polyurethane having a higher hydrophilicity to the surface of the adhesive modifying layer is higher than that when the adhesive modifying layer is dried under strong conditions. Further, even when the coating amount is changed and the evaporation rate of the solvent is controlled, the same effect cannot be obtained. When the coating amount is increased, it takes a long time to dry, and the ratio of water in the residual solvent of the coated surface is increased shortly before drying. That is, in the surface of the adhesive reforming layer, the ratio of the polyurethane component may be increased as compared with the case where the coating amount is small. The phase separation of the polyester component and the polyurethane component is carried out in the stretching step and the heat setting treatment step. However, if either of the resins starts to thermally crosslink, the mobility of each phase is greatly lowered, and the progress of phase separation is suppressed. That is, the phase separation structure can be controlled by controlling the heating conditions in the stretching step and the heat setting treatment step. As described above, in the drying step, the ratio of the presence of the polyester/polyurethane in the vicinity of the surface of the adhesive modifying layer is controlled, and the phase separation is controlled in the stretching step and the heat setting treatment step, and then the control can be closely controlled. The modified phase layer -40-200810924 surface phase separation structure and the existence ratio of each phase near the surface of the adhesion modifying layer. Further, by controlling the surface energy of the particles contained in the adhesive reforming layer, the particles are selectively biased to a polyester phase having a copolymerized polyester as a main component or a polyurethane as a main component. 0 of any of the polyurethane phases

The next modified layer contains a copolymerized polyester and a polyurethane as a main resin component. In the copolymerized polyester alone, the adhesion to the polyester-based base film is sufficient, but the adhesion to the hard coating layer containing the inorganic fine particles is inferior. Further, since it is a relatively brittle resin, cohesive failure is liable to occur during the cutting. On the other hand, the individual polyurethanes are excellent in adhesion to the hard coating layer containing inorganic fine particles, but are inferior in adhesion to the polyester base film. Further, when the adhesive modified base film is wound into a cylindrical shape, the anti-blocking property is inferior. Therefore, the hard coat film or the optical functional film produced by using the adhesive modified base film of the adhesive modified layer of the polyurethane monolithic system has a markedly lowered grade. In order to avoid such a problem, it is necessary to contain a large amount of particles in the adhesive reforming layer, to contain particles having a large particle diameter, or to increase the content of the particles. As a result, since the haze of the film is increased, it is particularly unsuitable as a base film of a hard coating film or an optical functional film which is required to be transparent. (3 -1) Preparation step of forming a coating liquid for the adhesion-modifying layer In the present invention, the adhesion-modifying layer is formed by a coating method. The materials used in the coating liquid are resins and dispersion media or solvents. In the present invention, the coating liquid for forming the adhesion modifying layer is preferably aqueous. Also, at -41 - 200810924

In the present invention, in addition to the resin component, particles and a surfactant are preferred embodiments. Further, an antistatic agent, an ultraviolet absorber, an organic lubricant, an antibacterial agent, an optical oxidation catalyst or the like may be used as needed. Further, in the coating liquid, a catalyst may be added to promote the thermal crosslinking reaction of the resin, and for example, various chemicals such as inorganic substances, salts, organic substances, basic substances, acidic substances, and metal-containing organic compounds may be used. . Further, in order to adjust the pH of the aqueous solution, an alkaline substance or an acidic substance may be added. The coating liquid is prepared by dispersing or dissolving the resin in a dispersion medium or a solvent under stirring, and then diluting it to a desired solid content concentration by using a surfactant and optionally various additives. Further, in order to uniformly disperse the resin component and the particles of the coating liquid, it is preferable to precisely filter the coating liquid in order to remove impurities such as coarse particle agglomerates and particles in the process. The type of the filter medium for precisely filtering the coating liquid is not particularly limited as long as it has the above properties, and may be, for example, a monofilament type, a felt type, or a mesh type. The material of the filter material for the fine filtration of the coating liquid is not particularly limited as long as it has the above-described properties and does not adversely affect the coating liquid, and may be, for example, stainless steel, polyethylene, polypropylene, or nylon. The filter material for finely filtering the coating liquid is preferably a filter material having a filter particle size (initial filtration efficiency··9 5%) of 25 μm or less, more preferably a filter material having a filtration performance of 5 μm or less, and particularly excellent filtration performance. Filter material below 1 μΐη. It is best to use a combination of filters with different filtration properties. When a filter material having a filter particle size of more than 25 μm is used, the removal of coarse aggregates is not sufficient. Therefore, the coarse aggregate which has not been removed by filtration is enlarged by the alignment stress of the one-axis alignment or the biaxial alignment step after drying -42-200810924, and it is easy to become an optical defect because an aggregate of 100 μm or more is observed. The raw materials used in the coating liquid will be described in detail below. (a) resin

In the present invention, as the resin constituting the adhesion modifying layer, a copolymerized polyester (PEs) and a polyurethane (PU) are used. In the coating liquid, the mass ratio of the solid content of the copolymerized polyester (PEs) to the polyurethane (PU) is preferably (PEs) / (PU) = 70 / 30 ~ 30 / 70, particularly good System 60/40 ~ 40/60. Further, the resin constituting the adhesion modifying layer may be a third resin in addition to the copolymerized polyester and the polyurethane. Further, a crosslinking agent can also be used. Further, in the present invention, the area ratio of the polyester phase on the surface of the adhesive modified layer and the resin component to the adhesive modified layer are as shown in Fig. 6 Ground, there is no correspondence. It is clearly shown in Fig. 6 that, for the resin component of the adhesion modifying layer, even if the mass ratio of the copolymerized polyester is 50%, the surface fraction of the PEs of the surface of the subsequent modified layer changes to 30. ~9 1% so far. This suggests that the composition and ratio of the copolymerized polyester to the polyurethane are different between the surface and the inside of the adhesion modifying layer. That is, this implies that the composition ratio of the copolymerized polyester to the polyurethane can be arbitrarily controlled in the thickness direction of the adhesive reforming layer. Further, when the ratio of the copolymerized polyester to the polyurethane is in the above range in the adhesive reforming layer, the hardness index of the surface of the adhesive modified layer can be made 3.0 to 15 . . When the hardness index of the surface of the modified layer is 3.0 nm lower, the adhesive layer becomes brittle. Therefore, in the process of forming a hard coating layer, a diffusion layer, or a ruthenium layer -43-200810924 with an acrylic resin as a constituent component, the cutting is performed at a high speed cutting in a processing step of cutting at a high speed at a high speed. In terms of force, it becomes difficult to obtain sufficient adhesion. Further, if the hardness index of the surface of the adhesive layer is more than 15 nm, the anti-blocking property is liable to lower. Further, the coating properties, adhesion properties, and solvent resistance of the base film tend to be insufficient.

In the present invention, the phase-separated structure of the water-dispersed copolymerized polyester component and the hydrophilic polyurethane component is presumed to be formed as follows. The two resin components mixed in a common solvent are in a state of being uniformly dispersed or dissolved in the coating liquid. After coating on the PET film, the coating surface through the drying step is in a uniform state without a clear phase separation structure. Then, the phase separation structure is expressed by the heat treatment in the stretching step and the heat setting treatment step. Namely, the phase in which the copolymerized polyester is used as a main component is separated from the phase in which the polyurethane is used as a main component. Further, it is considered that as the phase separation proceeds, the ratio of the copolymerized polyester component having a lower surface energy existing in the vicinity of the surface of the adhesion modifying layer becomes higher. (Copolymerized Polyester) In the adhesive modifying layer used in the present invention, the copolymerized polyester used is preferably an aromatic dicarboxylic acid component, and an ethylene glycol and a branched glycol as a glycol component. As a constituent. Examples of the branched diol component include 2,2-dimethyl·1,3-propanediol, 2-methyl-2-ethyl-1,3-propanediol, and 2-methyl-2-butylene. -1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-2-isopropyl-1,3-propanediol, 2-methyl-2-n-hexyl 1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2·ethyl-2-n-butyl-1,3-propanediol, 2-ethyl-2-n-hexyl-1, 3-propanediol, 2,2-di-n-butyl-indole, 3-propanediol-44- 200810924, 2-n-butyl-2-propyl·1,3-propanediol, and 2,2-di-n-hexyl· I, 3, propanol, etc. The molar ratio of the branched monool component is preferably 10% by mole for all of the diol components, and particularly preferably 20% by mole. On the other hand, the upper limit is preferably 80 %%%, particularly preferably 70% by mole, and particularly preferably 6% by mole. Further, diethylene glycol, propylene glycol, butanediol, hexanediol or 1,4-cyclohexanedimethanol may be used as needed. As the aromatic dicapric acid component, it is most preferable to citric acid and isononanoic acid. When the total dicarboxylic acid component is in the range of 1 〇 mol% or less, it may be added with other aromatic dicarboxylic acids, particularly diphenyl carboxylic acid and 2,6-naphthalenedicarboxylic acid. The group dicarboxylic acid is copolymerized.

The copolymerized polyester used as the resin component of the adhesive modifying layer of the present invention is preferably a water-soluble or water-dispersible resin. Therefore, in addition to the above dicarboxylic acid component, in order to impart water dispersibility to the polyester, it is preferred to use 5-sulfoisodecanoic acid or an alkali metal salt thereof in the range of 1 to 10 mol%, for example, sulfonate. P-quinic acid, 5-sulfoisodecanoic acid, 4-sulfonaphthylisophthalic acid-2,7-dicarboxylic acid and 5-(4-sulfophenoxy)isodecanoic acid or an alkali metal salt thereof. (Polyurethane) The polyurethane used in the subsequent modified layer is preferably a water-soluble or water-dispersible resin. For example, a resin containing a blocked isocyanate group and a thermally reactive water-soluble urethane having a terminal isocyanate group blocked by a hydrophilic group (hereinafter referred to as blocking) may, for example, be mentioned. Examples of the blocking agent for the isocyanate group include a hydrogensulfite and a sulfonic acid group-containing phenol, an alcohol, an indoleamine, or an active methylene-45-200810924 compound. . The blocked isocyanate system hydrophilizes or hydrolyzes the urethane prepolymer. The thermal energy of the above resin is imparted by a drying step or a heat setting treatment step in the production of a film, and since the blocking agent is detached from the isocyanate group, the above resin is mixed in a water-dispersible copolymerized polyester in a self-crosslinking network. It is immobilized and also reacts with the terminal group of the above resin or the like. The resin in the coating liquid adjustment is poor in water resistance due to hydrophilicity. However, when coating, drying, heat setting, and completion of thermal reaction, the hydrophilic agent of the urethane resin, that is, the blocking agent, is detached, so that a coating having good water resistance is obtained. membrane.

Among the above blocking agents, from the point of the heat treatment temperature, the heat treatment time, the point at which the blocking agent is detached from the isocyanate group, and the point which is industrially obtainable, the sulfite is optimal. Hydrogen salts. The chemical composition of the urethane prepolymer used in the above resin may be (1) an organic polyisocyanate having two or more active hydrogen atoms in the molecule, or a molecular weight having at least two active hydrogen atoms in the molecule. a compound having 200 to 20,000, (2) an organic polyisocyanate having two or more isocyanato groups in the molecule, or (3) a chain extender having at least two active hydrogen atoms in the molecule, having an end Isocyanate-based compound. The compound (1) may, for example, be a generally known compound having two or more hydroxyl groups, carboxyl groups, amine groups or sulfhydryl groups in the terminal or molecule. Preferred examples of the compound include polyether polyols and Polyether ester polyols and the like. In addition, examples of the polyether polyol include alkylene oxides such as ethylene oxide and propylene oxide, and polymerized compounds such as styrene oxide and epichlorohydrin, or random polymerizations thereof. A compound obtained by block polymerization or addition polymerization of a polyvalent alcohol. -46· 200810924 Examples of the polyester polyol and the polyether ester polyol include compounds which are mainly linear or branched. a polyvalent saturated or unsaturated carboxylic acid such as succinic acid, adipic acid, citric acid or maleic anhydride, or the like, and ethylene glycol, diethylene glycol, 1,4-butanediol, and neopentyl Polyvalent alkyl ether glycols such as polyvalent saturated and unsaturated alcohols such as diol, 1,6-hexanediol and trimethylolpropane, and relatively low molecular weight polyethylene glycol and polypropylene glycol Or a condensation reaction of a mixture of such alcohols.

Further, examples of the polyester polyol include polyesters obtained from lactones and hydroxy acids. Further, as the polyether ester polyol, a polyether ester obtained by adding ethylene oxide or propylene oxide to a polyester produced in advance can be used. Examples of the organic polyisocyanate of the above (2) include isomers of tolyl diisocyanate, aromatic diisocyanates such as 4,4-diphenylmethane diisocyanate, and benzodimethyl diisocyanate. Aliphatic diisocyanates such as aromatic aliphatic diisocyanates, isophorone diisocyanate and 4,4-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and 2,2,4-trimethyl An aliphatic diisocyanate such as hexamethylene diisocyanate or a polyisocyanate such as trimethylolpropane is preliminarily attached to the compound in a single or plural form. Examples of the chain extender having at least two active hydrogens in the above (3) include glycols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol. a polyvalent alcohol such as glycerin, trimethylolpropane or pentaerythritol, a diamine such as ethylenediamine, hexamethylenediamine or piperazine, or an amine alcohol such as monoethanolamine or diethanolamine. a thiodiglycol such as thiodiethylene glycol or water-47-200810924, in order to synthesize a urethane prepolymer, usually by a one-stage or multi-stage isocyanate addition polymerization method using the above chain extender The reaction is carried out at a temperature of 150 ° C or lower, preferably 70 to 120 ° C, for 5 minutes to several hours. The ratio of the isocyanate group to the active hydrogen atom is preferably 1 or more, but it is necessary to leave the free isocyanate group in the obtained urethane prepolymer. In addition, the content of the free isocyanate group is preferably 10% by mass or less, and the stability of the aqueous solution of the urethane polymer after the blocking is considered to be 7% by mass or less.

The obtained urethane prepolymer obtained is preferably blocked by using hydrogen sulfite. The reaction is carried out by mixing with bisulfite for about 5 minutes to 1 hour while stirring well. The reaction temperature is preferably 60 ° C or lower. It is then diluted with water to an appropriate concentration to serve as a thermally reactive water-soluble urethane composition. When the composition is used, it is prepared to an appropriate concentration and viscosity, but usually if heated to about 80 to 200 ° C, the bisulfite of the blocking agent will dissociate, and in order to regenerate the active isocyanate group, The addition polymerization reaction occurs in the molecule or in the molecule to form a polyurethane polymer or has an additive property to other functional groups. As an example of the resin (B) containing a blocked isocyanate group described above, the product name ELASTRON manufactured by Daiichi Kogyo Co., Ltd. is a representative example. ELASTRON is a method in which an isocyanate group is blocked by sodium hydrogen sulfite, and it has strong hydrophilicity at the molecular end, and is water-soluble due to the presence of an aminomethyl sulfonate group. (b) Solvent In the present invention, the solvent is not only a liquid in which a resin is dissolved, but also a dispersion medium for dispersing a resin into particles in a broad sense. In order to practice the present invention, various solvents such as an organic solvent and an aqueous solvent can be used. The solvent used for the coating liquid is preferably a mixture of water and ethanol such as ethanol, isopropyl alcohol or benzyl alcohol in a ratio of 30 to 50% by mass based on the total coating liquid. In addition, when it is less than 1% by mass, an organic solvent other than the alcohol may be mixed in a range in which it is likely to be dissolved. However, the total amount of the alcohol and other organic solvents in the coating liquid is less than 50% by mass.

When the amount of the organic solvent added is less than 50% by mass based on the total amount of the solvent, the drying property is improved during coating and drying, and the appearance of the coating layer is improved as compared with the case of water alone. When the amount of the organic solvent is 50% by mass or more in all the solvents, the evaporation rate of the solvent is increased, and the coating liquid is likely to change in concentration during coating. As a result, the viscosity of the coating liquid rises, the coatability is lowered, and the appearance of the coating film may be poor. Further, the risk of fire or the like is also increased due to volatilization of the organic solvent. In addition, when the amount of the organic solvent is less than 30% by mass, the ratio of the relative water is increased, and the highly hydrophilic urethane component is in the vicinity of the surface of the adhesive modified layer. Segregation. As a result, the area ratio of the PEs phase on the surface of the adhesion-modifying layer or the area ratio of the PU phase in the vicinity of the interface with the hard coating layer in the cutting surface of the adhesion-modifying layer is unlikely to be in an appropriate range. (pH adjustment of Ο coating liquid The coating liquid for forming an adhesive reforming layer in the present invention preferably has a pH of 5 or more and less than 8. When the pH of the coating liquid is less than 5, then -49 - 200810924

The area ratio of the PEs phase on the surface of the modified layer is increased, or the area ratio of the PU phase in the vicinity of the interface between the cutting surface of the adhesive modified layer and the hard coating layer is small, and the adhesion tends to be deteriorated. On the other hand, when the pH of the coating liquid is 8 or more, significant aggregation occurs depending on the type of the particles, and the haze is increased, and the transparency is deteriorated, which is not preferable. The pH adjusting agent is not particularly limited as long as it does not adversely affect the adhesion, the blocking resistance, and the coating property, or is negligible. For example, when the pH is raised, sodium hydrogencarbonate or sodium carbonate can be used, and when the pH is lowered, acetic acid or the like can be used. (d) When the aqueous coating liquid is applied onto the surface of the thermoplastic resin film, the coating liquid is uniformly applied in order to improve the wettability of the film, and a surfactant is usually used. In the present invention, in addition to the above, a surfactant may be used as one of means for controlling the phase separation structure of the surface or the inside of the adhesion-modifying layer. The surfactant is not particularly limited as long as it can obtain good coatability and an appropriate phase separation structure can be obtained on the surface or inside of the adhesive reforming layer. Among the surfactants, a fluorine-based surfactant which is excellent in applicability is preferably added in a small amount. Further, it is preferable that the area ratio of the PEs phase on the surface of the adhesion modifying layer or the area ratio of the pu phase in the vicinity of the interface between the hard coating layer and the cutting surface of the adhesion modifying layer is within an appropriate range. The coating liquid is blended with 0.01 to 0.18 mass% of a cationic surfactant or a nonionic surfactant. When an anionic surfactant is used, it is improved as shown above -50- 200810924

When the compatibility of the polyester and the polyurethane is copolymerized, it is difficult to obtain the phase separation structure defined in the present invention. The amount of the surfactant to be added can be appropriately selected within a range in which good adhesion to a functional layer such as a hard coating layer or a diffusion layer is not impaired, and good coating properties can be obtained. For example, in the case of a fluorine-based surfactant, it is suitable for pure water from a critical microcell concentration to less than 30 times. When the particles contained in the coating liquid become easily aggregated, the haze of the obtained laminated film is increased, and it is particularly unsuitable as a base film which is an optical functional film. Further, the surfactant component oozes out of the surface of the adhesive modifying layer, which also adversely affects the adhesion. On the other hand, below the critical microcell concentration, good coatability is not obtained. Further, the area ratio of the PEs phase on the surface of the adhesion modifying layer or the area ratio of the PU phase in the vicinity of the interface with the hard coating layer on the cutting surface of the adhesion modifying layer is difficult to control within an appropriate range. (Refining of Surfactant) The surfactant used in the present invention is preferably a purified one. Most of the surfactants listed on the market generally contain trace amounts of impurities. In particular, the amount of polyethylene glycol in the impureness prevents the acquisition of a good phase separation structure. In order to prevent this, it is preferred to carry out the pretreatment for removing impurities from the surfactant, and to use a refined surfactant. As a pretreatment step for removing impurities, a method of removing impurities may be carried out without deteriorating the surfactant, and is not particularly limited. For example, the following methods can be mentioned. For example, at least the surfactant and polyethylene glycol are dissolved in a soluble organic solvent, allowed to stand at a low temperature, and the surfactant of the main component is saturated -51 - 200810924, followed by filtration, and an interface having an improved purity is taken out. The method of the active agent. In the case of a perfluoroalkyl ethylene oxide adduct surfactant, it is dissolved in isopropanol on a warm bath at 30 ° C, and after standing at 0 ° C for 24 hours, the precipitate is removed by filtration. A surfactant having improved purity can be obtained. (e) particles

The haze of the subsequently modified base film is 1.5% or less. However, in applications where transparency is required, it is preferred to use an optically functional film using a hard coating film or the film. The above haze is preferably 1.0% or less. When the haze is more than 1.5%, when the film is used for a lens film for LCD or a base film for a backlight, the sharpness of the screen is lowered, which is not preferable. In order to make the haze of the adhesive modified base film 1.5% or less, it is preferred that the thermoplastic resin film does not contain particles. When the thermoplastic resin film does not contain particles, the handleability (slip property, travelability, adhesion, and air entanglement accompanying winding) is improved in order to improve scratch resistance or to be wound into a cylindrical shape or to be wound up. It is preferable to contain a specific amount of particles of a suitable amount in the adhesive reforming layer, and to form moderate irregularities on the surface of the adhesive modified layer. The particles are preferably particles having a high affinity with the copolymerized polyester or polyurethane, and it is preferred that the affinity differs in any of the phases. By causing the particles to be present in one of the phase-separated resins, the particles are moderately aggregated, and relatively small particles are added, i.e., the haze does not rise significantly, and excellent anti-blocking property can be obtained. Examples of the particles contained in the adhesive reforming layer include calcium carbonate, calcium phosphate, amorphous vermiculite, crystalline glass pigment, kaolin, talc, -52-200810924 titanium dioxide, aluminum oxide, and vermiculite. Inorganic particles such as alumina composite oxide particles, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, mica, crosslinked polystyrene particles, crosslinked acrylic resin particles, and crosslinked methyl methacrylate Heat-resistant polymer particles such as particles, benzoguanamine/formaldehyde condensate particles, melamine-formaldehyde condensate particles, and polytetrafluoroethylene particles. Among these particles, from the following points, it is preferable that the particles are meteorite particles.

The first advantage is that a film having a high transparency is easily obtained because the refractive index of the resin component of the adhesive layer is relatively close. The second advantage is that the vermiculite particles have a characteristic that is biased in the phase-separated polyurethane phase, and the polyurethane phase existing on the surface of the adhesive modified layer can be supplemented to have poor anti-blocking property. The inherent properties of the polyurethane resin. It is considered that this is because the surface energy of vermiculite particles and polyurethane is closer than that of copolymerized polyester, and the affinity is high. Further, the shape of the particles is not particularly limited, but from the viewpoint of imparting smoothness, particles close to spherical are preferable. The content of the particles in the next five-layered layer is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less. When the content of the particles in the modified layer is more than 20% by mass, the transparency is deteriorated, and the adhesion of the film is likely to be insufficient. On the other hand, the lower limit of the particle content is preferably 0.1% by mass, more preferably 1% by mass, particularly preferably 3% by mass, for the adhesion modifying layer. Further, in the adhesive reforming layer, two or more kinds of particles having different average particle diameters may be contained. -53- 200810924 Further, it is also possible to contain different average particle diameters of the same type of particles. In either case, the average particle diameter and the total content of the particles are within the above ranges. When the coating liquid is applied, in order to remove coarse aggregates of particles in the coating liquid, it is preferred to arrange a filter medium to precisely filter the coating liquid shortly before coating. Further, the average particle diameter of the particles is preferably from 20 to 150 nm, more preferably from 40 to 60 nm. If the average particle diameter is less than 20 nm, it is difficult to obtain sufficient anti-blocking

Sex, and the scratch resistance tends to be worse. On the other hand, when the average particle diameter of the particles exceeds 150 nm, the haze increases, and the particles are liable to fall off, which is not preferable. In the present invention, when only the particles A having an average particle diameter of 20 to 150 nm are obtained, sufficient anti-blocking properties and scratch resistance are not obtained. Therefore, in order to further improve the anti-blocking property and the scratch resistance, it is preferred to use a smaller amount of the particles B having a larger average particle diameter. The average particle diameter of the particles B having a large average particle diameter is preferably from 1 600 to 1 OOO nm, and particularly preferably from 200 to 800 nm. When the average particle diameter of the particles B is less than 16 nm, the scratch resistance, the sliding property, and the winding property are deteriorated. On the other hand, if the average particle diameter of the particles B exceeds 100 nm, the haze tends to be high. Moreover, it is preferable that the particle B is a particle in which the ratio of the average particle diameter in the agglomerated state to the average particle diameter of the primary particle is four times or more from the aggregated particles in which the primary particles are aggregated, and is inferior in scratch resistance. Good. When two kinds of particles are used, for example, the content ratio (P1/P2) of the particles A (average particle diameter: 20 to 150 nm) and the particles B (average particle diameter: 160 to 100 nm) in the adhesion-modifying layer is 5~ 30. The content of the particles B is 0.1 to 1% by mass based on the solid content of the adhesive layer. By controlling the content of the particles of the specific particle diameter of 2 - 54 - 200810924 within the above range, the average surface roughness of the three-dimensional center plane of the surface of the adhesive modified layer is appropriately adjusted to make transparency and handleability or prevention Adhesive coexistence is preferred. When the content of the particles B exceeds 1% by mass, the haze tends to increase remarkably. The measurement of the average primary particle diameter and the average particle diameter of the above particles was carried out by the following method.

The photograph of the particles was taken with an electron microscope, and the maximum diameter of 300 to 500 particles was measured at a magnification of 2 to 5 mm of the smallest particles, and the average 値 was regarded as the average primary particle diameter or the average particle diameter. Further, when the average particle diameter of the particles in the adhesion-modified layer of the laminated film is determined, a cross section of the laminated film is imaged at a magnification of 120,000 times using a transmission electron microscope (TEM), and the adhesion is improved. The largest diameter of the particles present in the cross section of the layer. The average particle diameter of the particles B formed by the aggregates was measured by using an optical microscope at a magnification of 200 times to take a cross section of the adhesive modified layer of 300 to 500 laminated films, and the maximum diameter thereof was measured. (1) Cross-linking agents Like mobile phones, PDAs, and mobile computers, the opportunities for using information terminals outside the home are increasing. Furthermore, as in touch panels used in car navigation and the like, materials used in high-temperature cars in summer are also increasing. Therefore, it is required that a hard coating film having a small change in quality in a severe environment of such high temperature and high humidity, that is, a film excellent in moisture and heat adhesion is required for such use. In such a use, when the hard coating film of the present invention is used, in order to improve the moist heat resistance of the adhesive reforming layer, a crosslinking agent is added to the coating liquid, and -55-200810924 is formed by the following heat treatment. An adhesive modification layer of a resin of a joint structure. As the crosslinking agent, at least one selected from the group consisting of an epoxy crosslinking agent, a melamine crosslinking agent, and an oxazoline crosslinking agent is used. The crosslinking agent can be selected in consideration of the affinity with the copolymerized polyester resin used in the coating liquid and the moisture-resistant heat adhesion required in the adhesive layer.

In particular, when high moisture and heat resistance is required, the above crosslinking agent is preferably an epoxy crosslinking agent or a melamine crosslinking agent. The epoxy-based crosslinking agent is not particularly limited. For example, a water-soluble epoxy crosslinking agent manufactured by NAGASE Chemical Industry Co., Ltd. (Deconal series; EX-521, EX-512, EX-421, EX-810, EX-) 811, EX-85 1, etc.) can be obtained as a commercial item. As a melamine-based crosslinking agent, for example, Sumitex series (M-3, MK, M-6, MC, etc.) manufactured by Sumitomo Chemical Co., Ltd. or methylated melamine resin (MW-22, MX-706, etc.) manufactured by Sanwa Chemical Co., Ltd. ) can be obtained as a commercial product. Further, as an oxazoline-based cross-linking agent, Epociros series (WS-700) manufactured by Nippon Shokubai Co., Ltd., and NX Linker FX manufactured by Shin-Nakamura Chemical Co., Ltd., etc., can be obtained as commercial products. The crosslinking agent is preferably 5 to 40% by mass, more preferably 1 in terms of the total amount (1% by mass) of the copolymerized polyester resin and the crosslinking agent in the adhesion-modifying layer. 0 to 30% by mass is contained in the coating liquid for forming an adhesive layer. When the content of the crosslinking agent is more than 40% by mass, the adhesion-modifying layer becomes brittle, and after forming a functional layer such as a hard coating layer or a diffusion layer from the acrylate-based resin, the processing procedure may not be sufficiently obtained as much as possible. Resistance to high-speed cutting. On the other hand, when the content of the crosslinking agent is less than 5% by mass, it is difficult to obtain the durability required in recent years. Further, in the coating liquid, in order to promote crosslinking, a catalyst may be added as needed. -56- 200810924 (3-2) Coating step

The step of applying the above aqueous coating liquid is preferably an in-line coating method applied in the production step of the film. More preferably, it is coated on the substrate film before the crystallization alignment is completed. The solid content concentration in the aqueous coating liquid is preferably 30% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the solid content concentration is preferably 1% by mass, more preferably 3% by mass, and particularly preferably 5% by mass. At a coating amount of the aqueous coating liquid, the film coated with the aqueous coating liquid is introduced into a tenter for alignment and heat setting, and is heated there to form a stable film by thermal crosslinking reaction. Polyester laminated film. (Coating amount) The coating amount at the time of drying (hereinafter referred to as wet coating amount) is preferably 2 g/m 2 or more and less than 10 μg/m 2 . When the wet coating amount is less than 2 g/m2, in order to obtain a designed dry coating amount (coating amount of the final adhesive reforming layer), it is necessary to increase the solid content concentration of the coating liquid. When the solid content concentration of the coating liquid is increased, the viscosity of the coating liquid is increased, and uneven coating unevenness is likely to occur. On the other hand, when the wet coating amount is l〇g/m2 or more, it is likely to be affected by the dry wind in the drying furnace, and coating unevenness is likely to occur. Further, in order to prevent the adhesion of dust, it is preferred to apply the coating liquid in an environment having a cleanliness level of 5,000 or less. Further, the coating amount of the final adhesive reforming layer (solid content per unit area of the film) is preferably controlled to 0.005 to 0.20 g/m2. In the prior art, if the coating amount is less than 〇.〇5g/m2, it is difficult to obtain sufficient adhesion. However, since the adhesive reforming layer has a specific phase-separated structure, even if the coating amount is less than 〇. 5 g/m 2 ', a laminated film having excellent adhesion to the functional layer and the substrate of -57 to 200810924 is obtained. If the coating amount is less than 〇.〇〇5g/m2', the adhesion becomes insufficient. Further, when the coating amount is less than 0.05 g/m2, it is preferred to use particles having an average particle diameter of 6 Å or less. When the average particle diameter of the particles exceeds 6 Onm, the particles become easily detached from the adhesive reforming layer during the production or processing of the adhesive base film. When the particles are in the form of a polyurethane crucible, if the coating amount is 0.005 g/m2 or more, the particles are hard to fall off. On the other hand, when the coating amount exceeds 0.20 g/m2, the amount of the polyurethane component segregated on the surface of the adhesion-modifying layer increases, and the blocking resistance

Further, the thickness of the adhesive modified layer can be measured by observing the cross section of the conductive modified layer by a microtome and observing it with an electron microscope. When the adhesive modifying layer is soft, it will be deformed when cut. For the sake of simplicity, if the amount of coating is known, the thickness can be converted from the density of the next layer. For example, when the density of the adhesive reforming layer is lg/cm3, the coating amount is lg/m2, and the thickness corresponds to 1 μm. Next, the density of the modified layer can be determined by multiplying the density of each material by the mass ratio of the material from the type of the resin or the particles constituting the adhesive modified layer, and determining the density of each material. It is estimated that the thickness of the adhesive layer is modified. (3-3) Drying step In the method for producing an adhesive-modified substrate film, the coating liquid is applied onto the thermoplastic resin film, and then the thin coating film is dried. In general, when the coating film is dried after the application of the coating liquid, the preheating zone of the tenter is used to dry the film. In this case, although depending on the size of the film forming apparatus and the traveling speed of the film, it generally starts from coating to drying -58-200810924

The time is at least 5 seconds. During this period, the balance of water and alcohol in the solvent of the coating liquid collapses, and the highly hydrophilic polyurethane component becomes easily segregated on the surface of the subsequent modified layer. Therefore, in the finally obtained modified modified base film, the area ratio of the PEs phase on the surface of the adhesive modified layer or the PU phase in the vicinity of the interface with the hard coating layer on the cut surface of the adhesive modified layer The area ratio is difficult to control within the proper range. In the present invention, a drying oven (plate dryer) dedicated to the drying of a coating film is placed in a direction exit as close as possible to the film of the coating device, and after the coating liquid is applied to the polyester film, the drying system is immediately focused. In the drying furnace, the temperature of the dry wind blown to the coated surface is preferably 1 20 ° C or more and less than 150 ° C. Further, the wind speed is preferably 30 m/sec or more. A more preferable drying temperature is above 130 °C and below 150 °C. When the drying temperature is lower than 120 ° C or the wind speed is lower than 30 m / sec, the drying speed becomes slow. The balance of water and alcohol in the solvent of the coating liquid collapses, and the ratio of water is relatively increased. Therefore, the highly hydrophilic polyurethane component is segregated on the surface of the adhesive reforming layer. Therefore, in the finally obtained modified modified base film, the area ratio of the PEs phase on the surface of the adhesive modified layer or the PU phase in the vicinity of the interface with the hard coating layer on the cut surface of the adhesive modified layer The area ratio is difficult to control within the proper range. On the other hand, when the drying temperature is 150 °C or higher, the thermoplastic resin film is liable to be crystallized, and the frequency of occurrence of cracking during lateral stretching increases. Further, in the above drying furnace, it is preferred to maintain the temperature at 120 ° C or higher and lower than 150 ° C while drying for 0 · 1 to 5 seconds. The drying time is preferably 0.5 to 3 seconds. If the drying time is less than 〇·i seconds, the drying of the coating film becomes insufficient -59-200810924, and the roller becomes insufficiently dried when passing through the roller disposed between the drying step and the lateral stretching step. Contaminated by the coated surface. On the other hand, when the drying time exceeds 5 seconds, the thermoplastic resin film is liable to be crystallized, and the frequency of occurrence of cracking during lateral stretching increases.

After drying the coating film at a temperature of 120 ° C or more and less than 150 ° C in the drying oven, it is preferred to immediately cool the adhesive-modified substrate film having the adhesion-modifying layer to a temperature near room temperature. . When the surface temperature of the adhesive-modified substrate film is taken out at a high temperature of 100 ° C or higher, the drying furnace is taken out, and when the adhesive-modified substrate film is brought into contact with a roll near room temperature, the film is likely to be scratched due to shrinkage of the film. . When the wind speed in the drying furnace is usually 30 m/sec or more, the dry surface of the drying oven blows the coated surface in an undried state, and drying streaks are likely to occur. However, in the present invention, by exhausting the air volume of the same amount or more as that of the blown air volume to the outside of the drying furnace, it is possible to perform at a wind speed of 3 Om/sec or more. Further, it is also important that the exhaust air flows toward the opposite side of the coater to prevent the exhaust air of the coater from being streaked on the coated surface. It is important that the passage time of the film is from less than 2 seconds, preferably less than 1.5 seconds, from the time of application to the drying of the furnace. When the time from application to drying in the drying furnace is 2 seconds or longer, the balance of water and alcohol in the solvent of the coating liquid collapses, and the highly hydrophilic polyurethane component becomes easily segregated on the surface of the adhesive reforming layer. . Therefore, in the finally obtained modified modified base film, the area ratio of the PEs phase on the surface of the adhesive modified layer or the PU phase in the vicinity of the interface with the hard coating layer on the cut surface of the adhesive modified layer The area ratio is difficult to control within the proper range. -60- 200810924 In order to maintain the passage time of the film from the time of application to the drying furnace to less than 2 seconds, it is necessary to select a suitable film traveling speed, but it is preferable to make the coater and the drying furnace inlet as close as possible. Further, in the drying furnace, in order to prevent the incorporation of dust from the dry air, it is preferable to use air cleaned by the HEPA filter. The HEPA filter used at this time preferably uses a filter having a property of blocking the ink of 0.5 μm or more with a nominal filtration accuracy of 0.5 μm or more.

The drying step is preferably carried out by sequentially changing the conditions of the drying temperature and the drying time, i.e., by a drying zone which is divided into 2 to 8 zones. It is particularly preferable to use a multi-stage drying device which is divided into 3 to 6 zones. For example, when the coating liquid is applied to one or both sides of a one-axis oriented thermoplastic resin film and dried by a multi-stage drying oven disposed directly above the coater, the following method is suitable, for example, when drying in four stages. Drying was carried out in a drying oven divided into 4 drying zones. For example, the first drying zone is dried at a temperature of 1 2 5 to 14 ° C for 1 to 4 seconds. The second drying zone is dried at a temperature of 55 to 1 0 ° C for 1 to 4 seconds. The third drying zone is at a temperature of 3 5 to 5 5 . (: 〇. 1~4 seconds of drying, the fourth drying zone is dried at a temperature of 2 5 to 3 5 ° C for 0.1 to 4 seconds. The range of the above drying conditions is the solid with the coating liquid. There is a slight variation in the concentration of the components, and it is not limited by the above-mentioned representative conditions. Further, it is important that the amount of air changes in each stage during hot air drying. For example, the following methods are preferred. In the first drying zone, the wind speed of the dry air is set to 20 to 50 m/sec -61 to 200810924, the air supply air volume of the dry air is set to 100 to 150 m/sec, and the exhaust air volume is set to 150 to 200 m3/sec. From the second drying zone to the fourth drying zone, the air supply air volume is set to 60 to 140 m/sec, and the exhaust air volume is set to 100 to 180 m/sec. In any of the drying zones, the dry airflow is set. On the side of the coater, the end of the film was grasped by a jig, and guided to a hot air zone at a temperature of 100 to 140 ° C and a wind speed of 10 to 20 m/sec, and stretched in the width direction by 2 to 6 times.

Further, the drying temperature and the total drying time may be appropriately adjusted while maintaining the temperature at 120 ° C to 150 ° C for 0.1 to 5 seconds, preferably 0.5 seconds to less than 3 seconds. The determination of each stage (zone) in the drying step may take into consideration the conditions such as the concentration of the dispersion, the amount of coating, the traveling speed of the film to be coated, the temperature of the hot air, the wind speed, the air volume, etc., and it is appropriate and appropriate at the manufacturing site. value. (3-4) Heat setting treatment step In the method for producing the adhesive modified base film, the transverse stretching step, the heat setting treatment step, and the cooling step are designed to be continuously divided into 1 〇 to 30 regions, and each zone is They can be separated independently of temperature control, and no severe temperature changes occur in each section. In particular, in the second half of the transverse stretching zone to the heat setting maximum temperature setting zone, the temperature rise in the stage can suppress the severe temperature change in the adjacent section. In the present invention, the temperature control system is particularly important in the drying step or the heat setting treatment step when manufacturing the adhesive-modified substrate film having a specific phase-separated structure on the surface or inside of the adhesion-modifying layer. Further, in order to form a crosslinked structure in the resin constituting the adhesive reforming layer, the temperature in the heat setting treatment step is very important 'this temperature has a large influence on the reaction speed of the -6 2 - 200810924. Hereinafter, the implementation thereof will be described in detail. As described above, in the heat setting treatment step, the heat treatment conditions affect the phase separation state of the subsequent reforming layer. That is, it is necessary to appropriately set the maximum temperature in the heat setting treatment step, the time required to reach the above maximum temperature, and the temperature required to proceed from the phase separation of the subsequent reforming layer to the maximum temperature in the heat setting treatment step. Time is important.

In the heat setting treatment step, the temperature of each heat setting zone varies somewhat depending on the kind of the resin constituting the thermoplastic resin film, but is also suitably set in the temperature range of 100 to 260 °C. Hereinafter, a representative thermoplastic resin, that is, polyethylene terephthalate, will be described as a thermoplastic resin film. The maximum temperature of the heat setting treatment step is preferably controlled at 210 to 240 ° C. The lower limit is 225 ° C and the upper limit is 23 5 ° C. Generally, the initial stage of the heat setting treatment is heat setting at a relatively high temperature of 210 to 240 ° C, and as the latter stage is formed, the temperature is preferably in the order of 100 to 200 ° C. In the heat setting treatment step, if the maximum temperature is lower than 210 °C, it is difficult to form a microphase separation structure or a nanophase separation structure in the adhesion modification layer. Therefore, it is difficult to sufficiently obtain the adhesion between the substrate and the functional layer required in recent years, so as to withstand the punching at the time of high-speed cutting, without peeling off at the interface, and the heat of the obtained adhesive modified substrate film. The shrinkage rate becomes large, so it is not suitable. Moreover, in the heat setting process step, if the maximum temperature exceeds 24 0 ° C, then -63- 200810924

Further, the surface area of the PEs on the surface of the modified layer is increased, and the adhesion between the functional layer such as the hard coating layer, the diffusion layer, the ruthenium layer, and the printing layer printed by the ultraviolet curable ink is easily lowered. Further, since the time required from the temperature at which the phase separation of the adhesion-modifying layer starts to proceed to the maximum temperature at which the heat-setting treatment step is reached becomes long, the polyester phase having the copolymerized polyester as a main component is the most The area where the width of the thin part exceeds 1 μm is in a state of being scattered. As a result, the functional layer such as the hard coating layer, the diffusion layer, the prism layer, and the printed layer printed on the ultraviolet curable ink is locally inferior in adhesion to the functional layer starting from the portion. The time required from the temperature at which the phase separation of the adhesive reforming layer proceeds significantly to the maximum temperature at which the heat setting treatment step is reached is specifically preferably set as follows. In the present invention, the passage time of the film is preferably from 3 seconds or more and less than 20 seconds from the temperature setting region where the phase separation of the adhesive reforming layer is significantly performed to the entrance of the highest temperature setting region of the heat setting treatment step. , Very good for more than 4 seconds and less than 15 seconds. If the passage time is less than 3 seconds, the time for exhibiting the phase separation structure defined by the present invention may be insufficient. On the other hand, when the passage time is 20 seconds or more, the phase separation system is excessively performed, and the portion where the width of the finest portion in which the copolymerized polyester is used as the main component exceeds Ιμηη is likely to be dispersed. As a result, the functional layer such as the hard coating layer, the diffusion layer, the enamel layer, and the printing layer printed by the ultraviolet curable ink is locally inferior in the adhesion layer, and is involved in the peeling of the macroscopic view starting from the portion. In the present invention, the temperature at which the phase separation of the adhesion-improving layer starts to proceed remarkably is estimated to be about 200 ° C in the range of the composition of the coating liquid shown in the examples of the present invention. However, since this temperature is of course different depending on the resin component of the adhesive reforming layer, it is not limited by this temperature. The heat setting process steps are more specifically described. Generally, the transverse stretching step, the heat setting processing step, the cooling step,

In order to suppress the severe temperature change of the adjacent zones, the zone is divided into 10 to 30 zones in the tenter, and each zone is independently temperature controlled. In particular, it is preferred that in the region set from the second half of the transverse stretching zone to the highest temperature of the heat setting treatment step, the temperature of each zone is gradually increased in temperature for the direction of the film, so that the heat setting zones are not Intense temperature changes can occur. In the present invention, it is important to rapidly and uniformly heat up the film passage time from the temperature setting region which is significantly performed from the phase separation to the entrance of the highest temperature setting region of the heat setting treatment step. In order to rapidly increase the temperature rise, a method of increasing the heat transfer efficiency in each heat setting zone, for example, a method of increasing the wind speed of the hot air blown by the film is effective. However, in this method, since temperature unevenness is generally likely to occur, unevenness may occur in the phase separation state of the adhesive reforming layer, or impurities such as oligomers slightly attached to the device in the heat setting zone may fly. The flying impurities will adhere to the film and are related to optical defects. On the other hand, if the wind speed is too low, a sufficient temperature increase rate cannot be obtained. Therefore, in the present invention, the wind speed is preferably l〇m/sec or more and less than 20 m/sec. In order to quickly and uniformly raise the temperature of the laminated film, the interval between the nozzles for blowing hot air is arranged at a relatively short interval of 500 mm or less -65- 200810924

It is valid. When the interval between the nozzles for blowing hot air is set to 500 mm or less, for example, when the nozzle interval is arranged to be 300 mm and 350 mm '400 mm, the maintenance of the apparatus becomes unfavorable, but it is important to complete the present invention. When the number of nozzles per zone corresponding to one section is about 6 to 12, the number of nozzles is determined in consideration of the nozzle interval, the amount of ventilation, and the ventilation time. In addition, the wind speed described in the present invention means that the wind speed of the surface of the film at the nozzle outlet which is blown by the hot air is measured by a thermal anemometer (Model No. 6161 manufactured by Nippon Co., Ltd.). A preferred embodiment of the heat setting treatment step is shown in the manufacture of an adhesive modified substrate film. The heat setting treatment step described above is continuously divided into a plurality of heat setting zones, and each zone can be separated independently of temperature control. The heat-fixing zone is divided into 2 to 10 segments of heat-setting zones to be continuously arranged, preferably divided into 4 to 8 segments, and the heat-fixing zone divided by the plurality of segments is used for the subsequent modification. Temperature control management of the substrate film is preferred. For example, in the case of a polyester film having an adhesion-modifying layer, heat-setting treatment can be carried out by continuously passing through a heat-setting zone divided into six stages as follows, so that each stage has a subtle temperature difference. A method of trimming portions of the film that are not coated at both ends. In the heat setting treatment temperature, the first heat setting zone is 200 ° C, the second heat setting zone is 225 ° C, the third heat setting zone is 230 ° C, and the fourth heat setting zone is 230 ° C. 5 The heat setting zone is 210 ° C, the 6th heat setting zone is 170 ° C, and the 7th heat setting zone is 120 ° C. Further, 3% relaxation treatment was carried out in the width direction in the sixth heat setting zone. -66- 200810924 The above stage is equivalent to 1 heat setting zone. The temperature of the heat setting zone of each of the segments preferably has a subtle temperature difference, i.e., a temperature difference of about 5 to 40 °C. The setting of the temperature difference is arbitrarily determined in consideration of factors such as the traveling speed of the thermoplastic resin film having the adhesion-modifying layer, the air volume, and the thickness of the adhesion-modifying layer.

When a base film of an optical functional film such as a lens film or a diffusion plate is used, a relatively thick film having a film thickness of 100 μm or more usually has a film length of at least 10 μm or more, and is sometimes wound into a film. A cylindrical shape of 2000 m or more is supplied to a processing step for laminating a tantalum layer or a diffusion layer. In the present invention, the area ratio of the PEs phase (the dark phase in the phase image) on the surface of the adhesion modifying layer, or the area of the PU phase in the vicinity of the interface with the hard coating layer in the cutting surface of the adhesion modifying layer. The ratio (showing the bright phase in the phase image) is preferably less than 1 5% of the difference between the maximum 値 and the minimum 面积 of the area ratio in the longitudinal direction when measured at intervals of 1 μm in the longitudinal direction of the film. More preferably, it is less than 10%. By setting the difference between the maximum 値 and the minimum 面积 of the area ratio in the longitudinal direction thereof to be 15% or less, a pressure-sensitive adhesive base film roll having stable adhesion and anti-blocking property can be obtained. In order to control the difference between the maximum 値 and the minimum 面积 of the area ratio in the longitudinal direction thereof to be less than 1 5%, it is important to continuously manufacture the long-length adhesive-modified substrate film roll used in the present invention. The film forming conditions such as coating conditions, drying conditions, and heat setting conditions are kept constant. However, the ratio of the mixed solvent used for the coating liquid is particularly likely to vary, and the ratio of the mixed solvent is kept constant, and the area ratio or the cutting surface of the PEs phase on the surface of the surface of the film-67-200810924 is reduced in the length direction of the film roll. It is important to change the area ratio of the PU phase. For example, the area ratio of the PEs phase on the surface of the adhesion modifying layer or the area ratio of the PU phase of the cutting surface can be controlled to 15% or less by the means described below. Further, the means for maintaining the ratio of the mixed solvent is not limited to the following method.

With respect to the capacity of the coating liquid (11 in Fig. 7), the capacity of the circulation groove (13 in Fig. 7) is increased to stabilize the concentration ratio of the mixed solvent. Specifically, as shown in Fig. 7, when the capacity of the coating liquid is 1, the capacity of the circulation tank is preferably 10 or more, and particularly preferably 50 or more. The capacity ratio (the capacity of the circulation tank/the capacity of the coating liquid) is less than 1 Torr, that is, the capacity of the circulation tank is too small, and the concentration of the mixed solvent tends to become large. In addition, when the capacity of the circulation tank is 1, the capacity of the preparation tank (14 of Fig. 7) is preferably 1 or more, more preferably 20 or more. Thereby, when the coating liquid is supplied from the mixing tank to the circulation tank, the capacity of the circulation tank can be kept constant during operation. Further, it is also effective to improve the accuracy (roundness and cylindricality) of the coating roller in the coating apparatus from the viewpoint of reducing the unevenness of the coating thickness of the adhesive reforming layer in the longitudinal direction of the film roll. Further, from the viewpoint of the change in the area ratio of the PEs phase on the surface of the adhesive reforming layer or the variation in the area ratio of the PU phase on the cutting surface in the longitudinal direction of the film roll, Also effective. The roundness of the above coating roller is as shown in US B 0621 'is the minimum area method determined by the recording roundness tester, and the index represented by the difference between the radii of the two concentric circles -68-200810924 . Furthermore, the unit of roundness of the roll is mm. Further, the cylindricality of the application roller moves the stage of the micrometer on which the roller is placed on the chassis in the axial direction, and is carried out in various measurement planes over the entire length in a state where the cylinder is in contact with the measuring device. The indicator is expressed as 1/2 of the maximum difference of the reading at this time. Moreover, the unit of the cylinder is mm. In the present invention, by increasing the roller precision (roundness and cylindricality), the variation in the thickness of the coating layer in the longitudinal direction can be reduced. Specifically, the roller precision (true roundness and cylindricality) is preferably less than 5/1 000 mm.

In addition, when the coating liquid is applied, the surface working degree of each roll of the reverse coater is 0.3 S or less, and the accuracy (roundness and cylindricality) of the coating roll and the measuring roll are made lower than 5/1. When it is 1000 mm or more and 2/1 000 mm or more, the variation of the wet coating amount can be suppressed, and the thickness variation of the coating film can also be suppressed. It is preferable to use a coating roller and a metering roller with a precision (roundness and cylindricality) of 3/1000 mm. Further, by setting the tension of the film to 4000 to 10,000 N/original width (the original width is 1 to 2 m), the planarity of the film on an industrial scale is maintained, and the amount of transfer of the coating liquid is made uniform. Moreover, the tension of the film varies depending on the thickness of the film, and flatness can be maintained by applying a relatively low tension to a relatively thin film. If the tension of the film exceeds 1 0000 N/original width, the film may be deformed or broken. On the other hand, if the tension of the film is less than 4000 N/original width, the planarity of the film at the time of coating may become insufficient, or the film may be meandered. As a result, the amount of the coating liquid transferred may become uneven in the longitudinal direction of the film, and the thickness of the coating layer may also vary greatly due to the large amount of wet coating of the film -69- 200810924

Moreover, in order to control the fluctuation of the area ratio (maximum 値 and minimum )) of the PEs phase of the surface of the adhesive reforming layer or the PU phase of the cutting surface in the width direction of the film roll, the film roll is controlled to 10% or less. In terms of the width direction, it is important to reduce the thickness variation of the coating layer. Therefore, it is effective to improve the planarity in the width direction at the time of coating. Specifically, after the application of the reverse roll, the nip rolls (16 of Fig. 7) were used for the purpose of grasping only the both end faces of the film. By grasping both ends of the film at the nip, the width of the film can be increased on an industrial scale. The planarity of the direction stabilizes the wet coating amount in the width direction of the film. Thereby, the variation in the thickness of the coating layer in the width direction of the film roll can be reduced. When the nip rolls do not grasp the both end portions of the film, the wet coating amount in the width direction and the longitudinal direction of the film greatly fluctuates, and the thickness variation of the coating layer is also larger. (4) Hard coating layer and other optical functional layers The hard coating film of the present invention is formed by laminating a modified layer containing a copolymerized polyester and a polyurethane on one or both sides of a thermoplastic resin film. a B-bonding modified base film and a hard coating layer C containing inorganic fine particles on one side of the adhesive modified layer B of the film, and comprising A/B/C or B/A/B/C The layer constitutes a hard coated film. The curable resin constituting the hard coating layer is preferably an ionizing radiation curable resin, and examples of the ionizing radiation curable resin include the following resins. The ionizing radiation curable resin is preferably a resin having an acrylate functional group, and particularly preferably a polyester acrylate or a urethane acrylate. Polyester acrylate is an acrylate or methacrylate of an oligomer of a polyester-based polyol (hereinafter, acrylate and/or methacrylate is also described as (A-70-200810924-based) acrylate) ), or a mixture thereof. Further, the urethane (meth) acrylate is composed of an oligomer of a polyol compound and a diisocyanate compound, which is (meth) acrylated. Examples of the monomer constituting the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. And methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, and phenyl (meth)acrylate.

Further, when it is necessary to further increase the hardness of the hard coating layer, it is preferred to use a polyfunctional monomer. For example, examples of the polyfunctional monomer include trimethylolpropane tri(meth)acrylate, hexanediol (meth)acrylate, tripropylene glycol di(meth)acrylate, and diethylene glycol di( Methyl) acrylate, pentaerythritol tri(meth) acrylate, dipentaerythritol hexa(meth) acrylate, 1,6-hexanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate ester. Examples of the oligomer of the polyester-based polyol include adipic acid and a diol (ethylene glycol, polyethylene glycol, propylene glycol, polypropylene diol, butylene glycol, polytetramethylene glycol, etc.) or triol. (polyglycerol, trimethylolpropane, etc.), a polyadipate polyol or a polysebacate polyol of a condensation product of sebacic acid with a diol and a triol. Further, part or all of the above aliphatic dicarboxylic acid may be substituted by another organic acid. For example, isophthalic acid, citric acid, or phthalic anhydride can be used as a component for increasing the hardness of the hard coating layer. When the hard coating agent is applied onto the surface of the adhesive modifying layer of the base film, in order to improve the leveling property, it may be diluted with a diluent as needed. Examples of the diluent include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexanol, heptane, octane, decane, and decane, and methyl ethyl ketone-71 - 200810924 and A ketone such as ethyl ketone or diisopropyl ketone. The amount of the diluent can be appropriately selected so as to be an appropriate viscosity. Examples of the inorganic fine particles contained in the hard coating layer C include amorphous vermiculite, crystalline glass tantalum, vermiculite, chromium oxide, titanium oxide, inorganic oxides such as alumina, and vermiculite-alumina. Composite oxide particles, magnesium carbonate, aluminum hydroxide, barium sulfate, calcium carbonate, calcium phosphate, kaolin, talc, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, mica

On the surface of the hard coating layer C, when the antireflection layer composed of the high refractive index layer/low refractive index layer or the high refractive index layer/medium refractive index layer/low refractive index layer is laminated, the hard coating layer C is made high. When the refractive index is increased, the high refractive index layer can be omitted from the antireflection layer. As a result, the cost can be reduced. In order to increase the refractive index of the hard coating layer C, it is effective to contain inorganic fine particles having a high refractive index in the hard coating layer. Examples of the inorganic fine particles having a high refractive index include chromium oxide and titanium oxide. In the hard coating layer, it is important that the content of the inorganic fine particles is 20% by mass or more and 80% by mass or less. When the content of the inorganic fine particles is less than 20% by mass, the scratch resistance is insufficient. On the other hand, when the content of the inorganic fine particles exceeds 80% by mass, the transparency tends to be lowered. Further, the average particle diameter of the inorganic fine particles is preferably from 5 to 100 nm from the viewpoint of transparency. However, such inorganic fine particles having a small average particle diameter are easily aggregated and are not stable. Therefore, in order to improve the dispersion stability of the inorganic fine particles, it is preferred to impart a photo-sensitive group to the surface of the inorganic fine particles, and to improve the affinity with the curable resin. -72-200810924 Such a hard coating agent containing inorganic fine particles can be commercially available. Product acquisition. For example, an ultraviolet curable resin (Desolite; Z7400A, Z7410A, Z7400B, Z7410B, Z7400C, Z7410C, Z7410D, Z7410E, Z7501, Z7503, Z752 1, Z7527) manufactured by JSR Corporation can be cited.

The ionizing radiation-curable resin is cured by irradiation with ultraviolet rays or electron beams. When irradiating ultraviolet rays, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a metal halide is used, in a wavelength range of 100 to 400 nm, preferably in a wavelength range of 200 to 400 nm, and 1 to 3 000 m J/ The energy of m2 is to illuminate the ultraviolet rays. Further, when the electron beam is irradiated, an electron beam having an acceleration voltage of 100 keV or less, preferably 100 to 300 keV, and a wavelength range of 100 nm or less is irradiated using a scanning type or a curtain type electron beam accelerator. The thickness of the hard coating layer is in the range of 0·1 to 30 μm, which can be determined by the use, and more preferably 1 to 15 μm. When the thickness of the hard coating layer is within the above range, the surface hardness of the hard coating layer is high and it is not easily damaged. Further, the hard coating layer is less likely to be brittle, and when the hard coating film is bent, cracks do not occur in the hard coating layer. The optical functional film described in the present invention is a film which is formed on the opposite surface of the hard coating layer C of the hard coating film of the present invention or on the optical layer of the laminated optical function layer, and has the following two embodiments. (a) On the opposite side of the hard coating layer C, an optical function of at least one layer selected from the hard coating layer, the light diffusion layer, the scorpion lens layer, the electromagnetic wave absorbing layer, the near-infrared ray shielding layer, and the transparent conductive layer is laminated. Optical properties of the layer -73- 200810924 film. (b) An optical functional film in which an antireflection layer or an antifouling layer is laminated on the hard coating layer C. Hereinafter, a lens film using a lens layer as an optical function layer and a light diffusion film using a light diffusion layer will be described as a representative example. (lens film)

The prism lens film or the Fresnel lens film is provided on one side of the adhesive-modified substrate film having an adhesion-modifying layer containing a copolymerized polyester and a polyurethane as a main constituent component. The ionizing radiation-hardening type hard coating layer of the inorganic fine particles is formed by laminating a tantalum lens layer or a Fresnel lens layer on the opposite surface. There is also a case where the lens film is referred to as a lens sheet, but the film in the present invention also includes a sheet. Next, the active energy ray-curable resin component constituting the 稜鏡 lens layer will be described. As the active energy ray-curable resin component, at least one of the radical polymerizable monomers or oligomers determines the performance of the lens sheet to be produced, and can be appropriately selected depending on the performance of the intended lens film. The resin component is used singly or in combination of two or more kinds, and a radical polymerizable monomer or oligomer is used. In particular, when two or more kinds of resins are used, the mechanical strength, the impact resistance, the heat resistance, the surface hardness, and the chemical resistance required for the lens film can be imparted. Further, as the radical polymerizable functional group, 60 parts by mass or more of a compound having an acryloyl group or a methacrylium group is used as a component, and when the active energy ray is irradiated, partial copolymerization is instantaneous. Not fluidized. Therefore, when the lens layer is formed, the optical distortion due to the convection -74 - 200810924 is reduced.

The resin component may, for example, be an ester type (meth) acrylate obtained by a condensation reaction of an aliphatic, alicyclic or aromatic monohydric alcohol or a polyhydric alcohol with an acryl acid or methacrylic acid, and has 2 in the molecule. a urethane poly(meth) acrylate obtained by the esterification reaction of one or more isocyanate-based isocyanate compounds with a hydroxyl group or a thiol group-containing (meth) acrylate, or has an intramolecular An epoxy poly(meth) acrylate obtained by ring-closing reaction of at least two epoxy-based compounds with a glycidyl group of acrylic acid or methacrylic acid, a saturated or unsaturated polyvalent carboxylic acid, a polyvalent alcohol, and (a) (meth)acryloyl-functional monomer, oligomer, or styrene, chlorostyrene, bromostyrene, dibromide such as polyester (meth) acrylate obtained by condensation reaction of acrylic acid A (meth)allyl compound such as a vinyl compound such as styrene or divinylbenzene, diethylene glycol bisallyl carbonate, diallyl phthalate or biphenyl diallyl. Preferred specific examples are shown below. The various resin components described below may be used singly or in combination of two or more. Further, a commercially available product is available as a resin for a 稜鏡 lens or a Fresnel lens. For example, a UV curable resin (Desolite; Z9590, Z9502) manufactured by JSR Corporation can be mentioned. (a) Aliphatic mono (meth) acrylate (methyl methacrylate), butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (b) Cyclomono-mono (meth) acrylate cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, (meth) propylene dicyclopentenoate, isobornyl (meth) acrylate, ( Methyl) propylene-75- 200810924 acid borneol ester (C) aromatic mono (meth) acrylate

Phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy-2-methylethyl (meth)acrylate, 3-(meth)acrylate Phenoxy-2-hydroxypropyl ester, 2-phenylphenyl (meth)acrylate, 2-phenylphenoxyethyl (meth)acrylate, 4-phenylphenoxyethyl (meth)acrylate Vinegar, (meth)propionic acid storage 2-phenylphenyl-2-methoxyethane, 2-naphthyl (meth)acrylate, 2-bromophenyl (meth)acrylate, (meth)acrylic acid 4-bromophenyl ester, 2,4-dibromophenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, phenylthioethyl (meth)acrylate, (methyl) ) phenylthioethoxyethyl acrylate, (d) ester bis(meth) acrylate bis(4-(methyl) propylene oxyethoxy phenyl) methane, bis (4-) (Methyl) propylene decyloxydiethoxyphenyl)methane, 2,2.bis(4-(methyl)propenyloxyethoxyphenyl)propane, 2,2-bis(4-( Methyl)propenyloxydiethoxyphenyl)propane, 2,2-bis(4-(A) Base) propylene decyloxypentaethoxyphenyl) propane, 2,2-bis(4-(methyl)propenyloxypropoxyphenyl)propane, 2,2_bis(4-(methyl) Propylene decyloxydipropoxyphenyl)propane, 2,2-bis(4-(methyl)propenyloxyethoxy-3,5-dibromophenyl)propane, 2,2-dual ( 4-(Methyl)propenyloxydiethoxy-3,5-dibromophenyl)propane, 2,2-bis(4-(methyl)propenyloxypentaethoxy-3,5 -dibromophenyl)propane, bis(4-(methyl)propenyloxyethoxyphenyl)anthracene, bis(4-(methyl)propenyloxydiethoxyphenyl)anthracene, double (4-(Methyl)propenylthiophenyl) sulfide, bis(4-(methyl)propenyloxyethylthiophenyl) sulfide, etc., -76- 200810924 (e) alicyclic skeleton Ester di(meth)acrylate bis(4-(methyl)propenyloxycyclohexyl)methane, bis(4-(methyl)propyl decyloxyethoxycyclohexyl)methane, bis (4) -(Meth)propenyloxydiethoxycyclohexyl)methane, bis(4-(methyl)propenyloxycyclohexyl)propane, bis(4-(methyl)acryloxyloxyethyl Oxycyclohexyl)propane, bis(4-(methyl)propenyloxydiethoxycyclohexyl)propane, dicyclopentane di(meth)acrylate, (f) ester diester of aliphatic skeleton Methyl acrylate

Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol (η=4~15) di(methyl) Acrylate, propylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol (η二 4~15) di(meth)acrylate, 1,4-butanediol di(a) Acrylate, polybutanediol (η = 2~15) di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxytrimethylacetate neopentyl glycol ester Acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, (g) polyfunctional (meth)acrylate trishydroxyl Propane tri(meth) acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate Ester, (h) urethane poly(meth) acrylate tris(isocyanatohexyl)isocyanurate, isophor Diisocyanate, bis(4,4"-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, m-xylylene diisocyanate, 2,4-toluene Polyisocyanate compound such as bis-isocyanate, -77-200810924 2,6-streptyl diisocyanate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid a reaction product of a hydroxyl group-containing (meth) acrylate such as butyl acrylate or 4-hydroxybutyl (meth) acrylate, (i) an epoxy poly(meth) acrylate

2,2-bis(4-glycidoxycyclohexyl)propyl, 2,2-bis(4-glycidoxyphenyl)propane, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether , bisphenol S diglycidyl ether, tetrabromobisphenol A diglycidyl ether, tetrabromobisphenol S diglycidyl ether-like epoxy compound and (meth)acrylic acid reactant, (j) polyester poly At least one of (meth) acrylate maleic acid, fumaric acid, citric acid, or succinic acid and at least one of ethylene glycol, propylene glycol, butanediol, trimethylolpropane, or pentaerythritol, and The reaction of the acrylic acid or the acrylic acid as the active energy ray-sensing catalyst is more preferably a radical source which is mainly induced by an active energy ray having a wavelength of 200 to 400 nm. Specific examples thereof include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl oxime, benzophenone, p-methoxybenzophenone, and the like. Ethoxyacetophenone, benzyldimethylketal, 2,2-diethoxyacetophenone, hydroxycyclohexyl phenyl ketone, methylphenyl acetonate, ethyl phenyl acetaldehyde a sulfur compound such as a ketone compound such as an acid ester or a 2-methyl-2-methylphenylpropane-1 ketone, a tetramethylthiuram monosulfide or a tetramethylthiuram disulfide A mercaptophosphine oxide such as 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. These may be used in combination of one type or two or more types. In these -78-200810924, 'better is benzophenone, benzoin isopropyl ether, methylphenylglyoxylate, 1-hydroxycyclohexyl phenyl ketone, benzyl dimethyl condensate Ketone, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. The content of the active energy ray-sensing catalyst is 0.005 to 5 parts by mass, more preferably 0.02 to 2 parts by mass, based on the total amount of the resin component of 1 part by mass.

Moreover, in the lens layer, various additives such as an antioxidant, a heat stabilizer, a weathering stabilizer, an ultraviolet absorber, a yellowing preventive agent, an organic slip agent, and the like may be blended in a range that does not impair the function of the lens. Pigments, dyes, blueants, organic or inorganic microparticles, chelating agents, antistatic agents' surfactants, leveling agents, nucleating agents, diffusing agents, and the like. On the surface of the adhesion-modifying layer of the adhesive-modified substrate film, a method of forming the active-line-curable resin as a constituent component of the lens layer is used, and various methods are selected depending on desired properties or uses. For example, a method of applying the resin to a rod cut into a crucible shape, or a method of causing the resin to flow into a mold having a shape of a lens layer such as a dome shape, and superimposing the adhesion property of the adhesive-modified substrate film The method of the surface of the layer. Further, the active line means an electromagnetic wave capable of polymerizing an acrylic vinyl group such as an ultraviolet ray, an electron beam, or a radiation (α line, β line, γ line, or the like). In practice, the UV system is simple. As the ultraviolet source, for example, an ultraviolet ray lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, and a carbon arc lamp are used. Further, the 'electronic line type device must be operated under a high-priced inert gas, but it is advantageous from the point of not containing a photopolymerization initiator or a photosensitizer, etc. -79-200810924 The thickness of the lens layer can be The purpose of the lens film or the shape of the lens unit is arbitrarily selected. Generally, the thickness of the lens layer is preferably from 1 to 5 mm, more preferably from 0.2 to 3 mm. When the thickness of the lens layer is thinner than 0.1 mm, the effect as a lens layer tends not to be obtained. On the other hand, if the thickness of the lens layer is thicker than 5 mm, the brightness tends to be insufficient. Further, the pitch of the lens unit is arbitrarily selected in accordance with the purpose of the lens film or the shape of the lens unit. Generally, the distance between the centers of the respective lens layers is preferably from 0.03 to 0. 5 m, more preferably from 0.05 to 0.3 m.

In particular, the dome-shaped lens film 'with a braided lens layer is preferable from the viewpoint of brightness and ease of formation. Further, the apex angle of the crucible is preferably from 80 to 150 degrees, more preferably from 85 to 130 degrees. (Light-diffusing film) In the present invention, the light-diffusing film is formed on one side of the adhesive-modified substrate film of the adhesive-modified layer having a copolymerized polyester and a polyurethane as a main constituent component. An ionizing radiation-hardening type hard coating layer containing inorganic fine particles is laminated, and a diffusion layer is laminated on the opposite surface. There is also a case where the light-diffusing film is referred to as a light-diffusing sheet, but the film in the present invention also includes a sheet. The light diffusion layer is composed of a composition containing a binder resin and a light diffusing agent. As the above resin, a resin having optical transparency is suitable. For example, an acrylic resin, a polyester resin, polyvinyl chloride, a polyurethane, or a polyoxyxylene resin can be given. This resin is, for example, marketed by Mitsubishi Snail Co., Ltd. under the trade name "Dianal Series". Further, as the particles used as the light diffusing agent, those suitable for the transparent particles are -80-200810924', and examples thereof include polyfluorene oxide resin particles, acrylic resin particles, nylon resin particles, urethane resin particles, and styrene resin. Particles, polyethylene resin particles, vermiculite particles, and polyester resin particles. These particles may be used singly or in combination of two or more. Further, the surface or the entirety of the above fine particles may be crosslinked. In the resin, the mixing ratio of the particles is preferably from 5 to 150 parts by mass based on 100 parts by mass of the resin from the viewpoint of obtaining sufficient light diffusibility while ensuring light transmittance. Further, the average particle diameter of the particles is usually from 1 to 70 μm, preferably from 5 to 5.

5 0 μηη. In other words, if the average particle diameter of the particles is outside the above range, the balance between the light transmittance and the light diffusibility may collapse, and the front luminance may not be increased. Further, when spherical particles are used as the particles, each of the spherical particles functions as one type of lens, and a more effective light diffusion effect can be obtained. In particular, true spherical particles are effective. The true spherical particles are, for example, true spherical vermiculite particles sold by Nippon Shokubai Co., Ltd. under the trade name of Epo star. A representative production method of the light-diffusing film is shown below. A coating liquid obtained by mixing and dispersing a binder resin, a solvent, and particles in a specific ratio by a conventional coating method is applied to an adhesive modified layer of an adhesive modified base film (for laminated hard coating) On the opposite side of the surface of the layer). Then, the coating layer is dried and cured by a drying method such as natural drying or hot air drying to form a light diffusion layer on the surface of the adhesive base film. A preferred method of formulating the coating liquid is as follows. First, the binder resin is dissolved in a solvent in a specific ratio. In the solution, the particles may be dispersed in a ratio of -81 - 200810924, optionally with other optional components, to prepare a mixed dispersion. At this time, the viscosity of the mixed dispersion was adjusted so as to be in the range of 1 to 500 poise. Further, the viscosity of the liquid can be measured using a Brookfield viscometer (B-shaped viscometer).

Next, the coating liquid was applied onto the surface of the adhesive reforming layer of the adhesive-modified substrate film and dried. The coating method of the coating liquid is selected in accordance with the viscosity of the solution or the thickness of the coating layer to be used. For example, as a coating method, a comma guiding method, a roll coating method, a dipping method, a knife coating method, a curtain flow method, a spray coating method, a spin coating method, and a lamination method can be given. Further, the thickness of the adhesive-modified substrate film is preferably from 50 to 200 μm from the viewpoint of use or workability. Further, the thickness of the light diffusion layer is preferably 2 to 30 μm. Further, the solvent is, for example, toluene, methyl ethyl ketone, xylene, cyclohexane or ethyl acetate. In addition, the mixing ratio of the solvent is appropriately set in accordance with the coating method, the workability, the type of the solvent, etc., but it is preferably 50 to 500 parts by mass for 100 parts by mass of the binder resin. Further, in the case of the particles, the mixing ratio of the solvent is in accordance with the coating method, the workability, the type of the solvent, etc., and the solvent is suitably set in the range of 20 to 500 parts by mass for 1 part by mass of the particles. . More preferably, the solvent is 50 to 300 parts by mass for 100 parts by mass of the particles. In other words, when the mixing ratio of the solvent is within the above range, the amount of the solvent in the particles is an appropriate amount to soften the resin. Further, as a subcomponent of the light-diffusing layer, for example, an isocyanate compound, an epoxy resin, a methylolated honey-82-200810924 amine resin, a methylolated urea resin, a metal salt, or the like may be contained. Crosslinking agent such as metal hydroxide, hydrazine derivative, phosphoric acid anionic active agent, sulfonic acid, quaternary ammonium salt, pyridyl salt, imidazoline derivative 'morpholine derivative, polyoxyethylene-alkylphenol, An antistatic agent such as an alkylamine or a sorbitan fatty acid ester or a decane coupling agent. Example

Next, the hard coating film of the present invention and an optical functional film using the same will be described using examples and comparative examples, but the present invention is of course not limited to the examples. Further, the physical properties or properties of the adhesive modified base film, the hard coated film, and the optical functional film described in the examples were evaluated by the following methods. (1) Phase separation structure of the adhesion modifying layer (1-1) Surface of the adhesion modifying layer of the adhesive modified base film (1-1-1) Observation of the phase image Surface of the modified layer The evaluation of the phase separation structure of the intermediate-adhesive modified layer was carried out in a phase measurement mode (phase mode) using a scanning probe microscope (SPI3 800N series/SPA3 00, manufactured by SII Nanotechnology Co., Ltd.). In the phase image, the larger the phase retardation, the brighter the performance, and the smaller the phase retardation, the darker the performance. A small phase delay means that the system is hard or has a relatively small adsorption force compared to others. In the adhesive modifying layer of the adhesive modified base film used in the present invention, the dark phase is a polyester phase and the bright phase is a polyurethane phase. The measurement principle of the phase measurement mode of the scanning probe microscope is described in the website of SII Nanotechnology Co., Ltd. (http://www. siint.com/technology/ -83-200810924 probe-applications.html) "1_2·Application In the PDF file of "1.SPM Phase Measurement" in the Phase column of "Mode".

The cantilever used for the measurement mainly uses DF3 (spring constant: about 1.6 Ν / Π 1), and new products are often used in order to prevent the sensitivity and decomposition ability from being lowered due to probe contamination. The scanner uses the FS-20A. Further, the phase image observation system was performed with a resolution of 512 x 512 pixels or more, and the field of view was 5 μηι><5 μηι. The measurement parameters such as the amplitude attenuation rate of the cantilever, the scanning speed, and the scanning frequency at the time of measurement are set to observable conditions in which linear scanning is performed, sensitivity is the highest, and decomposition ability is good. (1-1-2) Measurement of area ratio of polyester phase (a) Image analysis Image processing software (Adobe Photoshop 7.0) was used to read the obtained phase mode image (bit image format, 512x512 pixels) ) is displayed on the display in such a manner that the image size is 205 mm x 205 mm (refer to Fig. 1). Next, the black line is drawn at the boundary between the bright phase and the dark phase by the pencil tool of the same software (main diameter: 3 px) to make the boundary between the two phases clear (refer to Fig. 2). Furthermore, using the coating tool of the same software, the dark phase is painted black, and the bright phase is painted white to be divided into two (see Fig. 3). At this time, the dark portion having a diameter of 2 mm or less in the bright phase is judged by the size on the screen, and the particles are partially colored in the bright phase and are coated with white. For example, when using vermiculite particles, it is confirmed that such a bias is in the bright phase. The image of the two sides is represented by the same software, the brightness (black and white) is taken as the horizontal axis, and the degree is regarded as the vertical axis, and is represented by a strip chart, and the area ratio of the black portion (polyester phase) is obtained. As the adhesion modifying layer of the adhesive modified base film -84- 200810924 The area ratio of the polyester phase in the surface. (b) Paper gravimetric method The area ratio of the polyester phase in the surface of the next modified layer was measured by using a paper weight method in addition to image analysis. The measurement procedure is as follows.

The resulting phase mode image is saved as a digital image in the form of a bit map. Next, the image was printed and printed on a printer (manufactured by Xerox, DocuPrint C8 30) to the A4 version of the upper paper. For the output image (200mm x 20 0mm), in the bright room under the illumination of 500 lux, visually confirm the boundary between the bright phase and the dark phase in the image, and make it clear with a 4B pencil. At this time, the dark portion having a diameter of 0.1 μm or less which is present in the bright phase is confirmed to be a particle contained in the adhesion-modifying layer which is biased in the bright phase. Therefore, no line is drawn at the boundary between the bright phase and the dark portion inside, so that the dark portion is contained in the bright phase. Then, use a cutter to cut and divide the boundary between the bright phase and the dark phase. Next, the mass of the paper of the bright phase (polyurethane phase) and the dark phase (polyester phase) was measured, and the dark phase was obtained in units of % for the total mass of the paper of the bright phase and the dark phase ( The ratio of the mass of the polyester phase to the area ratio of the polyester phase in the surface of the adhesive modified layer, and (c) the variation range of the area ratio of the polyester phase (the difference between the maximum 値 and the minimum )) ( C-1) The roll formed by the adhesive-modified base film having a length of l〇〇〇m or more and a width of 50 mm or more is wound up in the longitudinal direction of the film roll. With respect to the longitudinal direction (MD) of the film, the area ratio of the polyester phase (in the phase -85 to 200810924 image showing the dark phase) in the surface of the adhesion-modifying layer was measured in the following place. Next, the area ratio of the polyester phase in the surface of the adhesion-modifying layer was determined in each place. Furthermore, the difference between the maximum 値 and the minimum 求 is obtained from their area ratios. The area ratio of the polyester phase in the surface of the modified layer is determined by using one end of the stable region of the physical stability of the film as the first end and the other end as the second end, and at the first end. The first measurement was performed on the inner side of 2 m or less, and the final measurement was performed on the inner side of the second end portion by 2 m or less, and the measurement was performed every 100 m from the first measurement place.

(c-2) Roll-up of the adhesive-modified substrate film having a length of l〇〇〇m or more and a width of 50 mm or more in the width direction of the film roll, and the film width in the width direction (TD) of the film Directions are made in 4 equal parts. Next, the area ratio of the polyester phase (the dark phase in the phase image) of the surface of the adhesive reforming layer was measured at the respective center portions. Next, the difference between the maximum 値 and the minimum 面 of the area ratio of the polyester phase in the surface of the adhesion-modifying layer in the width direction was determined. This measurement can be carried out by cutting a large roll before cutting the width direction of the film into a small size. (1 - 2) The cutting surface which is inclined with the adhesion modifying layer in the hard coating film is in the hard coating film of the present invention, and the adhesion modifying layer B is the intermediate layer of the thermoplastic resin film A and the hard coating layer C. . Therefore, it is difficult to directly observe the phase separation structure of the resin in the interface between the adhesion-modifying layer B and the hard coating layer C (the surface of the adhesion-modifying layer in the adhesive-modified substrate film). Therefore, the inventors of the present invention have found that the hard coating film can be cut in the thickness direction, and the phase separation structure of the resin in the thickness direction of the adhesion modifying layer can be measured from the cutting surface. Further, since the thickness of the adhesive reforming layer is usually thin, from -86 to 200810924, it is difficult to observe the phase separation of the resin from the cutting surface of the adhesive layer.

Therefore, for the thickness direction, the hard coating film is cut at an obliquely shallow angle. As a result, the observation area in the thickness direction of the adhesive reforming layer can be enlarged. According to this technique, the phase separation structure of the resin constituting the adhesion modifying layer can be observed in the vicinity of the interface between the adhesion modifying layer B and the hard coating layer C.

Hereinafter, a method for producing the sample for evaluation and a method for evaluating the area ratio of the polyurethane phase in the cut surface of the adhesive layer adjacent to the interface with the hard coating layer C will be described in detail. (1_2-1) Cutting specimens The hard coating film of the invention has a thermoplastic resin film as A, an adhesive layer as B, and a hard coating layer as C, which contains A/B/ A layered body of C or B/A/B/C layers. Further, in the optical functional film using the hard coating film, when another optical functional layer is used as D, it is a laminate comprising a layer of D (including C)/B/A/B/C. In the hard coating film or the optical functional film, the surface of the thermoplastic resin film A or the optical function layer D was cut from the oblique direction using the cutting device 1 (SA1CAS DN20-S type) under the conditions shown below. When the blade reaches the specified depth, press a button called "cut-in limit" to perform cutting at a certain depth. Further, in the case where the thermoplastic resin film to be cut is thick, it is preferable to perform cutting several times in the same place. (a) Cutting means: diamond knife (front angle: 40 degrees) (b) moving speed of the blade in the horizontal direction: 3 000 nm/s (c) moving speed of the blade in the vertical direction: 200 nm/s -87 - 200810924 The above "designated depth" means to cut most of the thermoplastic resin film, but does not reach the depth of the adhesion modifying layer. Further, the "cutting limit" means that the moving speed of the blade in the vertical direction is zero, and only the cutting in the horizontal direction is performed. Then, using the cutting device 2 (SAICAS NN-04 type) in the same place, high-precision cutting was performed from the oblique direction under the conditions described below to prepare a cutting sample. (d) Cutting means: diamond knife (front angle · 40 degrees)

(e) Movement speed of the blade in the horizontal direction: 500 nm/s (f) Movement speed of the blade in the vertical direction: 20 nm/s Further, the above cutting conditions are used for cutting the examples and comparative examples described in the present invention. Representative conditions for the resulting hard coated film. The three-dimensional cutting method using a three-dimensional cutting tool is also effective depending on the sample. Also, the blade width of a diamond knife is usually 1 mm, but 0.3 mm is also effective. In the examples and comparative examples described in the present invention, a diamond blade having a blade width of 1 mm was used. Therefore, when the material type of each layer of the hard coating film is different from the materials used in the examples and comparative examples described in the present invention, it is preferable to carry out preliminary tests to determine appropriate cutting conditions. Further, when cutting is performed on the surface of the optical function layer D (including the hard coating layer C), it is necessary to heat or cool at the time of cutting in accordance with the physical properties of the optical functional layer. For the heating or cooling, a low-temperature, high-temperature gas injection device (TTFC-L type, manufactured by DAIPLA.WINTES Co., Ltd.) can be used. The temperature or gas flow rate during heating or cooling can be adjusted according to the state of the cutting surface -88- 200810924

(1-2-2) Observation of phase image

In the cutting surface of the obtained cutting sample, the phase separation structure of the resin of the subsequent modified layer B, the phase image obtained by the phase measurement mode (phase mode) using the scanning probe microscope (SPM), The phase separation structure of the resin of the adhesive layer B was observed. The phase mode is usually a phase delay measurement mode that is performed while observing the state of the power mode (DFM mode; SPM by SII Nanotechnology Co., Ltd.). In the phase image of the cut surface of the adhesive layer B, the dark phase is a polyester phase and the bright phase is a polyurethane phase. The cantilever used for the measurement mainly uses DF3 (spring constant: about 1.6 N/m), and new products are often used in order to prevent the sensitivity and decomposition ability from being lowered due to probe contamination. The scanner uses the FS-100A. Further, the observation field of the phase image is 3 μm >< 3 μιη. The measurement parameters such as the amplitude attenuation rate of the cantilever, the scanning speed, and the scanning frequency at the time of measurement are set to observable conditions in which linear sweeping is performed, the sensitivity is the highest, and the decomposition ability is good. (1-2-3) Determination of the area ratio of the polyurethane phase The image attached to the application document also includes the image indicated by the color image, but for the relationship of the electronic file application, the color image is The JPEG file format is saved in grayscale. In addition, in order to prevent deterioration of image quality, black and white images are also stored in JPEG file format, and are represented by gray scales. (a) The phase image is read using SPIP software (Image 4.2.5, manufactured by Image Metrology). The phase image obtained is read in color from -89 to 200810924. (b) Emphasis on the contrast of the phase separation structure (refer to Fig. 8) The receiver's color equalization process is performed by the software to make the phase separation structure easy to see and emphasize contrast. (c) Determination of the observation range of the phase separation structure (refer to Figure 9)

Copy the phase image that has been subjected to color uniformization and paste it on the screen of the presentation software (Microsoft Power Point 2002). Next, a red line 20 is drawn at the interface (B/C) between the adhesive layer B and the hard coating layer C. At this time, when the interface is not clear, adjust the contrast. Further, from the interface (B/C) toward the adhesion-modifying layer B, the red line of the above-mentioned interface is reproduced in parallel at a depth of 20 nm in the vertical direction, and is pasted (line 21 of Fig. 9). Further, when the cutting sample is produced, the laminated body is cut from the oblique direction. Therefore, in the above-described cutting conditions, the position from the interface toward the adhesive modified layer B at a depth of 20 nm corresponds to a position at a distance of 500 nm from the interface in Fig. 9 . In this way, the range surrounded by the two red lines, that is, the range from the interface (B/C) to the depth of the adhesive layer B of 20 nm, is regarded as the resin in the cutting surface of the adhesive layer B. The range of phase separation structures. (d) Image processing of phase separation structure The image of Fig. 8 is stored as a JPEG file and attached to the image processing software (P h 〇t 〇sh ο p 6 , 0 · 1 version of A d 〇be) The screen and the threshold are expressed in black and white second-order modulation of 128 (refer to Fig. 10). Next, paste the image of the first image into the presentation software (Microsoft -90- 200810924

PowerPoint 200 2) screen. However, overlapping with the image of Fig. 9, the two red lines (20, 21) shown in Fig. 9 are shown on the video of Fig. 10 (see Fig. 11). The image of the eleventh image is displayed on the screen of the image processing software (Photoshop version 6.1 of Adobe). Further, a portion other than the adhesive reforming layer is coated with red using a brush tool (refer to Fig. 12). Use the same software to convert white, black, and red 3x images with brightness (black and white) as the horizontal axis and degrees as the vertical axis, represented by the strip chart.

Further, in the phase image of the adhesive layer Β shown in Fig. 2, the black portion means a polyester phase and particles, and the white portion means a polyurethane oxime. The area ratio of the polyurethane phase (white portion) of the adhesive modified layer B is determined by the following formula from the interface between the interface of the adhesive modified layer Β and the hard coating layer C to the depth of 20 nm. To calculate. Further, the "measured area" on the right side of the following equation means the range of the phase image line 20 (interface Β/C) of Fig. 11 and the line 21. Area ratio (%) of the polyurethane phase = (area of white portion / area of measurement) χ 1 00 (2) Where the width of the polyester phase is at least Ιμπι in the above-mentioned phase mode image, In the polyester phase in which the copolymerized polyester was used as the main component, it was investigated in the place where the width of the short-axis direction was the smallest, and the presence or absence of Ιμπι was investigated. (3) Fractal Dimension of Phase Separation Structure Using the above-described scanning probe microscope (SII Nanotechnology, SPI3 800N System/SPA300), the phase mode -91 - 200810924 image obtained by the phase measurement mode (phase mode) is used ( The bit map format, 512x512 pixels) is read into the image processing software (Adobe Photoshop 7.0) and displayed on the display so that the image size is 2〇5mmx205mm (see Fig. 1). Next, the black line is drawn at the boundary between the bright phase and the dark phase by the pencil tool (main diameter: 3 px) of the same software to make the boundary of the two phases clear (see Fig. 2). At this time, the dark portion having a diameter of 2 mm or less in the bright phase of the size on the screen is judged to be a particle having a bright phase, and the operation line for drawing the boundary line is not performed on the portion. For example, when using vermiculite particles, it can be confirmed that the bias is

The clarified image of the boundary line is saved as a bitmap image, and the fractal method is used to perform the fractal analysis, and the obtained fractal number 値 is regarded as the complexity of the boundary line indicating phase separation. Index. In the analysis of the grid counting method, the image analysis software (AT-Image version 3.2) is used. Specifically, the stored bitmap image is opened on the image analysis software (AT-Image version 3.2), and the luminance strip image is binarized according to the image taken in the manual (see Fig. 6). Moreover, the valve system is the second. For the binarized image, select the fractal dimension according to the image measurement in the manual to obtain the fractal dimension. At this time, in the calculation of the least square fractal element, the counting result of the grid of 6 pixels to 63 pixels on one side is used. Furthermore, the analysis of the fractal dimension of the grid counting method is a conventional method, and other image analysis software or programs used in the dimensional analysis can be used as long as the reproducibility of the analysis result can be sufficiently obtained. Functional software. Other softwares include image analysis software such as "Independent Administrative Corporation Agricultural Technology Research -92-200810924 Fragmentation Analysis System 3.33 Edition" and "Popimaging 3·40 Edition" by Digital Being Kids Co., Ltd. Mm body. (4) Average particle size of inorganic fine particles in hard-coated phase c

The sample of the hard coating film is embedded in a visible light-curable resin (for example, an epoxy resin), and is allowed to stand at room temperature to be cured. Next, an ultrathin section was prepared using an ultramicrotome equipped with a diamond knife, and dyed by osmium tetroxide. For the dyed ultrathin section, a cross section of the hard coating layer c was observed using a transmission electron microscope (TEM 2 010 manufactured by JEOL Ltd.), and photographs were taken. Further, the magnification of the photograph is suitably set in the range of 10,000 to 100,000 times in accordance with the particle diameter of the inorganic particles observed. Further, in the first embodiment of the present invention, the magnification is regarded as 80,000 times (acceleration voltage 200 kv). From this photograph, the average particle diameter on the basis of the number of inorganic fine particles in the hard coating layer C was determined. (5) Haze According to JIS K7136, a haze meter (NDH2000 manufactured by Nippon Denshoku Co., Ltd.) was used, and the haze was measured at three different places of the film sample, and the average enthalpy was used. (6) Anti-blocking property The adhesive modifying layers of the two sheets of the adhesive-modified substrate film were each overlapped. Subsequently, a pressure of lkgf/cm2 was applied thereto, and the mixture was allowed to adhere for 24 hours in an atmosphere of 50 ° C and 60% RH. Then, the interface between the adhesion-modifying layer and the adhesion-modifying layer of the two sheets of the adhesive-attached substrate film which were adhered to each other was peeled off, and the peeling state was judged based on the following criteria. 〇: The adhesive layer is not transferred and can be easily peeled off -93- 200810924 △: The peeling sound occurs, and then the modified layer is partially transferred to the opponent's surface X: 2 sheets of film are fixed and cannot be peeled off, even if the peeling substrate is gathered The ester film is also cracked (7) hardness index of the adhesive layer

On the surface of the adhesion-modifying layer of the adhesive-modified substrate film, a surface measuring instrument (HEIDON 14 manufactured by New East Asia Chemical Co., Ltd.) was used for the marking. In this case, as a needle for injury, a pure needle with a sapphire having a radius of 75 μm is attached at the front end. The traveling speed of the needle was 150 mm/min, and the weighting was measured on the surface shape of the adhesive layer by using a three-dimensional non-contact surface shape measuring device (Micromap 5 50 from MICROMAP) under the following conditions. , expressed as outline mode data. A representative example is shown in Figure 5. From the shape data of the obtained flaws, the height difference between the adjacent convex and concave portions was measured at 30 places, and their average enthalpy was obtained as the hardness index of the adhesive modified layer. In this case, the protrusion having a height of 3 〇 nm or more is determined to be a protrusion caused by the particles contained in the adhesive layer or the thermoplastic resin film, and is removed from the measurement data. Further, the protrusions having a height of i nm or less are similarly removed from the measurement data due to the influence of noise. (Measurement conditions) • Contour mode: Waveform mode • Objective lens: 1 〇 Times • Resolution: 1 60x 1 60 pixels • Measurement length __ 2 07.1nm (8) Adhesion to hard coating layer -94- 200810924 (8- 1) Adhesion between the adhesive layer B and the hard coating layer C

On the glass plate having a thickness of 5 mm to which a double-sided tape was adhered, the opposite surface of the hard coating film C or the optical functional film obtained in the examples and the comparative examples was adhered to the hard coating layer C. Next, using a blade guide having a gap of 2 mm, 100 square-shaped blade wounds penetrating the hard coating layer C and the adhesion-modifying layer B and reaching the thermoplastic resin film A were produced. Next, the tape (No. 405 made by NICHAN); 24 mm wide was attached to the square-shaped blade. When pasting, the air remaining in the interface is pressed by the eraser so that the tape is strongly and vertically peeled off after the close contact. The new tape is reapplied in the same way, and the tape is also peeled off vertically. The tearing operation of the tape was repeated 1 times in total, and the adhesion was visually determined by the following formula. Furthermore, some of the peelers in one square are also included in the number of stripped. Adhesiveness (%) = (1 - number of squares peeled off / 100) xl 〇〇 (8-2) Evaluation of adhesively modified base film Two types of light formed by solvent-diluted type and solvent-free type The hard coating layer of the curable acrylic resin and containing no particles was evaluated for the adhesion between the hard coating layer and the adhesion-modifying layer B in accordance with the above method. The sample for evaluating the adhesion between the adhesive-modified substrate film and the hard coating layer was produced in the following manner. (a) Adhesion to a hard coating layer composed of a solvent-diluted photocurable acrylic resin to the surface of the adhesive-modified layer B of the film sample, and 50 parts by mass of hard coating was applied by a wire rod Agent (Seikabeam EXF0 1 (B)), 25 parts by mass of toluene, 25 parts by mass of methyl ethyl ketone -95-200810924 A well-stirred coating agent, dried at 7 (TC for 1 minute) After removing the solvent, a hard coating film having a hard coating layer having a thickness of 3 μm was obtained under the conditions of a pressure of a mercury lamp of 200 mJ/cm 2 , an irradiation distance of 15 cm, and a traveling speed of 5 m/min. (b) With a solvent-free type Adhesion of hard coating layer composed of photocurable acrylic resin

Approximately 5 g of a hard coating agent (Seikabeam EXF01 (B) manufactured by Daisei Seiki Co., Ltd.) was placed on a glass plate having a thickness of 5 mm, and the surface of the adhesive layer of the film sample was brought into contact with the hard coating agent. The overlap was carried out by means of a manual load-bearing rubber roller having a width of 10 cm and a diameter of 4 cm from the film sample to be crimped by expanding the hard coating agent. Next, the hard coating layer was cured by irradiating ultraviolet rays from the film surface side under the conditions of a high pressure mercury lamp at 500 cm/cm2, an irradiation distance of 15 cm, and a traveling speed of 5 m/min. Then, the film sample having the hard coating layer was peeled off from the glass plate to obtain a hard coating film. (9) Pencil hardness The surface of the hard coating layer C was measured by a pencil hardness test in accordance with JIS-K5400. In the pencil hardness test, the test was repeated five times. In all the tests, if the appearance of the scratch or the like was not observed on the surface of the hard coating layer C, the hardness of the pencil used in the test was regarded as a pencil. hardness. For example, a pencil of 3H was used for 5 tests, and if no appearance abnormality occurred in all the tests, the pencil hardness of the material was at least 3 。. In this evaluation, 3 Η or more is regarded as 〇, and 2 Η or less is regarded as X. (Example 1) -96 - 200810924 (i) Preparation of coating liquid The coating liquid used in the present invention was prepared in accordance with the following method.

Dimethyl phthalate (95 parts by mass), dimethyl isononanoate (95 parts by mass), ethylene glycol (35 parts by mass), neopentyl glycol (145 parts by mass), zinc acetate (〇·1 The mass part) and the antimony trioxide (〇·1 part by mass) were put into the reaction vessel and the transesterification reaction was carried out at 180 ° C for 3 hours. Next, 5-sulfoisophthalic acid 5-sodium (6.0 parts by mass) was added, and the esterification reaction was carried out at 240 ° C for 1 hour, and then under a reduced pressure of 250 ° C (10 〇. 2 mmHg), it took 2 hours. The polycondensation reaction was carried out to obtain a copolymerized polyester having a number average molecular weight of 1,900 and a softening point of 6 °C. 7.5 parts by mass of a 30% by mass aqueous dispersion of the obtained copolymerized polyester (A), and 13.3 parts by mass of a self-crosslinking polyamine of an isocyanate group blocked with sodium hydrogen sulfite 20% by mass aqueous solution of formic acid ester (B) (ELASTRON H-3 manufactured by Dai-ichi Pharmaceutical Co., Ltd.), 0.3 parts by mass of catalyst for ELASTRON (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 39.8 parts by mass of water, and 37.4 parts by mass The isopropanol was mixed separately. Further, 0. 6 parts by mass of a fluorine-based nonionic surfactant (manufactured by Dainippon Ink and Chemicals, Megafac F142D), and a mass% of 2.3% by mass of colloidal vermiculite as particles A (Nissan Chemical Co., Ltd.) Industrial quality Snowtex OL; average particle size 40nm) 20% by mass aqueous dispersion, 0.5 parts by mass dry-type vermiculite as particle B (ArosilOX50 made by Arosil, Japan; average particle size 200nm, average primary particle size 40nm) 3.5 mass % aqueous dispersion. Next, the pH of the coating liquid was adjusted to 6.2 with a 5% by mass aqueous sodium hydrogencarbonate solution, and the filter was prepared by filtering a particle size (initial filtration efficiency: 95%) into a felt-type polypropylene filter. 200810924 Coating solution A. Further, the above surfactant is a pretreated person using the following method.

Isopropanol (IPA) was added to the above-mentioned interface-containing compound, and the solution was heated and dissolved in a 30 ° C warm bath to prepare a 15 mass% surfactant IPA solution. The solution was filtered with a quantitative filter paper (ADVANTECH Toyo N 5 · C) to remove insoluble matter and dust from the solution. After filtering the solution, the solution was placed in a closed glass container and allowed to stand in a freezer at 〇 °C for 24 hours. After 24 hours, the above-mentioned quantitative filter paper was used, and a solution containing the precipitated solid was suction-filtered. The solid on the filter paper was vacuum dried to obtain a solid, which was diluted with water to a 1% by mass aqueous solution, and used as a pretreated surfactant. Further, the surfactant obtained by the above pretreatment was analyzed by using a TLC-coated plastic sheet (Merck 矽 gel 60) using methanol as a developing solution. The sample spots were colored by iodine vapor, and as a result, it was confirmed that no spots corresponding to polyethylene glycol were detected. (2) Production of adhesively modified base film: For the raw material polymer, nine particles of polyethylene terephthalate (PET) resin having an intrinsic viscosity of 0.62 dl/g, which does not contain particles, are made at 135 ° C. Dry under reduced pressure (ITorr). Next, nine pieces of the dried PET resin were supplied to an extruder, melt-extruded into a sheet at about 285 ° C, and quenched and solidified on a metal roll maintained at a surface temperature of 20 ° C to obtain a cast film. At this time, as a filter medium for removing impurities in the molten resin, a sintered stainless steel filter material having a filter particle size (initial filtration efficiency: 95%) of 15 μm was used. The obtained cast thin film-98-200810924 film was heated to 95 5 t with 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 difference to obtain A shaft aligned PET film. Next, the coating liquid was finely filtered by a felt-type polypropylene filter material having a particle size (initial filtration efficiency: 95%) ,μηη, and coated on one side of the one-axis alignment PET film by a reverse roll method. Further, at this time, the coating roller and the measuring roller of the coater were made of a hardened chrome-plated surface having a surface of 0.2 S or less and a roundness of 3 to 1000 mm.

Then, in the drying furnace divided into four zones disposed directly above the coater, in the first zone (1 3 5 °C for 1 · 0 seconds) and the second zone (6 5 ° C for 2 · 2 seconds) The coated surface was dried in the third zone (40 ° C for 1.8 seconds) and the fourth zone (30 ° C for 1.8 seconds). Further, the coating amount was such that the final solid content was 0.08 g/m2. The film passage time is 〇8 seconds from the application of the film to the entrance of the drying furnace. Further, at this time, the wind speed of the dry air in the first zone is set to 30 m/sec, the air supply air volume of the dry air is 130 m 3 /sec, the exhaust air volume is 170 m 3 /sec, and the air supply from the second zone to the fourth zone is given. The air volume is 100m3/sec, and the exhaust air volume is 15 0m3/sec, so that the dry air does not flow to the coater side. Further, the tension of the film is 7000 N/original, and the both ends of the film are grasped by the nip rolls from the application to the entrance of the drying furnace, and the capacity of the coating liquid is applied during the coating at this time. The ratio of the capacity of the circulation tank to the capacity of the preparation tank is a coating apparatus having the following relationship. (a) The ratio of the capacity of the coating liquid to the capacity of the circulation tank = 1/50 (b) The ratio of the capacity of the circulation tank to the capacity of the mixing tank = 1/40 Next, grasp the film with a jig The end is guided to a hot air zone with a temperature of 1 20 °C and a wind speed of 15 m/s, and is stretched by 4.3 times in the width direction -99- 200810924

. Then, the width in the width direction is maintained as it is, and the first heat setting zone (temperature: 200 ° C) and the second heat setting zone are continuously passed in order (temperature: 225. 〇, third heat setting zone (temperature: 230 ° C), the fourth heat setting zone (temperature: 23 0 ° C), the fifth heat setting zone (temperature: 210 ° C), the sixth heat setting zone (temperature · 17 ° ° C), the seventh heat The setting zone (temperature · 120 ° C). Further, 3% relaxation treatment is performed in the width direction in the sixth heat setting zone. Then, the uncoated portion at both ends of the trimmed film is wound around the winding. The device is further cut into four equal parts in the width direction to obtain a roll of an adhesive modified polyester film having a width of 1000 mm, a film length of 1,000 m, and a film thickness of 125 μm. Further, the wind speed of the hot air in the heat setting zone is It is 15 m/sec, the passage time is 4.5 seconds in each zone, the nozzle spacing of the hot air is 305 mm, and the number of nozzles per zone is 8. Table 4 shows the physical properties of the adhesive substrate film and Further, Table 5 shows the length direction and width direction of the obtained roll of the adhesive modified polyester film. In the middle layer, the maximum area ratio of the polyester phase on the surface of the adhesion-modifying layer is the maximum 値, the minimum 雾, the maximum 値, and the minimum 雾, and the maximum 値 and minimum 密 of the adhesion of the hard coating layer. The anti-blocking property is 〇 at all the measurement points. (3) The production of the hard coating film is followed by the following method on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film. A hard coating layer C containing inorganic fine particles in one area layer to obtain a hard coating film. As a coating liquid for forming a hard coating layer, ultraviolet curable acrylate monomer, oxidized cone ultrafine particles, and methyl ethyl ketone are prepared as An organic/inorganic hybrid hard coating agent (Desolite Z7410B manufactured by JSR Co., Ltd.; solid content concentration: 50% by mass) of the main-100-200810924. The hard coating agent was applied to the adhesive modification so that the dry thickness became 8 μm. The surface of the adhesive substrate of the substrate was dried at 40 ° C for 1 minute. Then, ultraviolet rays were irradiated under a condition of 1000 mJ/cm 2 with a high pressure mercury lamp to harden the resin to form a hard coating layer C.

In the obtained hard coating layer, the content of the chromium oxide ultrafine particles having an average particle diameter of 1 is 31 parts by mass based on 1 part by mass of the acrylate resin. (Example 2) A fluorine-based cationic surfactant (Ftergent 3 1 0 manufactured by NEOS Co., Ltd.) pretreated in the same manner as in Example 1 was used as the "surfactant for the coating liquid" in Example 1. An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the aqueous solution of 10% by mass was changed to the coating liquid B. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 3) In the heat setting treatment step of Example 1, the temperature of each heat setting zone was set to 190 ° C in the first heat setting zone, and the second heat setting zone was 20 5 ° C, the third heat. By setting the zone at 220 ° C and the fourth heat-setting zone at 220 ° C, the same method as in Example 1 was used to obtain an adhesive modified polyester film.

-101 - 200810924 Next, 'on the surface of the adhesion-modifying layer B of the above-mentioned adhesive-modified base film', in the same manner as in Example 1, the hard coating layer C containing inorganic fine particles in one area layer was obtained to obtain a hard coating. film. (Example 4) In the first embodiment, the mass ratio of the copolymerized polyester to the polyurethane in the coating liquid was changed to 60/40, and the coating liquid C was changed to the following coating liquid C. In the same manner as in Example 1, an adhesive modified polyester film was obtained.

(Preparation of Coating Liquid c) 9.0 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1, and 9.0 parts by mass of the polyurethane (B) used in Example 1 A 20% by mass aqueous solution, 0.3 parts by mass of ELASTRON catalyst (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 40.6 parts by mass of water, and 37.3 parts by mass of isopropyl alcohol were separately mixed. Further, 0.6 parts by mass of the aqueous surfactant solution used in Example 1 and 2·3 parts by mass of colloidal vermiculite (Snowtex OL manufactured by Nissan Chemical Industry Co., Ltd.; average particle diameter: 40 nm) of 20% by mass were added. 0.5 mass part of a 0.5% by mass aqueous dispersion of dry-type vermiculite (Arosil 0X50 manufactured by Arosil, Japan; average particle diameter: 200 nm, average primary particle diameter: 40 nm) as a particle dispersion, and 5% by mass of sodium hydrogencarbonate The aqueous solution particles were used to adjust the pH, and the filter having a filtration performance of 5 μm and Ιμπι was passed in order to form a coating liquid C. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. -102-200810924 (Example 5) In the first embodiment, the mass ratio of the copolymerized polyester to the polyurethane in the coating liquid was changed to 40/60, and the coating liquid D was changed to the following. An adhesive modified polyester film (formulation of coating liquid D) was obtained in the same manner as in Example 1.

6.0 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1, 13.5 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1, 0.3 mass The ELASTRON was mixed with a catalyst (Cat64, manufactured by Daiichi Kogyo Co., Ltd.), 38.9 parts by mass of water, and 37.5 parts by mass of isopropyl alcohol. Further, 6 parts by mass of the 1% by mass aqueous solution of the surfactant used in Example 1 and 2.3 parts by mass of colloidal chopped stone as Particle A (Snowtex OL manufactured by Nissan Chemical Industry Co., Ltd.; average particle diameter: 40 nm) were added. 20% by mass of the aqueous dispersion, 0.5 parts by mass of the dry-type vermiculite (Arosil 0X50 manufactured by Arosil, Japan; average particle diameter: 200 nm, average primary particle diameter: 40 nm) as a particle B, and a 3.5% by mass aqueous dispersion of 5% by mass The aqueous solution of sodium hydrogencarbonate was adjusted to pH 6.2, and passed through a filter having a filtration performance of 5 μm and 1 μm to form a coating liquid D. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 6) A modified polyester was obtained in the same manner as in Example 1 except that the coating amount was changed to a final solid content of 0·12 g/m 2 in the same manner as in Example 1. film. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 7) In the same manner as in Example 1, except that the amount of the surfactant in the coating liquid was changed to 3% by mass of 〇·〇, and the coating liquid E described below was used. In the method, an adhesive modified polyester film was obtained.

(Preparation of the coating liquid E) In the preparation of the coating liquid of the first embodiment, a 10% by mass aqueous solution of a fluorine-based nonionic surfactant (Megafac F142D manufactured by Dainippon Ink and Chemicals Co., Ltd.) was changed to 0.3 parts by mass, and water was added. It was changed to 38.2 parts by mass, and isopropyl alcohol was changed to 39.3 parts by mass. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 8) The same procedure as in Example 1 was carried out except that the amount of the surfactant in the coating liquid was changed to 0.10% by mass in the same manner as in Example 1 except that the coating liquid F described below was used. The polyester film is then modified. (Preparation of the coating liquid F) In the preparation of the coating liquid of the first embodiment, a 10% by mass aqueous solution of a fluorine-based nonionic surfactant (Megafac F142D manufactured by Dainippon Ink and Chemicals Co., Ltd.) was changed to 1.0 part by mass, and water was added. Changed to 37.5 parts by mass, and -104-200810924 Isopropyl alcohol was changed to 39.3 parts by mass. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 9)

In addition to the first embodiment, the film passage time from the application to the drying furnace inlet was changed to 0.7 seconds, the drying time was changed to 0.8 seconds, and the passage time of each zone in the heat setting treatment step was changed to 3 · 5 An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the film thickness was changed to 100 μm. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 10) Except that in Example 1, the film passage time from the application to the drying furnace inlet was changed to 1.0 second, the drying time was changed to 1.9 seconds, and the respective zones in the heat setting treatment step were changed. An adhesive modified polyester film was obtained by the same method as in Example 1 except that the film thickness was changed to 8.8 seconds and the film thickness was changed to 8.8 μm. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 11) The same procedure as in Example 1 except that the pH of the coating-105-200810924 solution was adjusted to 7·9 in a 5% by mass aqueous sodium carbonate solution, and changed to the coating liquid G. In the method, an adhesive modified polyester film was obtained. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Embodiment 12)

An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the adhesive modified layer B was applied to both surfaces of the one-axis alignment polyester film in Example 1. Further, the film passage time from the application of the film to the entrance of the drying furnace was 0.8 seconds on one side and 1.0 second on the opposite side. On the above-mentioned adhesive modified base film, the layer C was hard-coated on the two-layer layer via the adhesive-modified layer B to obtain a hard-coated film. Further, the method of forming the hard coating layer C is as follows. On the surface of one of the adhesion-modifying layers B of the adhesive-modified substrate film, the inorganic coating-containing hard coating agent used in Example 1 was used to have a film thickness of 3 μm after curing. To coat, dry at 40 °C for 60 seconds. Further, ultraviolet rays of 300 mJ/cm2 were irradiated to harden the resin, and a hard coating layer C was formed on one surface. Next, on the surface of the adhesive layer B on the opposite side, the same hard coating agent as described above was applied to the U.S. rod so that the film thickness after curing was 3 μm, and the coating was applied at 40 ° C. Dry for 60 seconds. Further, ultraviolet rays of 50,000 mJ/cm2 were irradiated to harden the resin, and a hard coating layer C was formed on the other surface. -106-200810924 (Example 13) An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating liquid which was not subjected to the pretreatment of the surfactant was used in Example 1. In the surface of the adhesive modified layer of the obtained adhesive modified polyester film, the phase separation structure of the polyester phase of the scanning probe microscope (SPM) and the polyurethane phase is discernible, but Slightly unclear.

Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. In the adhesion-modifying layer B of the cut surface of the obtained hard coating film, the phase separation structure of the polyester phase and the polyurethane phase is also slightly unclear as described above. (Example 14) In the same manner as in Example 1, except that the mass ratio of the dispersion medium (water/IPA) of the coating liquid was changed to 50/50 in the first embodiment, the coating liquid I was used. An adhesive modified polyester film was obtained. (Preparation of Coating Liquid I) In the preparation of the coating liquid of Example 1, 7.5 parts by mass of the 30% by mass aqueous dispersion of the copolymerized polyester used in Example 1, and 11.3 parts by mass of the polymerization used in Example 1 were used. A 20% by mass aqueous solution of urethane, 0.3 parts by mass of a catalyst for ELASTRON (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 30. 4 parts by mass of water, and 46.8 parts by mass of isopropyl alcohol were separately mixed. Further, 0.6 parts by mass of the surfactant used in Example 1 was added, 1% by mass of water-soluble -107-200810924 solution, and 2.3 parts by mass of colloidal vermiculite as particle A (Snowtex OL, Nissan Chemical Industry, average pine) 20% by mass aqueous dispersion having a diameter of 40 nm) and 0.5 parts by mass of a 3.5% by mass aqueous dispersion of dry vermiculite (Arosil 0X50 manufactured by Arosil, Japan; average particle diameter: 200 nm, average primary particle diameter: 40 nm) as particles B. Subsequently, the pH was adjusted to 6.2 with a 5 mass% sodium hydrogencarbonate aqueous solution, and a filter having a filtration performance of 5 μm and 1 μm was passed in order to obtain a coating liquid I.

Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 15) In the same manner as in Example 1, except that the pH of the coating liquid was changed to 4.6 with acetic acid in Example 1, a laminate of a thickness of 125 μm was obtained by the same method as in Example 1. Ester film. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 16) In the same manner as in Example 1, except that the polyurethane was changed to the following polyurethane in Example 1, and the coating liquid was used, the adhesion was changed. Polyester film. Polyurethane is obtained by the following method. (Preparation of Polyurethane) 93 parts by mass of a composition of adipic acid//1,6-hexanediol/neopentyl glycol (mole 108-200810924 ratio: 4//3/2) Polyester diol (OHV; 111.8 eq/ton, AV: l.leq/ton), 22 parts by mass of phenyldimethyl diisocyanate, reacted at 95 to 100 ° C for 1 hour under a nitrogen stream to obtain an amine. Formate prepolymer (NCO/OH ratio: 1.50, free isocyanate group: theoretical 値 3.29 mass%, measured 値3.16 mass%).

The obtained urethane prepolymer was cooled to 60 ° C, and 4.5 parts by mass of methyl ethyl ketone oxime was added thereto, and reacted at 60 ° C for 50 minutes to obtain a partially blocked amine amide containing 1.3% by mass of free isocyanate. Acid ester prepolymer. Next, the urethane prepolymer was cooled to 55 ° C, and a mixed solvent of 9 parts by mass of isopropyl alcohol and 140 parts by mass of methanol was added to uniformly mix. Next, 9.3 parts by mass of a 50% by mass aqueous sodium hydrogensulfite solution and 5.4 parts by mass of a 30% by mass aqueous solution of N-methyltaurine were added, followed by vigorous stirring. Water solubility began to occur after about 30 minutes, and after 2 hours, the free-flowing sodium hydrogen sulfite became approximately zero, and the reaction was completed. Water was added thereto to obtain a white turbid and viscous 20% by mass aqueous solution. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 1) (1) Preparation of Coating Liquid L 33.7 parts by mass of dimethyl perruthenate, 20.0 parts by mass of dimethyl isononanoate, and 9.1 parts by mass of sulfodimethylisodecanoic acid 5- Sodium, 40.0 parts by mass of ethylene glycol, 10.0 parts by mass of diethylene glycol, 〇·〇 49 parts by mass of calcium acetate·1 water salt, transesterified at 200 to 23 ° C until the theoretical amount of -109- 200810924 Methanol is distilled off. Next, 0.09 parts by mass of orthophosphoric acid was added and polymerized under reduced pressure at 28 ° C to obtain a copolymerized polyester. Mixing 192 parts by mass of a polyether of ethylene oxide derived from allyl alcohol with a sulfonic acid group-containing polyether sulfonated with sodium metabisulfite (S03 content: 8.3% by mass, polyethylene oxide content: 83% by mass) ), 1013 parts by mass of polytetramethylene adipate (number average molecular weight: 2,250), 248 parts by mass of polypropylene oxide polyether (number average molecular weight: 55 0) starting from bisphenol A, under vacuum Dehydrated at l ° ° C.

The mixture was brought to 70 ° C, and a mixture of 178 parts by mass of isophorone diisocyanate and 244 parts of hexamethylene-1,6-diisocyanate was added thereto, followed by a range of 80 ° C to 90 ° C. The mixture was stirred under stirring until the isocyanate content became 5.6% by mass. The prepolymer was cooled to 60 ° C, and 56 parts by mass of a biuret polyisocyanate obtained from 3 mol of hexamethylene diisocyanate and 1 mol of water and 175 parts by weight of a different Buddha were sequentially added. The bis-maleamine obtained from ketone diamine and acetone gives a polyurethane aqueous dispersion. Each of the above-mentioned copolymerized polyester and polyurethane aqueous dispersion was blended in an amount of 20 parts by mass and 80 parts by mass in terms of a solid content, and an aqueous dispersion having a solid content of 10% by mass was prepared to obtain a coating liquid L. Further, in the coating liquid, particles and a surfactant are not blended. (2) Production of adhesively modified base film: For the raw material polymer, nine particles of polyethylene terephthalate resin having an intrinsic viscosity of 0.66 dl/g which is not contained in the raw material polymer, at 135 〇 (: 6 hours minus) After pressing and drying (lTorr), it was supplied to an extruder, melt-extruded at about 285 ° C to a sheet of 110-200810924, and rapidly solidified on a metal roll having a surface temperature of 60 ° C to obtain a cast film. In the same manner as in the first embodiment, the filter medium for removing impurities of the molten resin was used, and a stainless steel sintered filter material having a filter particle size (initial filtration efficiency: 95%) of 15 μm was used.

Then, the cast film was heated to 95 ° C with a heated roll group and an infrared heater, and then stretched by 3.5 times in the longitudinal direction by a roll group having a peripheral speed difference to obtain a one-axis aligned PET film. . Then, the coating liquid L was precisely filtered by a filter medium having a filter particle size (initial filtration efficiency: 95%) of 10 μm, and coated on one surface of the one-side alignment PET film by a reverse roll method. Next, the end of the film was grasped by a jig, and introduced into a hot air zone heated to 110 ° C to be stretched 3.5 times in the width direction after drying. At this time, the wind speed in the tenter was 15 m/sec, and the drying time was 20 seconds. The time from the application of the film to the entrance of the tenter is 1 〇.〇 second. Further, the coating amount was such that the final solid content was 〇15 g/m2. Next, the width of the film stretched in the width direction is maintained as it is, and the first heat setting zone (200 ° C), the second heat setting zone (205 ° C), the third heat setting zone, and the fourth heat are continuously passed in this order. Styling zone (210 ° C), 5th heat setting zone (2 15 °C), 6th heat setting zone (2 20 °C), 7th heat setting zone (170 °C). Further, after 3% relaxation treatment in the width direction in the seventh heat setting zone, the portions which were not coated at both end portions of the film were trimmed to obtain a second modified polyester film having a thickness of 1 2 5 . Further, the wind speed of the hot air in the heat setting zone was 15 m/sec, the passage time was 4.5 seconds in each zone, and the nozzle interval of the hot air was 700 mm, and the number of nozzles per zone was four. The phase separation structure of the copolymerized polyester and the polyurethane is not clear in the surface of the adhesive modified layer of the obtained adhesive modified polyester film -111-200810924. (3) Production of Hard Coating Film Next, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer c containing inorganic fine particles in one area layer is formed in the same manner as in Example 1. To obtain a hard coated film. (Comparative Example 2) (1) Preparation of coating liquid helium

3.0 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (Α) used in Example 1, 18.0 parts by mass of a 20% by mass aqueous solution of the polyurethane used in Example 1, 0.3 mass The ELASTRON was mixed with a catalyst (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 70.7 parts by mass of water, and 4.7 parts by mass of isopropyl alcohol. Further, 0.6 parts by mass of a 10% by mass aqueous solution of dodecylbenzenesulfonic acid as a surfactant and 2.3 parts by mass of colloidal vermiculite as a particle A (Snowtex OL manufactured by Nissan Chemical Industry Co., Ltd.; average particle diameter: 40 nm) were added. 20% by mass of the aqueous dispersion, 〇5 parts by mass of the dry method of the particle B as a particle B (Arosil 0X50 manufactured by Arosil, Japan; average particle size 2 〇 Onm, average primary particle diameter 40 nm) 3.5% by mass aqueous dispersion To become a coating liquid. Since the pH of the coating liquid is not adjusted by pH, it is 4·8. (2) Production of Substrate Modified Substrate Film For the raw material polymer, the particles of the polyethylene terephthalate resin having an intrinsic viscosity of 〇.62 dl/g which does not contain the particles used in Example 1 are nine, at 135 °. (: After 6 hours under reduced pressure (1 Torr), it was supplied to an extruder, melt extruded into a sheet at about 285 ° C, and quenched and solidified on a metal roll maintained at a temperature of 20 ° C to obtain a casting. In this case, as a filter material of the hetero-112-200810924 type for removing the molten resin, a sintered stainless steel filter material having a filter particle size (initial filtration efficiency: 95%) of 15 μm is used. In the infrared heater, the obtained cast film was heated to 95 ° C, and then stretched by 3.5 times in the longitudinal direction by a roll group having a peripheral speed difference to obtain a one-axis aligned PET film. Next, the particle size was filtered (initial Filtration efficiency: 95%) 10 μηι of a felt-type polypropylene filter material was subjected to precision filtration of the above coating liquid, and coated on one side of the one-axis alignment PET film by a reverse roll method.

Next, the end portion of the film was grasped by a jig, and introduced into a hot air zone heated to 80 ° C to dry the coated surface and then stretched 4.0 times in the width direction. At this time, the wind speed in the tenter was 15 m/sec, and the drying time was 20 seconds. The time from coating to the tenter inlet was 1 0.0 seconds. Further, the coating amount was such that the final solid content was 0.1 〇g/tn2. Further, in the heat setting treatment step, the first heat setting zone is 200 ° C, the second heat setting zone is 210 ° C, the third heat setting zone is 220 ° C, and the fourth heat setting is performed. The fauna is 22 °C, the 5th heat-set zone is 230 °C, the 6th heat-set zone is 23 5 °C, the 7th heat-set zone is 240 °C, and the width direction is not relaxed. An adhesive modified polyester film having a film thickness of 125 μm was obtained in the same manner as in Comparative Example 1. In the surface of the adhesive modified layer of the obtained adhesive modified polyester film, the phase separation structure of the polyester phase and the polyurethane phase was not observed. (3) Production of Hard Coating Film Next, in the same manner as in Example 1 on the surface of the adhesion modifying layer 上述 of the adhesive-modified substrate film, the inorganic micro-113-200810924 particles were contained in one area layer. The layer c is hard coated to obtain a hard coating film. In the adhesion-modifying layer B of the cut surface of the obtained hard coating film, the phase separation structure of the polyester phase and the polyurethane phase was also not observed in the same manner as described above. (Comparative Example 3) (1) Preparation of coating liquid N

7.5 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1, and 11.3 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1. 0.3 parts by mass of ELASTRON catalyst (Cat 6 4 manufactured by Daiichi Kogyo Co., Ltd.), 40.5 parts by mass of water, and 39.5 parts by mass of isopropyl alcohol were separately mixed. Further, 0. 6 parts by mass of a 10% by mass aqueous solution of a non-pretreated fluorine-based nonionic surfactant (Megafac F142D manufactured by Dainippon Ink and Chemicals Co., Ltd.) was added, and 3 parts by mass of ruthenium was added without using the particles 6. The aqueous dispersion of 3.5% by mass of the agglomerate vermiculite (Fuly 311^¥81 VIII Sylysia · 3 10 ; average particle diameter of 1·4 μιη) of the particle A was used as a coating liquid. Moreover, the pH adjustment of the coating liquid helium was not performed. The pH of the coating liquid N was 4.6. (2) Production of a Substrate Modified Substrate Film For the extrusion of a polyethylene terephthalate resin having an intrinsic viscosity of 〇.62 dl/g as a raw material polymer which does not contain the particles used in Example 1, The press was melt extruded into a sheet at about 28 ° C, and quenched and solidified on a metal roll maintained at a surface temperature of 20 ° C to obtain a cast film. In this case, as a filter medium for removing impurities of the molten resin, a sintered stainless steel filter material having a filter particle size (initial filtration efficiency: 95%) of 15 μm was used. -114· 200810924 The obtained cast film was heated to 95 ° C with 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 difference to obtain a one-axis alignment. PET film. Then, the coating liquid L was finely filtered by a felt-type polypropylene filter material having a particle size (initial filtration efficiency: 95%) of 10 μm, and applied to one surface of the one-axis alignment film by a reverse light method.

After coating, it was guided to a drying oven and dried at a temperature of 120 ° C for 3.2 seconds. Further, the coating amount was such that the final solid content was 〇.〇8 g/m2. The film passage time was 3.2 seconds from the application to the tenter inlet, the wind speed of the first zone of the drying furnace was 15 m/sec, and the wind speeds of the second zone to the fourth zone were dried in the same manner as in Example 1. The air supply air volume of the wind is 70 m3/sec in the first to fourth drying zones, and the exhaust air is naturally exhausted from the front and rear of the drying furnace. Then, the film was subjected to transverse stretching in the same manner as in Example 1 except that the transverse stretching ratio was 4.0 times, and the film was heat-set by the same method as in Comparative Example 1, and relaxed in the width direction to obtain a film thickness. It is an adhesive modified polyester film of 125 μm. In the surface of the adhesive modified layer of the obtained adhesive modified polyester film, the phase separation structure of the polyester phase and the polyurethane phase was not observed. (3) Production of Hard Coating Film Next, on the surface of the adhesion-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer is formed in the same manner as in Example 1. To obtain a hard coated film. In the adhesive modification layer of the cut surface of the obtained hard coating film, the phase separation structure of the polyester phase and the polyurethane phase was also observed in the same manner as described above. (Comparative Example 4) The film thickness was obtained in the same manner as in Example 1 except that in the first embodiment, the film passage time from the application of the coating liquid A to the entrance of the drying furnace was 3.2 seconds. It is a 125 μm adhesive modified polyester film.

Then, on the surface of the adhesive-modified layer Β of the above-mentioned adhesive-modified base film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 5) 3 parts by mass of the 30% by mass aqueous dispersion of the copolymerized polyester (Α) used in Example 1, and 18.0 parts by mass of the polyurethane used in Example 1 (Β) 20% by mass aqueous solution, 0.3 parts by mass of ELASTRON catalyst (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 37.3 parts by mass of water, and 37.8 parts by mass of isopropyl alcohol were separately mixed. Further, 0.6 parts by mass of a 10% by mass aqueous solution of the surfactant used in Example 1 and 2 J parts by mass of colloidal vermiculite (manufactured by Nissan Chemical Industries, Inc., Snowtex OL; average particle diameter: 40 nm) of 20% by mass were added. % aqueous dispersion, 0.5 parts by mass of a dry-type vermiculite as a particle B (Arosil 0X50 manufactured by Arosil, Japan; average particle diameter: 200 nm, average primary particle diameter: 40 nm), a 3.5% by mass aqueous dispersion, and 5% by mass of sodium hydrogencarbonate The aqueous solution was adjusted to pH 6.2 to become a coating liquid helium. An adhesive modified polyester film having a film thickness of 1 25 μm was obtained in the same manner as in Example 1 except that the coating liquid was used as the coating liquid. Next, on the surface of the adhesion-modified layer Β-116-200810924 of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating. film. (Comparative Example 6)

12.0 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1, 4.5 parts by mass of a 20% by mass aqueous solution of the polyurethane (B) used in Example 1, 0.3 mass The ELASTRON was mixed with a catalyst (Cat6 4 manufactured by Daiichi Kogyo Co., Ltd.), 42.3 parts by mass of water, and 37.2 parts by mass of isopropyl alcohol, and further added with 0.6 parts by mass of 10% by mass of the surfactant used in Example 1. Aqueous solution, 2.3 parts by mass of colloidal vermiculite as particle A (manufactured by Nissan Chemical Industries, Snowtex OL; average particle diameter: 40 nm), 20% by mass aqueous dispersion, 0.5 parts by mass of dry-type vermiculite as cerium particle B (Arosil, Japan) A 3.5 mass% aqueous dispersion of Arosil 0X50; an average particle diameter of 200 nm and an average primary particle diameter of 40 μm) was adjusted to pH 6.2 with a 5 mass% sodium hydrogencarbonate aqueous solution to obtain a coating liquid P. An adhesive modified polyester film having a film thickness of 125 μm was obtained in the same manner as in Example 1 except that the coating liquid P was used as the coating liquid. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 7) In the first embodiment, the temperature in each heat setting treatment step was 190 ° C in the first heat setting zone and 195 ° C in the second heat setting zone, and the third heat setting was performed. From the region to the fifth heat-set region, except for 20 ° C, an adhesive film of -117-200810924 polyester film having a film thickness of 1 2 5 μη was obtained by the same method as in Example 1. In the surface of the adhesive modified layer of the obtained adhesive modified polyester film, the phase separation structure of the polyester phase and the polyurethane phase was not observed. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film.

In the adhesion-modifying layer B of the cut surface of the obtained hard coating film, the phase separation structure of the polyester phase and the polyurethane phase was also not observed in the same manner as described above. (Comparative Example 8) An adhesive modified polyester film having a film thickness of 125 μm was obtained in the same manner as in Example 1 except that the wind speed in the drying furnace was changed to 15 m/sec. Then, on the surface of the adhesion-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 9) An adhesive modification of a film thickness of 125 μm was obtained in the same manner as in Example 1 except that the amount of the final solid component was changed to 0.20 g/m 2 in Example 1. Ester film. Then, on the surface of the adhesion-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 10) -118-200810924 In the same manner as in Example 1, except that the coating liquid Q in which the pH of the coating liquid was adjusted to 9.0 by the sodium carbonate aqueous solution of 5 mass% was used, An adhesive modified polyester film having a film thickness of 1 25 μm was obtained. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 11)

In the same manner as in Example 1, except that the interfacial agent was not blended in the coating liquid, and the coating liquid R was used in the same manner as in Example 1, an adhesive polymerization having a film thickness of 125 μm was obtained. Ester film. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 17) 7.5 parts by mass of a 30% by mass aqueous dispersion of the copolymerized polyester (Α) used in Example 1, and 11.3 parts by mass of the polyurethane used in Example 1 (Β) 20 mass ° /. The aqueous solution, 0.3 parts by mass of ELASTRON catalyst (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 40.5 parts by mass of water, and 39.5 parts by mass of isopropyl alcohol were separately mixed. Further, 0.6 parts by mass of a 10% by mass aqueous solution of the surfactant used in Example 1 and 4.3 parts by mass of aggregated vermiculite as a particle A (Sylysia 310 manufactured by Fuji SILYSIA Chemical Co., Ltd.; average particle diameter of 1·4 μm) were added. 3.5 mass% aqueous dispersion, adjusted to 6.2 with 5% by mass aqueous sodium hydrogencarbonate particles, and sequentially filtered through filtration, performance of 5 μm -119 - 200810924 and 1 μm Liquid s. Further, the coating liquid does not contain the particles B. An adhesive modified polyester film having a film thickness of 1 25 μm was obtained by the same method as in Example 1 except that the above-mentioned coating liquid s was used. Next, the adhesion modification of the above-mentioned adhesive modified base film was carried out. On the surface of the layer ,, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 12)

In the same manner as in Example 1, except that the amount of the interface active agent in the coating liquid was 0.60% by mass based on the solid content, the film thickness was 1 25 in the same manner as in Example 1 except that the coating liquid τ was used. An adhesive modified polyester film of μπι. Then, on the surface of the adhesive-modified layer Β of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example i to obtain a hard coating film. (Example 18) Except that in Example 1, the temperature in each heat setting treatment step was 200 ° C in the first heat setting zone and 210 ° C in the second heat setting zone, and the third heat setting zone was used. The temperature is 215 ° C, the fourth heat setting zone is 220 ° C, the fifth heat setting zone is 225 ° C, the sixth heat setting zone is 230 ° C, the seventh heat setting zone is 170 ° C, in the 7th heat setting zone. In the same manner as in Example 1, except for the 3% relaxation treatment in the width direction, the uncoated portions at both ends of the film were trimmed to obtain an adhesive modification polycondensation having a film thickness of 1 2 5 μm. Ester film. -120-200810924 Next, on the surface of the adhesion-modifying layer B of the adhesive-modified base film, a hard coating layer c containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating. film. (Comparative Example 13)

In addition to the 7.5 parts by mass of the 30% by mass aqueous dispersion of the copolymerized polyester (A) used in Example 1, and the 13.3 parts by mass of the polyurethane used in Example 1 in Example 1 ( B) 20% by mass aqueous solution, 0.3 parts by mass of ELASTRON catalyst (Cat64 manufactured by Daiichi Kogyo Co., Ltd.), 51.0 parts by mass of water, and 26.2 parts by mass of isopropyl alcohol were separately mixed. Further, 6 parts by mass of the 10% by mass aqueous solution of the surfactant used in Example 1 and 2.3 parts by mass of colloidal vermiculite which is used as a particle mash (Snowtex OL manufactured by Nissan Chemical Industry Co., Ltd.; average particle diameter: 40 nm) were added. 20% by mass of the aqueous dispersion, 0.5 parts by mass of the dry-type vermiculite (Arosil 0X50 manufactured by Arosil, Japan; average particle diameter: 200 nm, average primary particle diameter: 40 nm) as a particle B, and a 3.5% by mass aqueous dispersion of 5% by mass The aqueous solution of sodium hydrogencarbonate was adjusted to pH 6.2, and an adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating liquid U was used. Then, on the surface of the adhesion-modified layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Comparative Example 14) A hard coating layer composed of a solvent-diluted photocurable acrylate-based resin containing no inorganic fine particles was used as the hard coating material in the first embodiment (Seikabeam EXF, manufactured by Daisei Seika Co., Ltd.) In addition to -01B), a hard coating film containing no inorganic fine particles was laminated on one surface in the same manner as in Example 1 to obtain a hard coating film. In the obtained hard coating film, although the adhesion between the hard coating layer and the adhesion-modifying layer is excellent, the hardness is lowered and the curl is also increased. (Embodiment 19)

In addition to the 10% by mass aqueous solution of the fluorine-based nonionic surfactant (Megafac F142D manufactured by Dainippon Ink and Chemicals Co., Ltd.), a fluorine-based nonionic surfactant (large Japan) was used in addition to the coating liquid of the first embodiment. An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the coating liquid V was used in a 5% by mass aqueous solution of Megafac F444. Then, on the surface of the adhesive-modified layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. (Example 20) An adhesive modified polyester film was obtained in the same manner as in Example 1 except that the adhesive modified layer B was applied to both surfaces of the one-axis alignment polyester film. Further, the passage time of the film was 0.8 seconds on one side and 1.0 second on the opposite side from the application of the film to the entrance of the drying furnace. On the above-mentioned adhesive modified base film, a ruthenium lens film was obtained by hard coating layer C in one area layer and lenticular lens layer D in another area layer via the adhesive layer B. First, a method of forming the hard coating layer C will be described. On the surface of the adhesive-modified layer B of the adhesive-modified substrate film, the surface of the adhesive layer B-122-200810924, the hard coating agent containing the inorganic particles used in Example 1 was cured to a thickness of 3 μm. The way, coated with a Meiya rod, was dried at 40 t for 60 seconds. Further, ultraviolet rays of 300 mJ/cm2 were irradiated to cure the resin, and a hard coating layer C was formed on one surface. Next, a method of forming the pupil lens layer D will be described.

Injecting an ultraviolet curable resin liquid (Desolite Z95 90 manufactured by JSR Co., Ltd.) into a molding die having a prism shape in which a pitch of 〇.〇5 mm and a apex angle of 90° is injected, and the hard coating layer C is On the surface of the opposite adhesive reforming layer B, the above-mentioned forming mold is superposed. Next, from the side of the hard coating layer C, an ultraviolet ray of 80 w / c m was irradiated by an ultraviolet lamp (output: 6 · 4 k w ) to cure the resin, and then peeled off to form a ruthenium lens layer. (Example 21) A secondary modified polyester film was obtained in the same manner as in Example 1 except that the adhesive modified layer was applied to both surfaces of the one-axis alignment polyester film in Example 1. Further, from the application of the film to the inlet of the drying furnace, the passage time of the film was 0.8 seconds on one side and 1.0 second on the opposite side. On the above-mentioned adhesive modified base film, a light-diffusing film was obtained by hard-coating layer C on one area layer and light-diffusion layer D' on another area layer via adhesion-modified layer B. First, a method of forming the hard coating layer C will be described. On the surface of one of the adhesion-modifying layers B of the adhesive-modified substrate film, the hard coating agent containing inorganic particles used in Example 1 was used in a manner such that the film thickness after curing was 3 μm. The rod is coated and dried at 40 -123 - 200810924 °C for 60 seconds. Further, ultraviolet rays of 300 mJ/cm2 were irradiated to cure the resin, and a hard coating layer C was formed on one surface. Next, a method of forming the light diffusion layer IV will be described. The coating liquid for a light-diffusing layer shown below was applied onto the surface of the adhesion-modifying layer B opposite to the hard coating layer c, and dried at i 3 ot for 3 minutes. (Composition of coating liquid for light diffusion layer) (a) Particles [26·3 parts by mass]

Spherical acrylic resin particles (Ε 〇 〇star MA 1 0 1 〇, manufactured by Nippon Shokubai Co., Ltd.; average particle size ΙΟμπι) (b) Resin [19.5 parts by mass] Acrylic binder resin solution (Mitsubishi snail strain) Diane LR-1 065, solid content: 45 mass%) (c) Solvent [54.2 parts by mass] • Methyl ethyl ketone [24.2 parts by mass] • Propylene glycol monomethyl ether [15.0 parts by mass] • Propylene glycol Methyl ether acetate [15·0 parts by mass] (Example 22) The same procedure as in Example 1 was carried out except that the coating amount was changed to 0.02 g/m 2 in the final solid content. An adhesive modified polyester film was obtained. Then, on the surface of the adhesion-modifying layer B of the adhesive-modified substrate film, a hard coating layer C containing inorganic fine particles in one area layer was obtained in the same manner as in Example 1 to obtain a hard coating film. •124-

200810924 (Example 23) In the same manner as in the first embodiment, except for the coating device using the coating device capacity, the capacity of the circulation tank, and the capacity of the preparation tank, the coating apparatus was used in the same manner as in the first embodiment. The film of the adhesive-modified polyester film having a length of 2000 m and a width of 1 000 mm and a thickness of the film. (a) Capacity of the coating liquid / Capacity of the circulation tank = 1 / 5 (b) Capacity of the circulation tank / Capacity of the mixing tank = 1 / 50 (c) Roundness of the coating roller and the metering roller And the degree of the cylinder: 6 / iO 〇〇 mm (d) The nip roller is not provided between the coater and the drying furnace, and the surface of the adhesive-modified substrate film is modified as in the first embodiment. The ground layer is a hard coating layer C containing narrow particles in one area layer to obtain a hard coating film. In the examples 1 to 2 3 and the comparative examples 1 to 14, the coating box or the characteristic system are shown in Table 1, and the coating and drying conditions are shown in Table 3. The heat setting conditions are shown in Table 3. The thin alcohol and characteristics are shown in Table 4. Moreover, in the longitudinal direction and the width direction of the obtained roll of the adhesive film, the surface of the PEs is further large, the minimum flaw, the maximum haze of the haze, the minimum flaw, the maximum flaw of the hard joint, and the minimum flaw. The system is shown in Table 5. Furthermore, the adhesion is all 〇. The connection of the liquid has the following method, and the composition of the 1 2 5 μπι layer 无机 inorganic micro composition 2, the highest viscosity of the physical property polyester ratio. About -125- 200810924 [Table l]

Coating liquid composition coating liquid resin particle P1 particle Ρ2 solvent surfactant solid copolymerized PEs/PU average particle diameter addition amount average particle diameter addition amount 7JC/IPA mass ratio mm presence or absence of front compounding amount PH concentration concentration mass ratio μπι mass % μπι mass % mass mass % 0 〇 Example 1 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic 0.06 6.2 5.30 Example 2 50/50 0.04 0.45 0.20 0.02 60/40 Cation 0.06 6.2 5.30 Example 3 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 4 60/40 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 *Example 5 40/60 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 6 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 7 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.03 6.2 5.30 Example 8 50 /50 0.04 0.45 0.20 0.02 60/40 Nonionic 0.10 6.2 5.30 Example 9 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic 0.06 6.2 5.30 Example 10 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic 0 .06 6.2 5.30 Example 11 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic with 0.06 7.9 5.30 Example 12 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic with 0.06 6.2 5.30 Example 13 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion no 0.06 6.2 5.30 Love example 14 50/50 0.04 0.45 0.20 0.02 50/50 Non-ion has 0.06 6.2 5.30 Fee 15 15/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 4.6 5.30 Example 16 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 S Example 17 50/50 1.4 3.0 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 ΪExample 18 50/50 0.04 0.45 0.20 0.02 60/40 Nonionics 0.06 6.2 5.30 Example 19 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic 0.03 6.2 5.30 Example 20 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic 0.06 6.2 5.30 Example 21 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 22 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Example 23 50/50 0.04 0.45 0.20 0.02 60/40 Non The ion has 0.06 6.2 5.30 Comparative Example 1 20/80 — — — — 100/0 Non Ion - Μ - 10.00 Comparative Example 2 20/80 0.04 0.36 0.20 0.04 95/5 Anion No 0.06 4.8 10.93 Comparative Example 3 50/50 1.4 0.02 — — 60/40 Non-ion No 0.06 4.6 4.87 tb Comparative Example 4 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Comparative Example 5 20/80 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 Comparative Example 6 80/20 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.06 6.2 5.30 t匕Comparative Example 7 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic with 0.06 6.2 5.30 ttComparative Example 8 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic with 0.06 6.2 5.30 Comparative Example 9 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic 0.06 6.2 5.30 Comparative Example 10 50/50 0.04 0.45 0.20 0.02 60/40 Nonionic 0.06 9.0 5.30 Comparative Example 11 50/50 0.04 0.45 0.20 0.02 60/40 — — No 6.2 5.30 Comparative Example 12 50/50 0.04 0.45 0.20 0.02 60/40 Non-ion has 0.60 6.2 5.30 Comparative Example 13 50/50 0.04 0.45 0.20 0.02 72/28 Non-ion has 0.06 6.2 5.30 Comparative Example 14 50/50 0.04 0.45 0.20 0.02 60/40 Non The ion has 0.06 6.2 5.30 -1 2 6 - 200810924 [Table 2]

Coating/drying conditions Passing time from application to drying step inlet (seconds) Drying temperature CC) Drying time (seconds) Wind speed (m/s) Final coating amount (g/m2) Example 1 0.8 135 1.0 30 0.08 Example 2 0.8 135 1.0 30 0.08 Example 3 0.8 135 1.0 30 0.08 Example 4 0.8 135 1.0 30 0.08 Example 5 0.8 135 1.0 30 0.08 Example 6 0.8 135 1.0 30 0.12 Example 7 0.8 135 1.0 30 0.08 Example 8 0.8 135 1.0 30 0.08 Example 9 0.7 135 0.8 30 0.08 Solid surface 10 1.0 135 1.9 30 0.08 Example 11 08 135 1.0 30 0.08 Example 12 0.8/1.0 135 1.0 30 0.08 Example 13 0.8 135 1.0 30 0.08 Example 14 0.8 135 1.0 30 0.08 Example 15 0.8 135 1.0 30 0.08 Example 16 0.8 135 1.0 30 0.08 Example 17 0.8 135 1.0 30 0.08 Example 18 0.8 135 1.0 30 0.08 Example 19 0.8 135 1.0 30 0.08 Example 20 0.8 135 1.0 30 0.08 Example 21 0.8 135 1.0 30 0.08 Example 22 0.8 135 1.0 30 0.02 Example 23 0.8 135 1.0 30 0.08 Comparative Example 1 10 110 20 15 0.15 Comparative Example 2 10 80 20 20 0.10 Comparative Example 3 3.2 120 1.0 1 5 0.08 Comparative Example 4 3.2 135 1.0 30 0.08 Comparative Example 5 0.8 135 1.0 30 0.08 Comparative Example 6 0.8 135 1.0 30 0.08 Comparative Example 7 0.8 135 1.0 30 0.08 Comparative Example 8 0.8 135 1.0 15 0.08 Comparative Example 9 0.8 135 1.0 30 0.20 Comparative Example 10 0.8 135 1.0 30 0.08 Comparative Example 11 0.8 135 1.0 30 0.08 Comparative Example 12 0.8 135 1.0 30 0.08 Comparative Example 13 0.8 135 1.0 30 0.08 Comparative Example 14 0.8 135 1.0 30 0.08 -127- 200810924 [Table 3]

Heat setting condition Heat setting temperature (°C) Passing time of each zone (seconds) #1 Zone #2 Zone #3 #4 #5 1E #6 #7 1 Item: Example 1 200 225 230 230 210 170 120 4.5 Implementation Example 2 200 225 230 230 210 170 120 4.5 Example 3 190 205 220 220 210 170 120 4.5 Example 4 200 225 230 230 210 170 120 4.5 Example 5 200 225 230 230 210 170 120 4.5 Example 6 200 225 230 230 210 170 120 4.5 Example 7 200 225 230 230 210 170 120 4.5 Example 8 200 225 230 230 210 170 120 4.5 Example 9 200 225 230 230 210 170 120 3.5 Example 10 200 225 230 230 210 170 120 6.6 Examples 11 200 225 230 230 210 170 120 4.5 Example 12 200 Γ 225 230 230 210 170 120 4.5 Example 13 200 225 230 230 210 170 120 4.5 Example 14 200 225 230 230 210 170 120 4.5 Example 15 200 225 230 230 210 170 120 4.5 Selling example 16 200 225 230 230 210 170 120 4.5 Example 17 200 225 230 230 210 170 120 4.5 Example 18 200 210 215 220 225 230 170 4.5 Example 19 200 225 230 230 210 170 120 4.5 Implementation Example 20 200 225 230 230 210 170 12 0 4.5 Example 21 200 225 230 230 210 170 120 4.5 Example 22 200 225 230 230 210 170 120 4.5 Example 23 200 225 230 230 210 170 120 4.5 Comparative Example 1 200 205 210 213 215 220 170 4.5 Comparative Example 2 200 210 220 225 230 235 240 4.5 Comparative Example 3 200 205 210 213 215 220 170 4.5 Comparative Example 4 200 225 230 230 210 170 120 4.5 Comparative Example 5 200 225 230 230 210 170 120 4.5 t匕 Comparative Example 6 200 225 230 230 210 170 120 4.5 Comparative Example 7 190 195 200 200 200 170 120 4.5 Comparative Example 8 200 225 230 230 210 170 120 4.5 Comparative Example 9 200 225 230 230 210 170 120 4.5 Comparative Example 10 200 225 230 230 210 170 120 4.5 Comparative Example 11 200 225 230 230 210 170 120 4.5 Comparative example 12 200 225 230 230 210 170 120 4.5 Comparative example 13 200 225 230 230 210 170 120 4.5 Comparative example 14 200 225 230 230 210 170 120 4.5 -1 2 8 - 200810924

[Table 4] The PEs phase of the evaluation surface of the film of the subsequent modified film and the modified layer was over the width of the PEs phase of the width Ιμηη, and the adhesion of the modified haze layer to the hard haze anti-adhesion and HC layer (particle: Adhesion (%) Area rate dimension (four) Degree index (%) Solvent-free solvent dilution (%) (IV) Type HC layer type HC layer Example 1 68 1111 II/\\\ 1.86 125 5.1 0.58 〇95 100 Implementation Example 2 65 /\\\ 125 5.3 0.65 〇100 100 Example 3 52 > fnrT 1 π: J\\\ 1.75 125 7.0 0.45 〇100 100 Real 4 76 Charm yv vn 1.70 125 3,5 0.41 〇95 97 Example 5 48 M j\\\ 125 12.5 0.85 〇100 95 Example 6 52 M /\\\ 125 7.3 0.65 〇100 100 Example 7 75 ΑττΤ. m 125 6.5 0.61 〇92 95 Example 8 64 4rrfi MIL· /1 v\ 125 5.5 0.85 〇100 100 Example 9 70 No 1.89 100 5.3 0.55 〇100 100 Example 10 51 frTp 1.85 188 8.0 0.46 〇100 100 Example 11 61 M /l\V 125 5.3 0.73 〇100 100 Implementation Example 12 68 >f|Tr MIL· /\\\ 125 5.3 0.78 〇96 100 Example 13 66 4rrr. M 125 5.5 0.54 85 86 Example 14 70 No 125 5.2 0.56 〇 85 86 Example 15 87 125 4.0 0.47 〇 50 80 Example 16 69 No 125 5.0 0.57 〇 96 100 Example 17 69 Yes 125 5.3 3.40 〇100 100 Example 18 50 Yes 125 7.9 0.47 〇83 95 Example 19 68 125 7.9 0.47 〇95 100 Example 20 68 /rrr No 125 5.1 0.58 〇95 100 Example 21 68 Μ 125 5.1 0.58 〇95 100 Example 22 79 No 125 4.3 0.78 〇 91 93 Example 23 68 No 125 5.1 0.58 〇95 100 Comparative Example 1 8 No 1.25 125 15.5 1.05 X 75 50 Comparative Example 2 - Μ 125 15.3 0.75 X 84 60 Comparative Example 3 - > frrf Μ 125 5.5 0.41 X 100 95 Comparative Example 4 30 No 1.58 125 15.1 0.73 X 93 79 Comparative Example 5 15 ffTp No 125 15.7 0.98 X 95 60 Comparative Example 6 93 There are 1.40 125 2.8 0.47 〇 30 70 Comparative Example 7 - 4nr 125 4.1 0.62 X 78 65 Comparative Example 8 34 >frrr 125 6.0 0.70 X 100 98 Comparative Example 9 32 None 125 6.5 0.54 X 100 92 Comparative Example 10 33 irrL Μ 125 6.0 1.55 Δ 100 90 Comparative Example 11 91 4τττ Pick 125 3.5 0.38 〇25 70 Comparative Example 12 34 &gt ;frrr 125 5.9 1.53 Δ 98 87 Comparative Example 13 32 Young 125 6.8 2.20 X 95 88 Comparative Example 14 68 None 1.86 125 5.1 0.58 〇 95 100 -1 2 9 - 200810924

[Table 5] Area ratio (%) of the PEs phase in the surface of the subsequent modified layer Haze (%) Adhesion to the HC layer (%) Solvent-free HC layer/adhesive reforming layer Solvent-diluted HC layer /Subsequent modified layer maximum 値 minimum 値 maximum 値 minimum 値 maximum 値 minimum 値 maximum 値 minimum 値 Example 1 Length direction 73 63 0.59 0.56 100 94 100 96 Width direction 72 64 0.59 0.56 100 96 100 97 Example 23 Length direction 77 60 0.6 0.56 100 93 100 95 Width direction 75 61 0.6 0.56 100 91 100 94 -130- 200810924 [Table 6]

The structure of the hard coated film optical functional layer is followed by the modified layer B. The area ratio (%) of the HJ phase on the other face and the adhesion to the HC layer containing the inorganic fine particles (%) Pencil hardness Example 1 HC layer-45 95 〇 Example 2 HC layer - 46 96 〇 Example 3 HC layer - 52 96 〇 Example 4 HC layer - 33 94 〇 Example 5 HC layer - 59 92 〇 Example 6 HC layer - 52 99 〇 Example 7 HC layer - 41 91 〇 Example 8 HC layer - 47 98 〇 Example 9 HC layer - 43 94 〇 Example 10 HC layer - 52 96 〇 Example 11 HC layer - 48 94 〇 Example 12 HC layer HC layer 45 95 〇 Example 13 HC layer - 46 82 〇 Example 14 HC layer - 44 82 〇 Example 15 HC layer - 34 80 〇 Example 16 HC layer - 44 95 〇 Example 17 HC layer - 44 94 〇 Example 18 HC layer - 53 92 〇 Example 19 HC layer - 45 96 〇 Example 20 HC layer lens layer 45 96 〇 Example 21 HC layer light diffusion layer 45 95 〇 Example 22 HC layer one not determined 85 〇 Example 23 HC Layer - 45 95 * 〇Comparative Example 1 HC layer - 82 40 〇Compare 2 HC layer - 43 〇 Comparative Example 3 HC layer - 88 〇 Comparative Example 4 HC layer - 63 70 〇 Comparative Example 5 HC layer - 75 48 〇 Comparative Example 6 HC layer - 12 62 〇 Comparative Example 7 HC layer - 50 〇Comparative Example 8 HC layer-62 90 〇Comparative Example 9 HC layer - 62 89 〇Comparative Example 10 HC layer - 62 84 〇Comparative Example 11 HC layer - 29 45 〇Comparative Example 12 HC layer-61 83 〇Comparative Example 13 HC layer-62 83 〇Comparative example 14 HC layer - 45 98 X -1 3 1 - 200810924 Industrial use of the hard coated film of the present invention, while maintaining a high hardness, and a hard coating layer containing inorganic fine particles Since it is excellent in adhesiveness, it is suitable as a base material of an optical functional film for display, such as a 稜鏡 lens sheet, a light-diffusion film, an anti-reflection (AR) film, a transparent conductive film, an infrared absorption film, and an electromagnetic wave absorption film.

Further, the hard coating film of the present invention can be used for applications requiring shielding properties in addition to optical functional films for displays. In this case, as the thermoplastic resin film of the substrate, a white film containing a white pigment or a cavity is preferably used. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a phase of an adhesion modifying layer of a bond-modified substrate film used in a hard coating film of the present invention, which is observed in a phase measurement mode of a scanning probe microscope. Like the illustration. Fig. 2 is an explanatory view of the phase image emphasized by the image processing software in the phase image of Fig. 1, the outline of the interface between the bright phase and the dark phase. Fig. 3 is an explanatory view showing a phase image in which the dark color is applied to the image processing software in the phase image of the outline of the interface between the bright phase and the dark phase in Fig. 2. Fig. 4 is an explanatory view showing a boundary line between a bright phase and a dark phase in the phase image of the outline of the interface between the bright phase and the dark phase in Fig. 2; Fig. 5 is a view showing the surface shape of the flaw attached to the surface of the modified layer, and the height difference of the flaw when measured in a wave pattern using a three-dimensional non-contact surface shape measuring device. -132- 200810924 Figure 6 shows the area ratio of the PEs phase on the surface of the subsequent modified layer and the resin composition of the adhesive layer in Comparative Examples 1, 4, 6, and 8-14. The quality ratio of the PEs in the medium does not correspond to the specification. Fig. 7 is an explanatory view showing the arrangement of the coating liquid, the circulation tank, the arrangement of the preparation tank, and the circulation path of the coating liquid. Fig. 8 is an explanatory view showing the phase image of the contrast-modified layer which is observed by the color uniformization process in the cutting surface of the adhesive layer observed in the phase measurement mode of the scanning probe microscope when the hard coating film of the present invention is cut. .

Fig. 9 is an explanatory view showing the range of the phase separation structure to be observed by two red lines in the phase image of the color uniformization process of Fig. 8. Fig. 10 is an explanatory diagram of a phase image which is dimmed by the image processing software in the phase image of Fig. 8. Fig. 1 is an explanatory diagram of a phase image in which the two red lines of Fig. 9 are adhered to the same position in the second embodiment. Fig. 1 is an explanatory diagram of a phase image in which the image processing software is used to apply a portion not surrounded by two red lines in the phase image of Fig. 1 . [Explanation of main components] 1 Dark phase (polyester phase with copolymerized polyester as the main component) 2 Bright phase (polyurethane phase with polyurethane as the main component) 3 Caused by particles The protrusion 4 has a contour of the interface between the bright phase and the dark phase. The line 5 is emphasized. The contour of the surface of the modified layer is contoured. 6 The valley of the flaw 7 The top of the flaw - 133 - Example 1-23 Comparative Example 1. 4 - 6, 8 -1 4 Coating machine coating liquid tray, die circulation groove matching groove substrate film nip roller

Hard coating layer C Next modified layer B The thermoplastic resin film A shows that the line of the interface between the hard coating layer C and the adhesion modifying layer B is from the interface 20 to 20 nm perpendicular to the inside of the adhesion modifying layer. Depth, parallel moving line -134-

Claims (1)

200810924 X. Patent application scope: A hard coating film characterized in that the hard coating film is formed on one or both sides of a thermoplastic resin film A, and an adhesive layer B containing a copolymerized polyester and a polyurethane is formed. A/B/C or B/A/B/C laminated on the base material film and the hard coat layer C containing inorganic fine particles on the surface of the adhesive layer B on either side of the film a layered structure in which the adhesion-modifying layer B has a microphase-separated structure or a nanophase-separated structure of a polyester (PEs) phase and a polyurethane (PU) phase, and is phase-measured using a scanning probe microscope When the cutting surface of the hard coating film is observed in a mode, the adhesion-modifying layer B defined by the following formula (1) is in a range from the interface between the adhesion-modified layer B and the hard coating layer C to a depth of 20 nm. The area ratio of the polyurethane phase (in the phase image showing the bright phase) is 30% or more and 60% or less, and the area ratio (%) of the PU phase = (the surface area of the PU phase / the measurement area) x l 〇〇 ·· (1). 2. A hard coating film characterized in that the hard coating film is formed on one or both sides of a thermoplastic resin film A, and an adhesive layer B containing a copolymerized polyester and a polyurethane is formed. A modified base film and A/B/C or B/A/B/ laminated with the inorganic fine particle-containing hard coating layer C on the surface of the adhesive layer B on either side of the film. A layer composition of C, wherein the adhesion modifying layer B has a microphase separation structure or a nano phase separation structure of a polyester (PEs) phase and a polyurethane (PU) phase, and a phase is formed using a scanning probe microscope When the surface of the adhesion-modifying layer B is observed in the measurement mode, the area ratio of the polyester phase (the dark phase in the phase image) of the surface of the adhesion-modifying layer B defined by the following formula (2) is -1 3 5 - 200810924 The range of 5μπιχ5μπι is more than 35% and less than 90%, and the area ratio (%) of PEs phase = (area of PEs phase/measured area) χ1〇〇...(2) 3 ·If the scope of patent application is 1 Or a hard coating film of two, wherein the content of the inorganic fine particles in the hard coating layer C is 20 to 8 % by mass. 4. The hard coated film according to claim 1 or 2, wherein the thermoplastic resin film does not contain or contain 50 ppm or less of the particles, and the subsequent modified layer contains 〇·丨~2 〇 mass Q/❶. particle. 5. A hard coated film according to item 4 of the patent application, wherein the particles are vermiculite particles. An optical functional film which is a hard coating layer, a light diffusion layer, and a braided layer on the opposite side of the hard coating layer C as in the first or second aspect of the patent application. At least one optical function layer selected from the lens layer, the electromagnetic wave absorbing layer, the near-infrared ray shielding layer, and the transparent conductive layer. An optical functional film which is an optical functional film in which an antireflection layer or an antifouling layer is laminated on a hard coating layer C of a hard coating film according to the first or second aspect of the patent application. -136-